Melting curve and fluid equation of state of carbon dioxide at high pressure and high temperature

The melting curve and fluid equation of state of carbon dioxide have been determined under high pressure in a resistively heated diamond anvil cell. The melting line was determined from room temperature up to 11.1+/-0.1 GPa and 800+/-5 K by visual observation of the solid-fluid equilibrium and in situ measurements of pressure and temperature. Raman spectroscopy was used to identify the solid phase in equilibrium with the melt, showing that solid I is the stable phase along the melting curve in the probed range. Interferometric and Brillouin scattering experiments were conducted to determine the refractive index and sound velocity of the fluid phase. A dispersion of the sound velocity between ultrasonic and Brillouin frequencies is evidenced and could be reproduced by postulating the presence of a thermal relaxation process. The Brillouin sound velocities were then transformed to thermodynamic values in order to calculate the equation of state of fluid CO2. An analytic formulation of the density with respect to pressure and temperature is proposed, suitable in the P-T range of 0.1-8 GPa and 300-700 K and accurate within 2%. Our results show that the fluid above 500 K is less compressible than predicted from various phenomenological models.     

金属钾和碳酸钠高压合成金刚石

以金属钾和碳酸钠为反应原料, 在压力为2 GPa, 温度为500 ℃的密封白金坩埚中反应18 h, 所得产物通过粉末X射线衍射和显微拉曼分析进行了表征, 证实合成出了微米级的金刚石. 对金刚石的合成机理进行了研究, 推测其反应过程为碳酸钠在铂和钾的作用下分解出CO2, CO2与钾反应得到金刚石. 研究结果表明金刚石可以在温和的条件下合成.     

Equation of state and anharmonicity of carbon dioxide phase I up to 12 GPa and 800 K

We present an extended investigation of phase I of carbon dioxide by x-ray diffraction and spectroscopic techniques at simultaneous high pressure and high temperature, up to 12 GPa and 800 K. Based on the present and literature data, we show that a Mie-Gru?neisen-Debye model reproduces within experimental uncertainties the equation of state of CO(2) over the entire range of stability of phase I. Using infrared and Raman spectroscopy, we have determined the frequencies of the zone-center lattice modes as a function of pressure and temperature. We have then extracted the volume and temperature dependencies of the optical lattice mode frequencies and their respective Gru?neisen parameters. We find a large difference between the thermodynamic Gru?neisen parameter obtained from the P-V-T data and those associated with the optical lattice modes. This suggests, within the quasiharmonic approximation, that acoustic modes have a dominant contribution to the anharmonicity of the system.     

The chemistry of cyanuric acid (H3C3N3O3) under high pressure and high temperature

We have studied cyanuric acid (H(3)C(3)N(3)O(3)) at static pressures up to 8.1 GPa and simultaneous temperatures up to 750 K, using primarily infrared absorption spectroscopy and visual observation. The corresponding phase diagram compares favorably with theoretical predictions of metastable organic materials. Two reactions were observed and characterized; both are irreversible. Below 2 GPa, melting is accompanied by a decomposition reaction, and upon cooling, cyanuric acid is not recovered. Above 2 GPa, heating results in a solid product recoverable at ambient conditions. Corresponding infrared spectra suggest that pressure leads to the formation of heterocycles of increasing complexity and biological potential, with the composition determined by the pressure of formation. Cyanuric acid is of interest at these conditions because it and its monomer, isocyanic acid, are "prebiotic" compounds found in stellar dust clouds, meteorites, and other remnants of the early Earth.     

High-pressure vibrational spectroscopy of sulfur dioxide

Solid sulfur dioxide was investigated by vibrational spectroscopy over a broad pressure and temperature range, extending to 32.5 GPa at 75-300 K in diamond anvil cells. Synchrotron infrared spectra provided the first measurements of the pressure dependence of the lattice modes in the far-IR region. Below 17.5 GPa, two fundamentals exhibit splittings enhanced by pressure. The asymmetric stretching mode of SO(2) exhibits a remarkable pressure-induced softening. The observations are consistent with the ambient pressure Raman measurements indicating that SO(2) crystallizes in an acentric cell, but are inconsistent with a previously proposed interpretation that the structure of the high-pressure phase consists of (SO(2))(3) clusters. Dramatic changes in the Raman spectra are found above 17.5 GPa at room temperature. These indicate major changes in structure and possible formation of SO(2) clustering with an enlarged unit cell. The behavior at low temperature differs from that at room temperature. These findings provide constraints on the phase diagram of sulfur dioxide.     

