Calorimetric study of water's two glass transitions in the presence of LiCl

Ruiz, Guadalupe N.; Amann‐Winkel, Katrin; Bove, L. E.; Corti, Horacio R.; Loerting, Thomas

doi:10.1039/c7cp08677f

Cited by 18 publications

(22 citation statements)

References 52 publications

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“…The former value is in agreement with the one published by Amann-Winkel et al (4.8 J K −1 mol −1 ) [14]. Please note that Ruiz et al have observed a spike as part of the glass transition in eHDA [15]. They have suggested the spike to be caused by adiabatic cooling caused by the 25% expansion at the polyamorphic transition.…”

Section: Differential Scanning Calorimetrysupporting

confidence: 91%

“…b Ruiz et al [15] suggested 2.3 AE 0.5 J K −1 mol −1 on the basis of the first plateau in the c p curve that is not observed in Fig. 7.…”

Section: Isotope Effect On δC P and On Timescales Near The Glass Tmentioning

confidence: 92%

“…In pure water, the calorimetric end point of its second glass transition is hard to access because the polyamorphic transition intervenes [14]. A recent study by Ruiz et al [15] shows, however, that the presence of LiCl allows for the observation of the end point before the polyamorphic transition commences. The nature of eHDA above T g is still unclear and contested, so we focus here on resolving the question on the molecular motions taking place at water's recently discovered second glass transition, especially on the question of whether or not a liquid state is attained.…”

Section: A the Glass Transition In Undoped High-density Amorphous Icementioning

confidence: 99%

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Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

et al. 2019

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Based on calorimetry and dielectric spectroscopy, the influence of dopants as well as H/D-isotope substitution on the dynamics and thermodynamics of expanded high-density amorphous ice (eHDA) is studied. We find that dopants do not significantly alter the phase behavior, the dielectric relaxation times, and the calorimetric glass transition of eHDA. These observations starkly contrast those made for crystalline ices such as ice I h , ice V, ice VI, and ice XII, where suitable dopants enhance the dielectric dynamics by several orders of magnitude and can trigger hydrogen order-disorder transitions, then taking place below the orientational glass transition temperature of undoped samples. This conspicuous contrast to the behavior of crystalline ices strongly argues against point-defect dynamics in amorphous ices and against a previously suggested "crystallinelike" nature of the amorphous ices. Furthermore, H/D substitution also does not affect the calorimetric glass transition in eHDA much, whereas for crystalline ices, the heat capacity increase at the glass transition is roughly halved. In addition, the H/D-isotope shift of the glass transition onset is much larger for crystalline ices than it is for amorphous ices. This observation favors the notion of eHDA's glass transition as a glass-to-liquid transition and is evidence against a mere molecular-reorientation unfreezing at water's second glass transition. Comparing the isotope effect on activation energies for dielectric relaxation with ice V suggests that in amorphous ice water molecules move translationally above T g. Thus, the present work strongly supports that above this glass transition, water does indeed exist in its contested high-density liquid state.

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Section: Differential Scanning Calorimetrysupporting

confidence: 91%

“…b Ruiz et al [15] suggested 2.3 AE 0.5 J K −1 mol −1 on the basis of the first plateau in the c p curve that is not observed in Fig. 7.…”

Section: Isotope Effect On δC P and On Timescales Near The Glass Tmentioning

confidence: 92%

Section: A the Glass Transition In Undoped High-density Amorphous Icementioning

confidence: 99%

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Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

et al. 2019

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“…20 The presence of inorganic salts offers an attractive route to studying the amorphous forms of aqueous solutions, as, compared to pure water, these salts lower the homogeneous crystallization temperature and (at high concentrations) increase the glass transition temperature; thus, the ice crystallization is often suppressed. 6,[21][22][23] All alkali chloride solutions nevertheless exhibit a non-glass forming region, where standard cooling rates of up to about 1000 K min −1 are not sufficient to facilitate vitrification. [23][24][25] Such a scheme usually accompanies dilute solutions, the ones far below the eutectic concentration.…”

Section: Introductionmentioning

confidence: 99%

Vitrification and increase of basicity in between ice Ih crystals in rapidly frozen dilute NaCl aqueous solutions

