Novel methodology for the calculation of the enthalpy of enclathration of methane hydrates using molecular dynamics simulations

Methane hydrates are encountered in a plethora of industrial and geological or environmental applications. In the current study, we present a novel methodology which is based on molecular dynamics simulations for the calculation of the enthalpy of enclathration of sI methane hydrates. Simulations are performed along the three-phase (Hydrate – Liquid water – Vapour; H–L_w–V) equilibrium line in the temperature range 274–310?K. The methodology takes into account the two different types of cages that are present in the sI methane hydrate and provides results for the enthalpy of enclathration for both types of cages, while it avoids performing calculations with the metastable, completely empty hydrate lattice. The formulation proposed is general and can be also applied to sII hydrates, while it can be modified/extended appropriately for use in the case of sH hydrates. Comparison is provided with available data from the literature and good agreement is observed.     

Scattering measurements from a dissolving bubble

A laboratory-scale study on acoustic scattering from a single bubble undergoing dissolution in undersaturated fresh water is presented. Several experiments are performed with the acoustic source driven with five-cycle tone bursts, center frequency of 120 kHz, to insonify a single bubble located on axis of the combined beam of the set of transducers. The bubble is placed on a fine nylon thread located in the far field of the transducer set, arranged in bistatic configuration, in a tank filled with undersaturated water. Backscattered waveforms from the bubble target are acquired every few seconds for several hours until the bubble has completely dissolved, and detailed dissolution curves are produced from the acoustic data. The rate of bubble dissolution is calculated using the solution developed by Epstein and Plesset [J. Chem. Phys. 18, 1505-1509 (1950)]. The results of the experiments performed are in agreement with the calculations.     

The importance of chemical mechanisms in sonochemical modelling

A state-of-the-art chemical mechanism is introduced to properly describe chemical processes inside a harmonically excited spherical bubble placed in water and saturated with oxygen. The model uses up-to-date Arrhenius-constants, collision efficiency factors and takes into account the pressure-dependency of the reactions. Duplicated reactions are also applied, and the backward reactions rates are calculated via suitable thermodynamic equilibrium conditions. Our proposed reaction mechanism is compared to three other chemical models that are widely applied in sonochemistry and lack most of the aforementioned modelling issues. In the governing equations, only the reaction mechanisms are compared, all other parts of the models are identical. The chemical yields obtained by the different modelling techniques are taken at the maximum expansion of the bubble. A brief parameter study is made with different pressure amplitudes and driving frequencies at two equilibrium bubble sizes. The results show that due to the deficiencies of the former reaction mechanisms employed in the sonochemical literature, several orders of magnitude differences of the chemical yields can be observed. In addition, the trends along a control parameter can also have dissimilar characteristics that might lead to false optimal operating conditions. Consequently, an up-to-date and accurate chemical model is crucial to make qualitatively and quantitatively correct conclusions in sonochemistry.     

Molecular simulation of phase coexistence in adsorption in porous solids

In this work a recently proposed method, the gauge-cell Gibbs ensemble Monte Carlo, is extended to deal with polar substances. The behaviour of water, a hydrogen bonding, weakly adsorbing fluid, is compared with that of methane, a strongly adsorbing, non-polar fluid, in the vicinity of the phase transition. The mechanisms of condensation for the two species are seen to be significantly different in nature. A systematic study of the effect of the pore width on the phase equilibrium of water is also performed. Our results show that the narrowing of the pore shifts the equilibrium transition pressure to lower values and reduces the extent of vapour metastability, but exerts little influence on the stability of the liquid phase.     

