Measurements of the Hydrate Phase

This section will outline the developments and significance of applying mesoscopic and molecular-level methods to measure hydrate thermodynamic and kinetic properties. The characteristics of these different techniques are also listed in Tables 6.2 and 6.3. 

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Microscopic time-resolved measurements of the hydrate phase during gas hydrate formation, decomposition, and inhibition began only in the mid-1990s. These techniques include in situ synchrotron x-ray diffraction (Koh et al., 1996 Klapproth et al., 2003 Uchida et al., 2003), neutron diffraction (Henning et al., 2000 Koh et al., 2000 Halpern et al., 2001 Staykova et al., 2003), Raman spectroscopy (Subramanian and Sloan, 2002 Komai et al., 2004), and NMR spectroscopy (Moudrakovski et al., 2001 Kini et al., 2004 Gupta et al., 2007). 

There are comparatively few measurements of the hydrate phase composition, due to experimental difficulty. Hydrate phase difficulties arise because water is often occluded in the hydrate mass, separation of hydrate and water is difficult, and the hydrate phase of mixtures is often inhomogeneous in experiments. Consequently, the ratio of water to hydrocarbon is often inaccurate. As discussed in Chapter 6, only over the last two decades have experimental techniques (e.g., diffraction and NMR and Raman spectroscopy) become accurate enough to determine the degree of filling of hydrate cavities with different types of molecules. 

The modem era of hydrate research is marked by the industrial adoption of the van der Waals and Platteeuw statistical thermodynamics model for the hydrate phase. The spectroscopic measurement of the hydrate phase, abetted with molecular simulation, led to accuracy improvements, and industrial applications to energy, seafloor stability, and climate change. With the above historical advances, consider modem thermodynamics of the hydrate phase itself. 

Chapter 6 provides a listing of the hydrate phase equilibria and transport property data since 1934 for natural gas pure components, mixtures, and inhibitors together with common measurement techniques. Details of hydrate phase measurements using spectroscopy and diffraction are also discussed. 

The most productive two-phase (H-V or H-Lhc) equilibrium apparatus was developed by Kobayashi and coworkers. The same apparatus has been used for two-phase systems such as methane + water (Sloan et al., 1976 Aoyagi and Kobayashi, 1978), methane + propane + water (Song and Kobayashi, 1982), and carbon dioxide + water (Song and Kobayashi, 1987). The basic apparatus described in Section 6.1.1.2 was used in a unique way for two-phase studies. With two-phase measurements, excess gas was used to convert all of the water to hydrate at a three-phase (Lw-H-V) line before the conditions were changed to temperature and pressures in the two-phase region. This requires very careful conditioning of the hydrate phase to prevent metastability and occlusion. Kobayashi and coworkers equilibrated the hydrate phase by using the ball-mill apparatus to convert any excess water to hydrate. 

Kinetic measurements are changing from macroscopic to microscopic scales. Initially, kinetics consisted of macroscopic measurements of the fluid phases associated with hydrates - such as gas consumption rates or liquid turbidity, fundamentally in Bishnoi s laboratory.Subsequently, mesoscopic measurements of hydrate cry-stais, -82 particle size distribution, and film growth rates are available. Microscopic kinetic hydrate phase measurements are emerging. A review of microscopic hydrate science for both kinetics and thermodynamics is presented by... 

Figure 2.7 Comparison between measured and calculated heat flows of a portland cement hydrated at 23°C using a w/c of 0.50. Heat flow was calculated from quantitative XRD anaiyses using the dissolution enthalpies of the clinker phases and the precipitation enthalpies of the hydrate phases. (From Jansen, D. et al., Cement and Concrete Research, 42(1), 134-138, 2012a. With permission.)...

Carson and Katz5 studied another part of the methane-propane-water system. These authors investigated its behavior when an aqueous liquid, a hydrocarbon liquid, a gas, and some solid were present. It was found that the system was univariant so that the solid consisted of a single phase only. This phase is a hydrate which proved to contain methane and propane in various ratios. They then concluded that these hydrates behaved as solid solutions. It is clear that Carson and Katz measured a part of the four-phase line HllL1L2G. 

Most primary and secondary minerals found in soil systems are barely soluble in the soil solution. The amount of mass from the bulk phase to hydrated ions in soil solution is negligible compared to the total mass of the solid phase. In arid and semi-arid soils, concentrations of most trace metals in soil solution may be controlled by their carbonates and to some extent by their hydroxides. Other than carbonates, trace elements in arid and semi-arid soils may also occur as sulfate, phosphate or siliceous compounds, or as a minor component adsorbed on the surface of various solid phase components. The solubility of carbonates, sulfates and other common minerals of trace elements in arid and semi-arid soils will be discussed in Chapter 5. Badawy et al. (2002) reported that in near neutral and alkaline soils representative of alluvial, desertic and calcareous soils of Egypt, the measured Pb2+ activities were undersaturated with regard to the solubility of... 

When drug polymorphs cannot interconvert as a result of being suspended in aqueous solution, a different bioavailability of the two forms usually results [126], For instance, the peak concentration of chloramphenicol in blood serum was found to be roughly proportional to the percentage of the B-polymorph of chloramphenicol palmitate present in a matrix of the A-polymorph [133]. The same concept has been found to apply to hydrate species, where the higher solubility and dissolution rate of the anhydrous phase relative to the trihydrate phase resulted in measurably higher blood levels when using the anhydrate as... 

In principle, Gibbs free energies of transfer for trihalides can be obtained from solubilities in water and in nonaqueous or mixed aqueous solutions. However, there are two major obstacles here. The first is the prevalence of hydrates and solvates. This may complicate the calculation of AGtr(LnX3) values, for application of the standard formula connecting AGt, with solubilities requires that the composition of the solid phase be the same in equilibrium with the two solvent media in question. The other major hurdle is that solubilities of the trichlorides, tribromides, and triiodides in water are so high that knowledge of activity coefficients, which indeed are known to be far from unity 4b), is essential (201). These can, indeed, be measured, but such measurements require much time, care, and patience. 

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