The Stability Limit and other Open Questions on Water at Negative Pressure

Caupin, Frédéric; Stroock, Abraham D.

doi:10.1002/9781118540350.ch3

Cited by 24 publications

(34 citation statements)

References 100 publications

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“…2A), based on isochoric cooling of a micrometer-size inclusion of water in quartz. Tensions as large as −140 MPa have been reported, and confirmed by others (7,19,20), which exceed by far the limit of other techniques (16,17). It was already recognized in the work of Angell that the high-density water inclusions that were able to survive cooling to room temperature without cavitation were also able to be supercooled below 08C.…”

Section: Significancesupporting

confidence: 60%

See 1 more Smart Citation

Anomalies in bulk supercooled water at negative pressure

Pallares

Azouzi

González

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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116

129

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Water anomalies still defy explanation. In the supercooled liquid, many quantities, for example heat capacity and isothermal compressibility κ T , show a large increase. The question arises if these quantities diverge, or if they go through a maximum. The answer is key to our understanding of water anomalies. However, it has remained elusive in experiments because crystallization always occurred before any extremum is reached. Here we report measurements of the sound velocity of water in a scarcely explored region of the phase diagram, where water is both supercooled and at negative pressure. We find several anomalies: maxima in the adiabatic compressibility and nonmonotonic density dependence of the sound velocity, in contrast with a standard extrapolation of the equation of state. This is reminiscent of the behavior of supercritical fluids. To support this interpretation, we have performed simulations with the 2005 revision of the transferable interaction potential with four points. Simulations and experiments are in near-quantitative agreement, suggesting the existence of a line of maxima in κ T (LMκ T ). This LMκ T could either be the thermodynamic consequence of the line of density maxima of water [Sastry S, Debenedetti PG, Sciortino F, Stanley HE (1996) Phys Rev E 53:6144-6154], or emanate from a critical point terminating a liquid-liquid transition [Sciortino F, Poole PH, Essmann U, Stanley HE (1997) Phys Rev E 55:727-737]. At positive pressure, the LMκ T has escaped observation because it lies in the "no man's land" beyond the homogeneous crystallization line. We propose that the LMκ T emerges from the no man's land at negative pressure.scenarios for water | Widom line | Berthelot tube W ater differs in many ways from standard liquids: ice floats on water, and, upon cooling below 48C, the liquid density decreases. In the supercooled liquid, many quantities, for example heat capacity and isothermal compressibility, show a large increase. Extrapolation of experimental data suggested a powerlaw divergence of these quantities at −458C (1). Thirty years ago, the stability-limit conjecture proposed that an instability of the liquid would cause the divergence (2) (Fig. 1A). This is supported by equations of state (EoSs), such as the International Association for the Properties of Water and Steam (IAPWS) EoS (3), fitted on the stable liquid and extrapolated to the metastable regions. Ten years later, the second critical point interpretation, based on simulations (4), proposed that, instead of diverging, the anomalous quantities would reach a peak, near a Widom line (5, 6) that emanates from a liquid-liquid critical point (LLCP) terminating a first-order liquid-liquid transition (LLT) between two distinct liquid phases at low temperature (Fig. 1B). The two scenarios differ in the shape of the line of density maxima (LDM) of water ( Fig. 1 A and B). A recent work (7) has added one point on this line at large negative pressure, but this was not enough to decide between the two scenarios.It has been argued (8) that ...

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Section: Significancesupporting

confidence: 60%

“…Negative pressures occur in nature, e.g., in the sap of trees, under the tentacles of octopi, or in fluid inclusions in minerals (16,17). The study of the largest tensions achievable in water was pioneered by the group of Angell (18).…”

mentioning

confidence: 99%

Anomalies in bulk supercooled water at negative pressure

Pallares

Azouzi

González

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

Self Cite

116

129

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“…It can be seen inFig. 1-B that nucleation pressure thresholds calculated using ∞ yield quantities far below the spinodal pressure of liquid water[34,60,61].…”

mentioning

confidence: 99%

The effects of ultrasound pressure and temperature fields in millisecond bubble nucleation

