Phase Equilibrium in Complex Liquids under Negative Pressure

Imre, Attila R.; Drozd-Rzoska, Aleksandra; Kraska, Thomas; Martinás, Katalin; Rebelo, Luís Paulo N.; Rzoska, Sylwester J.; Višak, Zoran P.; Yelash, Leonid

doi:10.1007/1-4020-2704-4_16

Cited by 3 publications

(9 citation statements)

References 22 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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“…On condensation, the negative internal pressure changes continuously into a negative absolute pressure. The latter has been discussed for complex liquids and solids with sufficiently high cohesive energies [ 8 ]. In conventional thermodynamics, a negative pressure state means that an increase of volume results in a decrease of entropy, warning that this is uniquely defined only for cases where either there is no work or no heat exchange performed during a process, and if heat and work appear simultaneously, only the internal energy can be measured [ 9 ].…”

Section: Deficiencies Of Bulk Thermodynamicsmentioning

confidence: 99%

What Is Heat? Can Heat Capacities Be Negative?

Roduner

2023

Entropy

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In the absence of work, the exchange of heat of a sample of matter corresponds to the change of its internal energy, given by the kinetic energy of random translational motion of all its constituent atoms or molecules relative to the center of mass of the sample, plus the excitation of quantum states, such as vibration and rotation, and the energy of electrons in excess to their ground state. If the sample of matter is equilibrated it is described by Boltzmann’s statistical thermodynamics and characterized by a temperature T. Monotonic motion such as that of the stars of an expanding universe is work against gravity and represents the exchange of kinetic and potential energy, as described by the virial theorem, but not an exchange of heat. Heat and work are two distinct properties of thermodynamic systems. Temperature is defined for the radiative cosmic background and for individual stars, but for the ensemble of moving stars neither temperature, nor pressure, nor heat capacities are properly defined, and the application of thermodynamics is, therefore, not advised. For equilibrated atomic nanoclusters, in contrast, one may talk about negative heat capacities when kinetic energy is transformed into potential energy of expanding bonds.

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“…For the latter the prefactor τ T 0 ranges from ∼10 −12 s for molecular liquids ( [1,2,4,6,41] and references therein) to ∼10 −16 s for vitrifying, orientationally disordered crystals [42,43]. Generally, the thermodynamic domain of the liquid state is limited by a spinodal, defining the stability limits for homogeneous nucleation [75][76][77][78][79][80][81]. Hence, one may expect the τ T 0 prefactor to be related to the relaxation time at the high temperature liquid-gas stability limit.…”

Section: A Pressure Counterpart Of the Vft Relationmentioning

confidence: 99%

“…Herein we present such a comparison, for both the temperature and the pressure paths to the glass transition. Modified forms of the PVFT and AvM relations are proposed, for removing some inherent inconsistencies as well as enabling extension into the negative pressures (isotropically stretched liquid) domain [75][76][77][78][79][80][81]. All of this led to a revised answer to the question 'Does fragility depend on pressure?'…”

Section: Introductionmentioning

confidence: 99%

On the pressure evolution of dynamic properties of supercooled liquids

Drozd-Rzoska

Rzoska

Roland

et al. 2008

J. Phys.: Condens. Matter

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A pressure counterpart of the Vogel-Fulcher-Tammann (VFT) equation for representing the evolution of dielectric relaxation times or related dynamic properties is discussed:, where P = P − P SL , P 0 is the ideal glass pressure estimation, D P is the pressure fragility strength coefficient, and the prefactor τ P 0 is related to the relaxation time at the stability limit (P SL ) in the negative pressure domain. The discussion is extended to the Avramov model (AvM) relation τ (T,

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Phase Equilibrium in Complex Liquids under Negative Pressure

Cited by 3 publications

References 22 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

What Is Heat? Can Heat Capacities Be Negative?

On the pressure evolution of dynamic properties of supercooled liquids

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