The Local Atomic Structures of Liquid CO at 3.6 GPa and Polymerized CO at 0 to 30 GPa from High‐Pressure Pair Distribution Function Analysis

The local atomic structures of liquid and polymerized CO and its decomposition products were analyzed at pressures up to 30 GPa in diamond anvil cells by X‐ray diffraction, pair distribution function (PDF) analysis, single‐crystal diffraction, and Raman spectroscopy. The structural models were obtained by density functional calculations. Analysis of the PDF of a liquid CO‐rich phase revealed that the local structure has a pronounced short‐range order. The PDFs of polymerized amorphous CO at several pressures revealed the compression of the molecular structure; covalent bond lengths did not change significantly with pressure. Experimental PDFs could be reproduced with simulations from DFT‐optimized structural models. Likely structural features of polymerized CO are thus 4‐ to 6‐membered rings (lactones, cyclic ethers, and rings decorated with carbonyl groups) and long bent chains with carbonyl groups and bridging atoms. Laser heating polymerized CO at pressures of 7 to 9 GPa and 20 GPa resulted in the formation of CO₂.     

Melting and dissociation of ammonia at high pressure and high temperature

Raman spectroscopy and synchrotron x-ray diffraction measurements of ammonia (NH(3)) in laser-heated diamond anvil cells, at pressures up to 60 GPa and temperatures up to 2500 K, reveal that the melting line exhibits a maximum near 37 GPa and intermolecular proton fluctuations substantially increase in the fluid with pressure. We find that NH(3) is chemically unstable at high pressures, partially dissociating into N(2) and H(2). Ab initio calculations performed in this work show that this process is thermodynamically driven. The chemical reactivity dramatically increases at high temperature (in the fluid phase at T > 1700 K) almost independent of pressure. Quenched from these high temperature conditions, NH(3) exhibits structural differences from known solid phases. We argue that chemical reactivity of NH(3) competes with the theoretically predicted dynamic dissociation and ionization.     

Water-in-CO2 emulsions: reaction vessels for the production of tetra-ethyl pyrone

Water-in-CO2 (W/C) emulsions formed using a nickel Triton X-100 surfactant complex (Ni-surfactant) were used as microreactors for the carbon-carbon coupling reaction between hex-3-yne and CO2 to produce tetra-ethyl pyrone (TEP). The structure of the product, which was isolated in the CO2 phase, was determined using gas chromatography mass spectrometry (GC-MS) and infrared spectroscopy. The Ni-surfactant acted as both an emulsion forming agent and a water soluble catalyst for this carbon-carbon coupling reaction. The optimum yield of TEP was determined to be 69% after 72 h, at a temperature of 70 degrees C and a pressure of 206 bar. The ease with which the emulsion could be collapsed allowed the facile separation of products from the catalyst and any unreacted starting material. Product selectivity in the W/C emulsions was found to be greater than that obtained using conventional organic methodologies.     

Spectroscopic studies of the molecular interactions in n-ethylamines and 2-nitropropane/n-ethylamine mixtures

New experimental results are reported on molecular interactions in the n-ethylamines and 2-nitropropane (2-NP)/n-ethylamine mixtures studied by Raman spectroscopy under pressure in a diamond anvil cell (0-50 GPa) and, at ambient pressure, by infrared spectroscopy. Modifications of the infrared spectra in 2-NP in presence of triethylamine (TEA) or diethylamine (DEA) have been observed at ambient pressure and interpreted as a specific molecular interaction. High-pressure fluorescence in the vicinity of the liquid-solid phase transition of the 2-NP/DEA and 2-NP/monoethylamine mixtures, is highlighted and discussed.     

High pressure-temperature Raman measurements of H2O melting to 22 GPa and 900 K

The melting curve of H(2)O has been measured by in situ Raman spectroscopy in an externally heated diamond anvil cell up to 22 GPa and 900 K. The Raman-active OH-stretching bands and the translational modes of H(2)O as well as optical observations are used to directly and reliably detect melting in ice VII. The observed melting temperatures are higher than previously reported x-ray measurements and significantly lower than recent laser-heating determinations. However, our results are in accord with earlier optical determinations. The frequencies and intensities of the OH-stretching peaks change significantly across the melting line while the translational mode disappears altogether in the liquid phase. The observed OH-stretching bands of liquid water at high pressure are very similar to those obtained in shock-wave Raman measurements.     

Raman and infrared vibrational modes of tricosane paraffin under high pressure

This paper reports an experimental study about the pressure dependence of the vibrational modes of tricosane paraffin (C₂₃H₄₈) investigated by in situ Raman and infrared spectroscopy in a diamond anvil cell (DAC). The main vibrational bands were followed up to 11 GPa and the observed behavior indicated a conformational disorder induced by pressure, corresponding to a transition from ordered to disordered state of the linear chains from 2 to 5 GPa followed by a transition to an amorphous state under pressure above 5 GPa. However, this behavior was reversible after compression–decompression cycle showing that this linear compound was structurally and chemically stable up to 11 GPa at room temperature.     