A simulation study of the pore size dependence of transport selectivity in cylindrical pores

The equilibrium adsorption and transport properties of mixtures of methane and carbon dioxide, modelled as spherical molecules, have been studied in cylindrical model pores with graphitic properties over a range of cylinder radii. The equilibrium isotherms exhibit packing transitions similar to those observed for single adsorbates; as a consequence, optimum separation factors are found at particular radii, depending on the fugacity (or pressure) in the system. The equations of non-equilibrium thermodynamics have been developed so as to represent the flux of each component in a Fickian form, as a coefficient multiplying the gradient of the total density. Diffusion coefficients were calculated from streaming velocity correlations and NEMD was used to obtain the ‘apparent’ viscous component. The results show that diffusion coefficients from equilibrium molecular dynamics and viscous diffusion coefficients from non-equilibrium calculations are identical within the errors of the calculation. It follows that equilibrium and dynamic separation factors have the same values over a range of pore sizes.     

On the stability of bubbles trapped at a solid–liquid interface: A thermodynamical approach

In this paper we present a condition for thermodynamic equilibrium of gas bubbles of dimensions larger that a few tens of nanometers trapped at a solid–liquid interface. It is defined an intensive adimensional function that relates bubble stability with wettability and surface corrugation related parameters. From it, we deduce that bubbles can be stable on smooth, highly hydrophobic surfaces and that, on weakly hydrophobic surfaces, bubbles may be stabilized by topographical heterogeneities like pores and grooves.     

亚临界水中超声激励空化泡动力学分析

考察亚临界水中压力和温度对超声空化泡动力学的影响。应用非线性Rayleigh-Plesset方程模拟空化泡运动过程,并利用Matlab软件编程求数值解,用碘量法测定超声在亚临界水中的声空化产额。结果表明:当亚临界水的压力相似文献   

Nanopore wall effect on surface tension of methane

Local pressure is known to be anisotropic across the interfaces separating fluids in equilibrium. Tangential pressure profiles show characteristic negative peaks as a result of surface tension forces parallel to the interface. Nearby attractive forces parallel to the interface are larger than the repulsive forces and, hence, constitute the surface tension. In this work, using molecular dynamics simulations of methane inside nano-scale pores, we show this surface tension behaviour could be significantly influenced by confinement effects. The layering structure, characterised by damped oscillations in local liquid density and tangential pressures, extends deep into the pore and can be a few nanometers thick. The surface tension is measured numerically using local pressures across the interface. Results show that the tension is smaller under confinement and becomes a variable in small pores, mainly controlled by the thickness of the liquid density layering (or liquid saturation) and the pore width. If the liquid saturation inside the pore is high enough, the vapour–liquid interface is not interfered by the pore wall and the surface tension remains the same as the bulk values. The results are important for understanding phase change and multi-phase transport phenomena in nanoporous materials.     

Effect of static pressure on acoustic energy radiated by cavitation bubbles in viscous liquids under ultrasound

The effect of static pressure on acoustic emissions including shock-wave emissions from cavitation bubbles in viscous liquids under ultrasound has been studied by numerical simulations in order to investigate the effect of static pressure on dispersion of nano-particles in liquids by ultrasound. The results of the numerical simulations for bubbles of 5 μm in equilibrium radius at 20 kHz have indicated that the optimal static pressure which maximizes the energy of acoustic waves radiated by a bubble per acoustic cycle increases as the acoustic pressure amplitude increases or the viscosity of the solution decreases. It qualitatively agrees with the experimental results by Sauter et al. [Ultrason. Sonochem. 15, 517 (2008)]. In liquids with relatively high viscosity (～200 mPa s), a bubble collapses more violently than in pure water when the acoustic pressure amplitude is relatively large (～20 bar). In a mixture of bubbles of different equilibrium radius (3 and 5 μm), the acoustic energy radiated by a 5 μm bubble is much larger than that by a 3 μm bubble due to the interaction with bubbles of different equilibrium radius. The acoustic energy radiated by a 5 μm bubble is substantially increased by the interaction with 3 μm bubbles.     