Andrade

Haqshenas

Pahk

et al. 2019

Ultrasonics Sonochemistry

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A phenomenological implementation of Classical Nucleation Theory (CNT) is employed to investigate the connection between high intensity focused ultrasound (HIFU) pressure and temperature fields with the energetic requirements of bubble nucleation. As a case study, boiling histotripsy in tissue-mimicking phantoms is modelled. The physics of key components in the implementation of CNT in HIFU conditions such as the derivation of nucleation pressure thresholds and approximations regarding the surface tension of the liquid are reviewed and discussed. Simulations show that the acoustic pressure is the ultimate trigger for millisecond bubble nucleation in boiling histotripsy, however, HIFU heat deposition facilitates nucleation by lowering nucleation pressure thresholds. Nucleation thus occurs preferentially at the regions of highest heat deposition within the HIFU field. This implies that bubble nucleation subsequent to millisecond HIFU heat deposition can take place at temperatures below 100 °C as long as the focal HIFU peak negative pressure exceeds the temperature-dependent nucleation threshold. It is also found that the magnitude of nucleation pressure thresholds decreases with decreasing frequencies. Overall, results indicate that it is not possible to separate thermal and mechanical effects of HIFU in the nucleation of bubbles for timescales of a few milliseconds. This

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“…While the effect of volume on cavitation pressure is expected to be small, mechanisms such as heterogeneous nucleation on less hydrophilic solid surfaces or ubiquitous hydrophobic impurities have been invoked. 30 Identification of nucleation pathways is outside the scope of the present paper.…”

Section: Thermodynamics Of Solution-vapor Equilibriummentioning

confidence: 96%

How Solutes Modify the Thermodynamics and Dynamics of Filling and Emptying in Extreme Ink-Bottle Pores

et al. 2019

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We investigate the filling and emptying of extreme ink-bottle porous mediamicrometer-scale pores connected by nanometer-scale pores-when changing the pressure of the external vapor, in a case where the pore liquid contains solutes. These phenomena are relevant in diverse contexts, such as the weathering of building materials and artwork, aerosol formation in the atmosphere, and the hydration of soils and plants. Using model systems made of vein-shaped microcavities interconnected by a mesoporous matrix, we show experimentally that the presence of nonvolatile solute shifts the condensation and evaporation transitions and in a way that is consistent with a modified Kelvin-Laplace equation that takes into account the osmotic pressure of the solution. Emptying occurs far below saturation, when the Kelvin stress, mediated by the large curvature of the liquid-vapor interfaces in the nanopores, is large enough to 1 induce spontaneous bubble nucleation in the micro-veins. Filling, on the other hand, occurs close to equilibrium (i.e., at saturation, p sat for pure water and p s < p sat for a solution), driven by the weak capillary pressure of the liquid-vapor interface in the micro-veins. Interestingly, solutes allow the system to reach situations where the vapor is supersaturated with respect to the solution (p s < p < p sat). We show that in that latter situation, a condensation layer covers the outer surface of the porous system, preventing the generation of Kelvin stresses but inducing osmotic stresses and flows that are vapor-pressure-dependent. The timescales and dynamics reflect these different driving forces: emptying proceeds through discrete, stochastic nucleation events with very fast, unsteady bubble growth associated with a poroelastic relaxation process, while filling occurs collectively in all veins of the sample through a slower steady-state process driven by a combination of osmosis and capillarity. The dynamics can however be rendered symmetrical between filling and emptying if bubbles pre-exist during emptying, a case that we explore using cycling of the vapor pressure around equilibrium.

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The Stability Limit and other Open Questions on Water at Negative Pressure

Cited by 24 publications

References 100 publications

Anomalies in bulk supercooled water at negative pressure

Anomalies in bulk supercooled water at negative pressure

The effects of ultrasound pressure and temperature fields in millisecond bubble nucleation

How Solutes Modify the Thermodynamics and Dynamics of Filling and Emptying in Extreme Ink-Bottle Pores

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