In situ studies of methanol decomposition and oxidation on Pd(111) by PM-IRAS and XPS spectroscopy

Methanol decomposition and oxidation on Pd(111) at millibar pressure were studied by in situ polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS), on-line gas chromatography and pre- and postreaction X-ray photoelectron spectroscopy (XPS). Various dehydrogenation products such as methoxy CH3O, formaldehyde CH2O, formyl CHO, and CO could be spectroscopically identified. Methanol oxidation proceeds via dehydrogenation to formaldehyde CH2O, which either desorbs or is further dehydrogenated to CO, which is subsequently oxidized to CO2. Carbonaceous overlayers that are present during the reaction may favorably affect the selectivity toward CH2O. The reaction takes place on metallic Pd, and no indications of an involvement of Pd surface oxide were observed.     

Pressure-induced chemical decomposition and structural changes of boric acid

A combined synchrotron X-ray diffraction, Raman scattering, and infrared spectroscopy study of the pressure-induced changes in H(3)BO(3) to 10 GPa revealed a new high-pressure phase transition between 1 and 2 GPa followed by chemical decomposition into cubic HBO(2), ice-VI, and ice- VII at approximately 2GPa. The layered triclinic structure of H(3)BO(3) exhibits a highly anisotropic compression with maximum compression along the c direction, accompanied by a strong reduction of the interlayer spacing. The large volume variation and structural changes accompanying the decomposition suggest high activation energy. This yields a slow reaction kinetics at room temperature and a phase composition that is highly dependent on the specific pressure-time path followed by the sample. The combined results have been used to propose a mechanism for pressure-induced dehydration of H(3)BO(3) that implies a proton disorder in the system.     

高压下铌酸锌钶铁矿结构相变的原位拉曼光谱和X射线衍射研究

通过原位高压拉曼光谱和X射线衍射对ZnNb₂O₆晶体在29 GPa以下的结构转变进行了研究.拉曼光谱显示, 多数拉曼峰强度减弱, 且随着压力增加向高波数方向移动.压力频移曲线分别在10, 16 和20 GPa处形成了拐点.原位X射线衍射谱在10.6 GPa以上有旧峰消失和新峰出现.结果分析表明, ZnNb₂O₆钶铁矿结构压缩过程中发生了一个可逆压致相变, 此相变从10 GPa左右开始, 到16 GPa左右完成, 继续增加压力到20 GPa以上则形成无序状态.     

CO gas sensing by ultrathin tin oxide films grown by atomic layer deposition using transmission FTIR spectroscopy

Ultrathin tin oxide films were deposited on SiO2 nanoparticles using atomic layer deposition (ALD) techniques with SnCl4 and H2O2 as the reactants. These SnO(x) films were then exposed to O2 and CO gas pressure at 300 degrees C to measure and understand their ability to serve as CO gas sensors. In situ transmission Fourier transform infrared (FTIR) spectroscopy was used to monitor both the charge conduction in the SnO(x) films and the gas-phase species. The background infrared absorbance measured the electrical conductivity of the SnO(x) films based on Drude-Zener theory. O2 pressure was observed to decrease the SnO(x) film conductivity. Addition of CO pressure then increased the SnO(x) film conductivity. Static experiments also monitored the buildup of gas-phase CO2 reaction products as the CO reacted with oxygen species. These results were consistent with both ionosorption and oxygen-vacancy models for chemiresistant semiconductor gas sensors. Additional experiments demonstrated that O2 pressure was not necessary for the SnO(x) films to detect CO pressure. The background infrared absorbance increased with CO pressure in the absence of O2 pressure. These results indicate that CO can produce oxygen vacancies on the SnO(x) surface that ionize and release electrons that increase the SnO(x) film conductivity, as suggested by the oxygen-vacancy model. The time scale of the response of the SnO(x) films to O2 and CO pressure was also measured by using transient experiments. The ultrathin SnO(x) ALD films with a thickness of approximately 10 A were able to respond to O2 within approximately 100 s and to CO within approximately 10 s. These in situ transmission FTIR spectroscopy help confirm the mechanisms for chemiresistant semiconductor gas sensors.     