Time resolved spectroscopic NMR imaging using hyperpolarized 129Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized 129Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

水蒸气对声致发光单气泡稳定性的影响

在考虑水蒸气凝结与水的蒸发过程的基础上，推导了球形气泡形状稳定性方程-利用这个方程以及气泡运动时的气体扩散平衡条件，分别研究了环境水温217℃时声驱动频率为206kHz（溶于水中的氩气含量是其饱和度的14％）、环境水温0℃时声驱动频率为319kHz（溶于水中的氮气分压为20kPa，其中含1％氩气），以及环境水温20℃时声驱动频率为338kHz（溶于水中的氮气分压为20kPa，其中含1％氩气）可控制条件下气泡稳定性问题-理论计算结果与前人的实验数据比较，发现考虑水蒸气以后比忽略水蒸气对单气泡稳定区域 关键词： 声致发光 水蒸气 形状不稳定性 扩散平衡     

Effect of Diameter of Granules on Dissociation of Methane Hydrate

The kinetics of dissociation of methane hydrate in air at an external pressure of 1 bar was experimentally studied. It is shown that to describe the mechanism of dissociation of gas clathrate, it is necessary to take into account not only the degree of deviation of temperature and pressure from equilibrium values, but also the diameter of granules. As the diameter decreases, the rate of decomposition of methane hydrate increases significantly. Change in the grain size affects formation of pores and dissociation. The experiment demonstrated a self-preservation mechanism for granule diameters of more than 1 mm. In the case of powder with an average diameter of less than 0.3 mm, there was no self-preservation. The rate of dissociation depends on the combined effect of diffusion, crystallization, and creep.     

Diffusion-filtration model of methane escape from a coal seam

Methane desorption from a coal seam is theoretically investigated using a model including both the diffusion of methane in coal lumps and its filtration through net-shaped pores and cracks. The methane density distribution along the seam at an arbitrary time instant is found. Explicit dependences of the amount of the methane escaped from the seam on the lump size, open and closed porosity, viscosity and solubility of methane, and pressure and temperature in the seam are determined. An effective diffusion coefficient in lumps containing methane-filled closed pores is found. In the case of hindered diffusion, the methane can be subdivided into the “fast” and “slow” fractions.     

Flow of an electrically conducting bubble liquid in the field of an electromagnetic force

Physical processes accompanying the flow of a conducting bubble liquid in crossed electric and magnetic fields are considered. Based on the general equations of mechanics of multiphase media, we develop a one-dimensional model of the flow of and heat exchange in a compressible bubble liquid when the phases are not in thermal and velocity equilibrium. The model is numerically investigated. It is demonstrated that, when the bubble liquid flows along the electromagnetic force vector, the bubbles lag behind the carrying flow and are compressed and warmed up. This causes oscillations of the bubble volume, as well as oscillations of the parameters of both the disperse and carrying phase. In particular, the compression of the bubbles reduces the volumetric gas content, as well as increases the effective conductivity of the flow and the electromagnetic force in the downstream direction. This sets conditions for crisis of the bubble flow when the electromagnetic force expels the bubbles against the main stream. On the basis of the solutions obtained, the efficiency of a gas compressor is calculated.     

An acoustic estimate of methane concentration in a water column in regions of methane bubble release

A remote acoustic method is presented for estimating the methane flux into water from rising bubbles. With the proposed method and data of hydroacoustic measurements in the Sea of Okhotsk, the dissolved methane concentration profile that forms in the water column in regions of methane bubble release is estimated. Comparison of the aforementioned methane concentration profile with results of direct measurements shows good quantitative and qualitative agreement. This testifies to the fair accuracy of the proposed acoustic method and is indicative of the dominant role of bubble transport in the formation of the concentration of dissolved methane in the water column in such regions.     

