Phase diagram of aqueous solution at high pressure and low temperature

Abstract

This paper presents a constant mass high pressure isothermal calorimeter and describes the range of applications that this type of equipment can deal with. As an example, the thermophysical properties of an aqueous solution of MgSO₄ at low temperature and at high pressure have been investigated. The main results showed that the phase change heat of the solution decreased with increasing pressure and the phase change temperature of the eutectic concentration was depressed under high pressure. Those changes could be related to the MgSO₄ solubility and to water latent heat changes.     

Time dependent canonical perturbation theory II: Application to the Henon-Heiles system

In this communication, we report the results of the application of time-dependent perturbation theory to the Henon-Heiles system. We show that the predictions of the perturbation theory hold good for short times, and try to explain the increase of error in the predicted results with the increase in energy.     

Fusion curves and thermodynamic properties of carbon tetrachloride, chloroform, bromoform and silicon tetrachloride at pressure up to 3500 MPa

The fusion temperature as a function of pressure for carbon tetrachloride, chloroform, bromoform and silicon tetrachloride at pressures up to 3500MPa has been determined. The experimental data were fitted by the equation Tfus=T0（1 ＋ Δp/a1）^a2 exp（-a3Δp） and the changes of the maolar enthalpy and molar internal energy on fusion were calculated using the parameters of the fitted equation. Comparisons with the data from the literature show that the experimental data, parameters of fitted equations, changes of the molar enthalpy and molar internal energy are reliable.     

Structural and elastic properties of barium chalcogenides (BaX,X=O,Se, Te) under high pressure

In the present paper we have investigated the high-pressure, structural phase transition of Barium chalcogenides (BaO, BaSe and BaTe) using a three-body interaction potential (MTBIP) approach, modified by incorporating covalency effects. Phase transition pressures are associated with a sudden collapse in volume. The phase transition pressures and associated volume collapses obtained from TBIP show a reasonably good agreement with experimental data. Here, the transition pressure, NaCl-CsCl structure increases with decreasing cation-to-anion radii ratio. In addition, the elastic constants and their combinations with pressure are also reported. It is found that TBP incorporating a covalency effect may predict the phase transition pressure, the elastic constants and the pressure derivatives of other chalcogenides as well.      

压强对苯分子费米共振的影响

测量了在0—13GPa压强下苯分子的拉曼光谱,结果表明:所有拉曼谱带随压强的增加发生蓝移,并伴随某些谱带的劈裂和相对强度的变化;而对于苯分子的ν1+ν6—ν8两费米共振谱带,根据Betran理论,计算出它们的频率间隔Δ0随压强的增加而增大,这是由于合频ν1+ν6频移随压强增加速度大于相应于基频ν8速度的结果,进而导致了费米共振耦合系数ω和强度比Rf/a减小.当压强增加至11GPa时,费米共振现象消失,该现象用高压下相变给予解释.本结果丰富了环境变化对分子费米共振影响的研究内容,对谱线认证、归属有参考价值.     

A study on the electrical property of HgSe under high pressure

Using a microcircuit fabricated on a diamond anvil cell, we have measured in-situ conductivity of HgSe under high pressures, and investigated the temperature dependence of conductivity under several different pressures. The result shows that HgSe has a pressure-induced transition sequence from a semimetal to a semiconductor to a metal, similar to that in HgTe. Several discontinuous changes in conductivity are observed at around 1.5, 17, 29 and 49GPa, corresponding to the phase transitions from zinc-blende to cinnabar to rocksalt to orthorhombic to an unknown structure, respectively. In comparison with HgTe, it is speculated that the unknown structure may be a distorted CsCl structure. For the cinnabar-HgSe, the energy gap as a function of pressure is obtained according to the temperature dependence of conductivity. The plot of the temperature dependence of conductivity indicates that the unknown structure of HgSe has an electrical property of a conductor.     

Volume compression of thallium to 45 GPa

Abstract

High-pressure structural transition and volume compression for thallium were investigated to 45 GPa in a diamond anvil cell using the angular dispersive X-ray diffraction technique. Except for the known polymorphic transition at 3.7 GPa, no other structural change was observed in this pressure range. The equation of state of the high pressure phase has been obtained: its initial bulk modulus, B₀ = 33.1 GPa, is lower by 10% than that of the hexagonal phase at normal pressure.     

