Solid–fluid phase transitions under extreme pressures including negative ones

Imre, Attila R.; Drozd-Rzoska, Aleksandra; Horváth, Ákos; Kraska, Thomas; Rzoska, Sylwester J.

doi:10.1016/j.jnoncrysol.2008.06.033

Cited by 12 publications

(11 citation statements)

References 56 publications

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“…Triple points with negative pressure are always metastable, because the vapor phase is the stable phase, whereas positive-pressure triple points may be stable. In the case of d-camphor, the four additional triple points are located in the negative pressure area (i.e., the area for expanded condensed phases [17][18][19][20] ), resulting in enantiotropy at ordinary pressure and above. The stability hierarchy in between the triple points III-II-I, III-II-L, and II-I-L is shown schematically in an inset in Figure 2.…”

Section: Resultsmentioning

confidence: 99%

“…Because a large part of the triple points can be found in the negative pressure domain, a few words on negative pressure may be appropriate. Although for the topological method, negative pressure is mainly a calculation tool to obtain triple points and phase hierarchy, it is an existing experimental condition, namely, if there is a constant pull on the sample, forcing it to expand against equilibrium conditions (therefore all phases are metastable under negative pressure). − From a physical point of view, there is no difference between push or pull (except for the sign of the force); thus, the Clapeyron equation will remain valid under negative pressure. Measurements in the negative pressure domain would be possible, but because all phase transitions will be between metastable phases, it is at least at present very difficult to control experimental conditions in such a way that useful information about those transitions can be obtained.…”

Section: Resultsmentioning

confidence: 99%

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Topological and Experimental Approach to the Pressure−Temperature−Composition Phase Diagram of the Binary Enantiomer System d- and l-Camphor

Rietveld¹,

Espeau²,

Tamarit

et al. 2011

J. Phys. Chem. B

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In 1981, Jacques, Collet, and Wilen already put forward the idea to use pressure to influence equilibria in binary enantiomer systems in analogy with temperature (Jacques et al. Enantiomers, Racemates and Resolutions; John Wiley & Sons: New York, 1981). Whereas temperature is used routinely to study phase equilibria, pressure is an all but forgotten parameter. This is therefore possibly the first paper on the influence of pressure on a binary enantiomer system: d- and l-camphor. The study consists of two parts, a topological approach, which uses data obtained from routine measurements (differential scanning calorimetry, X-ray diffraction), and the experimental determination of phase transitions as a function of pressure and temperature. This has resulted in two topological pressure-temperature phase diagrams of the pure enantiomer d-camphor and of the racemic mixture dl-camphor; both have been verified by the experiments as a function of pressure. In turn, these results have been used to construct part of the pressure-temperature-composition phase diagram of d- and l-camphor. A method to obtain the excess Gibbs energy from these binary phase diagrams as a function of pressure is proposed.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Topological and Experimental Approach to the Pressure−Temperature−Composition Phase Diagram of the Binary Enantiomer System d- and l-Camphor

Rietveld¹,

Espeau²,

Tamarit

et al. 2011

J. Phys. Chem. B

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“…1). In the same way, the concept of spinodals can be generalized fruitfully to solids, which exhibit explosive fragmentations (the so-called spallation), when they are submitted to sudden and strong negative pressures by means of shockwaves (Imre et al, 2008).…”

Section: Introductionmentioning

confidence: 99%

Experimental superheating of water and aqueous solutions

Shmulovich

Mercury

Thiéry

et al. 2009

Geochimica et Cosmochimica Acta

101

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The metastable superheated solutions are liquids in transitory thermodynamic equilibrium inside the stability domain of their vapor (whatever the temperature is). Some natural contexts should allow the superheating of natural aqueous solutions, like the soil capillarity (low T superheating), certain continental and submarine geysers (high T superheating), or even the water state in very arid environments like the Mars subsurface (low T) or the deep crustal rocks (high T). The present paper reports experimental measurements on the superheating range of aqueous solutions contained in quartz as fluid inclusions (Synthetic Fluid Inclusion Technique, SFIT) and brought to superheating state by isochoric cooling. About 40 samples were synthetized at 0.75 GPa and 530-700 °C with internally-heated autoclaves. Nine hundred and sixty-seven inclusions were studied by micro-thermometry, including measuring the temperatures of homogenization (Th: L + V → L) and vapor bubbles nucleation (Tn: L → L + V). The Th-Tn difference corresponds to the intensity of superheating that the trapped liquid can undergo and can be translated into liquid pressure (existing just before nucleation occurs at Tn) by an equation of state. Pure water (840-935 kg m −3 ), dilute NaOH solutions (0.1 and 0.5 mol kg −1 ), NaCl, CaCl 2 and CsCl solutions (1 and 5 mol kg −1 ) demonstrated a surprising ability to undergo tensile stress. The highest tension ever recorded to the best of our knowledge (−146 MPa, 100 °C) is attained in a 5 m CaCl 2 inclusion trapped in quartz matrix, while CsCl solutions qualitatively show still better superheating efficiency. These observations are discussed with regards to the quality of the inner surface of inclusion surfaces (high P-T synthesis conditions) and to the intrinsic cohesion of liquids (thermodynamic and kinetic spinodal). This study demonstrates that natural solutions can reach high levels of superheating, that are accompanied by strong changes of their physicochemical properties.

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“…( 43), remains. It may be solved, taking into account, that liquids or solids can be isotopically stretched, which is equivalent to negative pressures and passing 𝑃 = 0 without any hallmark [120,121]. The stretching is possible until an absolute stability limit spinodal 𝑃 𝑆𝐿 < 0, where intermolecular interactions break, is reached.…”

Section: Distortion-sensitive Tests Of Previtreous Dynamics Under Pre...mentioning

confidence: 99%

New paradigm for configurational entropy in glass-forming systems

Drozd-Rzoska

Rzoska

Starzonek

2022

Sci Rep

Self Cite

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We show that on cooling towards glass transition configurational entropy exhibits more significant changes than predicted by classic relation. A universal formula according to Kauzmann temperature $${T}_{K}$$ T K is given: $$S={S}_{0}{t}^{n}$$ S = S 0 t n , where $$t=\left(T-{T}_{K}\right)/T$$ t = T - T K / T . The exponent $$n$$ n is hypothetically linked to dominated local symmetry. Such a behaviour is coupled to previtreous evolution of heat capacity $$\Delta {C}_{P}^{config.}\left(T\right)=\left(nC/T\right){\left(1-{T}_{K}/T\right)}^{n-1}$$ Δ C P c o n f i g . T = n C / T 1 - T K / T n - 1 associated with finite temperature singularity. These lead to generalised VFT relation, for which the basic equation is retrieved. For many glass-formers, basic VFT equation may have only an effective meaning. A universal-like reliability of the Stickel operator analysis for detecting dynamic crossover phenomenon is also questioned. Notably, distortions-sensitive and derivative-based analysis focused on previtreous changes of configurational entropy and heat capacity for glycerol, ethanol and liquid crystal is applied.

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Solid–fluid phase transitions under extreme pressures including negative ones

Cited by 12 publications

References 56 publications

Topological and Experimental Approach to the Pressure−Temperature−Composition Phase Diagram of the Binary Enantiomer System d- and l-Camphor

Topological and Experimental Approach to the Pressure−Temperature−Composition Phase Diagram of the Binary Enantiomer System d- and l-Camphor

Experimental superheating of water and aqueous solutions

New paradigm for configurational entropy in glass-forming systems

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