Aspects of the internal reforming of methane in solid oxide fuel cells

The tubular concept of the Siemens Westinghouse SOFC is reviewed. The efforts to reduce costs by on-cell reformation of methane on high power density cells are outlined. The problems concerning the internal reformation of methane are discussed from a thermodynamic point of view. Investigations of the steam reformation of methane on Ni-YSZ anodes are reported to clarify the kinetics. The suitability of this material as a catalyst for this reaction is confirmed. On stripes of anodes a steady state utilisation of methane was reached only after many hours, significantly complicating the experiments. This delay was not seen with anodes in cell configurations, suggesting a different process. In neither arrangement the shift reaction was in thermodynamic equilibrium. This reaction seems to be correlated with the reformation. Experiments on stripes with pure mixtures of methane and steam revealed the dissolving of Ni into the gas phase at the leading edge of the sample. This effect can be suppressed by adding a small amount of hydrogen. With gas compositions typical for SOFC operation no degradation of the electrodes was detected during 1000 hours. Assuming an isothermal sample and equilibrium of the shift reaction, the reaction rate was best described being first order in the partial pressures of methane and water for varying lengths of the stripes. But this function failed to describe the variation of the methane utilisation with composition of the input gas, showing that the complexity of the reformation is not fully understood. The reaction rate was found to be too high for on-cell reformation in SOFC stacks. Simulations of a planar design yielded such large temperature gradients that they are likely to result in a disintegration of the cell structure. The same is expected for the tubular design. Tailored catalysts and new cell designs are required to overcome the heat management problem. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized ¹²⁹Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

Modeling photothermal and acoustical induced microbubble generation and growth

Previous experimental studies showed that powerful heating of nanoparticles by a laser pulse using energy density greater than 100 mJ/cm², could induce vaporization and generate microbubbles. When ultrasound is introduced at the same time as the laser pulse, much less laser power is required. For therapeutic applications, generation of microbubbles on demand at target locations, e.g. cells or bacteria can be used to induce hyperthermia or to facilitate drug delivery. The objective of this work is to develop a method capable of predicting photothermal and acoustic parameters in terms of laser power and acoustic pressure amplitude that are needed to produce stable microbubbles; and investigate the influence of bubble coalescence on the thresholds when the microbubbles are generated around nanoparticles that appear in clusters.

We develop and solve here a combined problem of momentum, heat and mass transfer which is associated with generation and growth of a microbubble, filled with a mixture of non-vaporized gas (air) and water vapor. The microbubble’s size and gas content vary as a result of three mechanisms: gas expansion or compression, evaporation or condensation on the bubble boundary, and diffusion of dissolved air in the surrounding water. The simulations predict that when ultrasound is applied relatively low threshold values of laser and ultrasound power are required to obtain a stable microbubble from a single nanoparticle. Even lower power is required when microbubbles are formed by coalescence around a cluster of 10 nanoparticles. Laser pulse energy density of 21 mJ/cm² is predicted for instance together with acoustic pressure of 0.1 MPa for a cluster of 10 or 62 mJ/cm² for a single nanoparticle. Those values are well within the safety limits, and as such are most appealing for targeted therapeutic purposes.     

气泡成核过程的格子Boltzmann方法模拟

利用精确差分格子Boltzmann模型探讨水在特定温度下的亚稳态及不稳定平衡态, 获得等温相变过程中形成气泡和液滴的条件, 模型预测结果与理论解符合良好. 在该等温模型的基础上耦合能量方程, 通过调节流体-壁面相互作用力获得不同的气泡与固壁间接触角, 从而建立了一种新的描述气液相变的格子Boltzmann理论模型. 利用该新模型模拟不同流体-壁面相互作用力下凹坑气泡成核过程, 再现了气泡成核过程中的三阶段特性; 探讨了接触角、曲率半径及气泡体积随气泡成核过程的变化关系, 获得了与文献结果定性符合的曲率-气泡体积关系曲线. 关键词： 格子Boltzmann方法 气泡成核过程 气液相变 接触角     

Measurements of frequency spectra of transmission coefficients to ultrasound through trapped microbubbles

Techniques which use hydrophobic polycarbonate thin sheets containing randomly spaced, fairly uniform small pores immersed in water to trap air bubbles have been found to be useful in biophysical experiments. The utilization of broadband polyvinylidene fluoride transducers in this work made it possible to measure a continuous frequency spectrum of the transmission coefficient of the trapped bubbles. The results of the measurements show: (1) the frequency response curve of the bubble ensemble is much broader than that of a single bubble predicted by theory; and (2) as the incident sound pressure at a micropore membrane increases from 110 to 660 Pa the resonance frequency of bubbles shifts to lower values by as much as 7%.