Raman spectroscopy of natural cordierite at high water pressure up to 5 GPa

The high‐pressure behaviour of cordierite, a widespread ring aluminosilicate with channels incorporating fluid compounds (H₂O, CO₂), is characterized by the absence of phase transitions up to 2.5 GPa. However, the distortion of the ring tetrahedra observed previously at 2.3 GPa is supposed to introduce a phase transition at higher pressure, which has not been checked so far. This work presents a high‐pressure Raman spectroscopic study of natural cordierite compressed in water medium up to 4.7 GPa in a diamond anvil cell. At P > 4 GPa, a disordering of both the framework and intrachannel H₂O subsystem is apparent from significant broadening of Raman peaks and the evolution of short‐range order parameters. This is followed by abrupt shifts of the framework and O–H stretching modes at about 4.5 GPa, indicating a first‐order phase transition. Its reversibility is seen from the recovery of the initial spectrum at P < 3 GPa. The shift amplitudes of different framework modes indicate the predominance of distortion over contraction of the framework polyhedra upon this transition. The disordering of the H₂O subsystem in the high‐pressure phase is likely a consequence of distortion of the channel‐forming framework elements, which is supposed to be a driving force of this transition. Copyright © 2011 John Wiley & Sons, Ltd.     

Employment of a novel ultrasonic method to investigate high pressure phase transitions in oleic acid

In this work, the variation of sound velocity with hydrostatic pressure for oleic acid is evaluated up to 350 MPa. During the measurement, we identified the phase transformation of oleic acid and the presence of the hysteresis of the dependence of sound velocity on pressure. From the performed measurements, it can be seen that the dependence of sound velocity on pressure can be used to investigate phase transformations in natural oils. Ultrasonic waves were excited and detected using piezoelectric LiNbO₃(Y-36 cut) 5 MHz transducers. The phase velocity of the longitudinal ultrasonic waves was measured using a cross-correlation method to evaluate the time of flight.     

Electric permittivity and dielectric loss of castor oil during its transformation to the high pressure phase

Abstract

The changes of permittivity and dielectric loss of commercially pure castor oil observed during its transition to the high pressure phase are described. Discussion about physical properties of this phase is shortly presented too.     

Anomalies in the velocity of longitudinal ultrasonic waves in cesium under the pressure up to 5 GPa

Abstract

The velocity of longitudinal ultrasonic waves, ν₁,(P), in polycrystalline cesium was measured at 293 ±1K in the pressure interval 0–5 GPa. v ₁(P) alterations at BCC-FCC phase transition at 2.3 GPa and at the electronic-structure transformation at 4.3 GPa were obtained. Decrease of v ₁(P) to 4.3 GPa after a maximum at ～3.8 GPa were found, that gave evidence to the appearance of a corresponding soft mode in the FCC-Cs phonon spectrum. The peculiarities of dependence v ₁(P) correlate with s-conduction electrons promotion to the empty d-band in accordance with the theoretically predicted continuous electronic s-d transformation in Cs.     

A high pressure Raman study of TeO2 to 30 GPa and pressure-induced phase changes

The effect of pressure on the Raman modes in TeO₂ (paratellurite) has been investigated to 30GPa, using the diamond cell and argon as pressure medium. The pressure dependence of the Raman modes indicates four pressure-induced phase transitions near 1 GPa, 4.5 GPa, 11 GPa and 22 GPa. Of these the first is the well studied second-order transition fromD ₄ ⁴ symmetry toD ₂ ⁴ symmetry, driven by a soft acoustic shear mode instability. The remarkable similarity in the Raman spectra of phases I to IV suggest that only subtle changes in the structure are involved in these phase transitions. The totally different Raman spectral features of phase V indicate major structural changes at the 22GPa transition. It is suggested that this high pressure-phase is similar to PbCl₂-type, from high pressure crystal chemical considerations. The need for a high pressure X-ray diffraction study on TeO₂ is emphasized, to unravel the structure of the various high pressure phases in the system.     

On the formation of photoinduced high pressure phases in sulfur below 10 GPa

Abstract

We investigate the phase transformations in sulfur for pressures up to 10 GPa by time resolved Raman spectroscopy. The transition to the photosensitive phase p-S is stimulated by the blue laser line between 3 and 9 GPa. The kinetics of this transition as derived from the time evolution of the intensities of characteristic Raman excitations shows the typical features of an activated first order phase transition. This transformation proceeds via a disordered (amorphous) intermediate state.