FTIR研究HCO自由基与NO2反应的动力学

为了减少和控制油品在燃烧时 NOx的排放 ,对 NOx再燃烧进程的动力学研究一直受到人们的关注 [1,2].迄今为止 ,对于该进程中的一些可能参与的基元化学反应知道甚少 .从实验测得的总速率常数看 ,在室温下 ,主反应 HCO自由基与 NO2的反应是一个相当快速的反应 [3],其总速率常数约为 3.3× 1013 cm3· mol－ 1· s－ 1.但是 ,有关该反应体系的产物分布情况及其反应机理目前还未见报导 .该反应体系在热力学上存在着下列 放热反应 [4]:　　反应 [1a－ 1e]可在低压条件下发生 ,而反应 [1f－ 1g]只能在高压范围内产生 [5,6].本文是以高纯度的甲…     

Dimerization and polymerization of isoprene at high pressures

The high-pressure reactivity of isoprene has been studied at room temperature up to 2.6 GPa by using the diamond anvil cell technique in combination with Fourier transform infrared spectroscopy. Both dimerization and polymerization reactions take place above 1.1 GPa. At this pressure, the two processes are well separated in time, the dimerization being the only one occurring in the first 150 h. Both processes simultaneously occur as the pressure increases. The reaction product is composed of a volatile fraction, identified as sylvestrene, and a transparent rubberlike solid formed by cis-1,4- and 3,4-polyisoprene. The activation volume of the dimerization reaction has been obtained from the kinetic data. The photoinduced reaction, studied at room temperature for two different pressures, takes place through a two-photon absorption process, and the threshold pressure is lowered to 0.5 GPa. At this pressure, both the dimerization and polymerization processes occur, but the dimerization is not as selective as in the purely pressure-induced reaction. 4-Ethenyl-2,4-dimethylcyclohexene is obtained in addition to sylvestrene. By increasing the pressure, the photoinduced reaction becomes more selective, and the monomer is quantitatively transformed into the same polymer obtained in the purely pressure-induced reaction.     

Structural and chemical properties of the nitrogen-rich energetic material triaminoguanidinium 1-methyl-5-nitriminotetrazolate under pressure

The structural and chemical properties of the bi-molecular, hydrogen-bonded, nitrogen-rich energetic material triaminoguanidinium 1-methyl-5-nitriminotetrazolate C(3)H(12)N(12)O(2) (TAG-MNT) have been investigated at room pressure and under high pressure isothermal compression using powder x-ray diffraction and Raman and infrared spectroscopy. A stiffening of the equation of state and concomitant structural relaxation between 6 and 14 GPa are found to correlate with Raman mode disappearances, frequency discontinuities, and changes in the pressure dependence of modes. These observations manifest the occurrence of a reversible martensitic structural transformation to a new crystalline phase. The onset and vanishing of Fermi resonance in the nitrimine group correlate with the stiffening of the equation of state and phase transition, suggesting a possible connection between these phenomena. Beyond 15 GPa, pressure induces irreversible chemical reactions, culminating in the formation of a polymeric phase by 60 GPa.     

Polymorphism of dense, hot oxygen

The phase diagram and polymorphism of oxygen at high pressures and temperatures are of great interest to condensed matter and earth science. X-ray diffraction and Raman spectroscopy of oxygen using laser and resistively heated diamond anvil cells reveal that the molecular high-pressure phase ε-O(2), which consists of (O(2))(4) clusters, reversibly transforms in the pressure range of 44 to 90 GPa and temperatures near 1000 K to a new phase with higher symmetry. The data suggest that this new phase (η') is isostructural to a phase η reported previously at lower pressures and temperatures, but differs from it in the P-T range of stability and type of intermolecular association. The melting curve increases monotonically up to the maximum pressures studied (～60 GPa). The structure factor of the fluid measured as a function of pressure to 58 GPa shows continuous changes toward molecular dissociation.     

The phase diagram of ammonium nitrate

The pressure-temperature (P-T) phase diagram of ammonium nitrate (AN) [NH(4)NO(3)] has been determined using synchrotron x-ray diffraction (XRD) and Raman spectroscopy measurements. Phase boundaries were established by characterizing phase transitions to the high temperature polymorphs during multiple P-T measurements using both XRD and Raman spectroscopy measurements. At room temperature, the ambient pressure orthorhombic (Pmmn) AN-IV phase was stable up to 45 GPa and no phase transitions were observed. AN-IV phase was also observed to be stable in a large P-T phase space. The phase boundaries are steep with a small phase stability regime for high temperature phases. A P-V-T equation of state based on a high temperature Birch-Murnaghan formalism was obtained by simultaneously fitting the P-V isotherms at 298, 325, 446, and 467 K, thermal expansion data at 1 bar, and volumes from P-T ramping experiments. Anomalous thermal expansion behavior of AN was observed at high pressure with a modest negative thermal expansion in the 3-11 GPa range for temperatures up to 467 K. The role of vibrational anharmonicity in this anomalous thermal expansion behavior has been established using high P-T Raman spectroscopy.