Above 9 GPa a further phase change to S, is kinetically characterized and follows similar rules i.e. the integral intensities of selected S, Raman lines exhibit a sigmoidal time dependence. In both high pressure phases a broad Raman excitation between 800 and 1000 cm^?1 is observed.     

First-principles investigation of the electronic, elastic and thermodynamic properties of VC under high pressure

An investigation of the electronic,elastic and thermodynamic properties of VC under high pressure has been conducted using first-principles calculations based on density functional theory (DFT) with the plane-wave basis set,as implemented in the CASTEP code. At elevated pressures,VC is predicted to undergo a structural transition from a relatively open NaCl-type structure to a more dense CsCl-type one. The predicted transition pressure is 520 GPa. The elastic constant,Debye temperature and heat capacity each as a function of pressure and/or temperature of VC are presented for the first time.     

高压下RhB的相变、弹性性质、电子结构及硬度的第一性原理计算

采用密度泛函理论中的赝势平面波方法系统地研究了高压下RhB的结构相变、弹性性质、电子结构和硬度.分析表明,RhB在25.3 GPa时从anti-NiAs结构相变到FeB结构,这两种结构的弹性常数、体弹模量、剪切模量、杨氏模量和弹性各向异性因子的外压力效应明显.电子态密度的计算结果显示,这两种结构是金属性的,且费米能级附近的峰随着压强的增大向两侧移动,赝能隙变宽,轨道杂化增强,共价性增强,非局域化更加明显.此外,硬度计算结果显示,anti-NiAs-RhB的金属性比较弱,有着较高的硬度,属于硬质材料.     

Influence of high pressure on the relative permittivity of oleic acid

Oleic acid (OA) is a monounsaturated omega-9 fatty acid which undergoes a first-order phase transition when it is influenced by high pressures. The transition results in a change of molecular structure, which was investigated by means of X-ray techniques [J. Przedmojski and R.M. Siegoczyński, X-ray diffraction investigation of oleic acid under high pressure, Phase Transit. 75 (2002), pp. 373–377]. Despite a significant change in the structure, the permittivity of the acid remains barely influenced during and after the phase transition. A rise in relative permittivity has been observed due to the increasing number of molecules per volume unit within a compression cycle. However, no significant fall in the permittivity has been observed as a result of the transition which occurs in the case of edible oils. This may be caused by a strongly dimerised structure and dipole–dipole interaction in the liquid at ambient pressure.     

Determination of the phase boundary of GaP using in situ high pressure and high-temperature X-ray diffraction

The high pressure behavior of gallium phosphide, GaP, has been examined using the synchrotron X-ray diffraction technique in a diamond anvil cell up to 27?GPa and 900?K. The transition from a semiconducting to a metallic phase was observed. This transition occurred at 22.2?GPa and room temperature, and a negative dependence of temperature of this transition was found. The transition boundary was determined to be P (GPa)?=?22.6???0.0014?×?T (K).     

The hydrogen‐bond effect on the high pressure behavior of hydrazinium monochloride

The first high pressure study of solid hydrazinium monochloride has been performed by in situ Raman spectroscopy and synchrotron X‐ray diffraction (XRD) experiments in diamond anvil cell (DAC) up to 39.5 and 24.6 GPa, respectively. The structure of phase I at room temperature is confirmed to be space group C2/c by the Raman spectral analysis and Rietveld refinement of the XRD pattern. A structural transition from phase I to II is observed at 7.3 GPa. Pressure‐induced position variation of hydrogen atoms in NH₃⁺ unit during the phase transition is attributed to the formation of N―H…Cl hydrogen‐bonds, which play a vital role in the stability and subsequent structural changes of this high energetic material under pressure. This inference is proved from the abnormal pressure shifts and obvious Fermi resonance in NH stretching mode of N₂H₅⁺ ion in the Raman experiment. Finally, a further transition from phase II to III accompanied with a slight internal distortion in the N₂H₅⁺ ions occurs above 19.8 GPa, and phase III persists up to 39.5 GPa. Copyright © 2015 John Wiley & Sons, Ltd.