Imrichová

Veselý

Gasser

et al. 2019

The Journal of Chemical Physics

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The freezing of ionic aqueous solutions is common in both nature and human-conducted cryopreservation. The cooling rate and the dimensions constraining the solution are known to fundamentally influence the physicochemical characteristics of the sample, including the extent of vitrification, morphology, and distribution of ions. The presence of some salts in an aqueous solution often suppresses the ice crystallization, allowing bulk vitrification during relatively slow cooling. Such a process, however, does not occur in NaCl solutions, previously observed to vitrify only under hyperquenching and/or in sub-micrometric confinements. This work demonstrates that, at freezing rates of ≥100 K min −1 , crystallized ice I h expels the freeze-concentrated solution onto the surfaces of the crystals, forming lamellae and veins to produce glass, besides eutectic crystallization. The vitrification covers (6.8% ± 0.6%) and (17.9% ± 1.5%) of the total eutectic content in 0.06M and 3.4 mM solutions, respectively. The vitrified solution shows a glass-to-liquid transition succeeded by cold crystallization of NaCl ⋅ 2H 2 O during heating via differential scanning calorimetry. We establish that ice crystallization is accompanied by increased basicity in freeze-concentrated solutions, reflecting preferential incorporation of chloride anions over sodium cations into the ice. After the sample is heated above the glass transition temperature, the acidity gradually returns towards the original value. The morphology of the samples is visualized with an environmental scanning electron microscope. Generally, the method of vitrifying the freeze-concentrated solution in between the ice I h crystals via fast cooling can be considered a facile route towards information on vitrified solutions.

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“…Although there is supporting evidence for polymorphism in water (1)(2)(3)(4)(5)12), the debate is still continuing for LLT in real water because of the experimental difficulty in accessing it in pure water (recent efforts to access LLT of pure water from the low-temperature side) (4,(13)(14)(15)(16)(17). There have also been efforts to access LLT of water by using aqueous solutions (18)(19)(20)(21)(22)(23)), yet which is often controversial. Thus, an unambiguous example of LLT is highly desirable for establishing its presence firmly.…”

mentioning

confidence: 99%

Link between molecular mobility and order parameter during liquid–liquid transition of a molecular liquid

Murata

Tanaka

2019

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

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Liquid-liquid transition (LLT) is the transformation of one liquid to another via first-order phase transition. For example, LLT in a molecular liquid, triphenyl phosphite, is macroscopically the transformation from liquid I in a supercooled state to liquid II in a glassy state. Reflecting the transformation from the liquid to glassy state, the LLT is accompanied by considerable slowing down of overall molecular dynamics, but little is known about how this proceeds at a molecular level coupled with the evolution of the order parameter. We report such information by performing time-resolved simultaneous measurements of dielectric spectroscopy and phase contrast microscopy/Raman spectroscopy by using a dielectric cell with transparent electrodes. We find that the temporal change in molecular mobility crucially depends on whether LLT is nucleation growth type occurring in the metastable state or SD type occurring in the unstable state. Furthermore, our results suggest that the molecular mobility is controlled by the local order parameter: more specifically, the local activation energy of molecular rotation is controlled by the local fraction of locally favored structures formed in the liquid. Our study sheds light on the temporal change in the molecular dynamics during LLT and its link to the order parameter evolution.liquid-liquid transition | phase ordering dynamics | order parameter | local molecular dynamics | dielectric relaxation Significance Contrary to a common sense that a liquid state is unique for a pure system, there have been a number of indications for the presence of more than two liquid states. The transition between the liquid states is called "liquid-liquid transition." There has so far been little information on how local molecular dynamics changes during the transformation. Here, we reveal the correlation between the order parameter and molecular dynamics by real-time dielectric spectroscopy measurements during the transformation from liquid I to liquid II in a molecular liquid, triphenyl phosphite. Our results suggest that the local order parameter controls local dynamics. Our finding sheds light on the nature of liquid-liquid transition from a perspective of molecular-level dynamics.

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Calorimetric study of water's two glass transitions in the presence of LiCl

Abstract: Based on calorimetric data we show that water's two distinct glass transitions can be accessed up to the endpoint in dilute LiCl solutions. By contrast, in pure water both endpoints are masked.

Cited by 18 publications

References 52 publications

Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

Nature of Water’s Second Glass Transition Elucidated by Doping and Isotope Substitution Experiments

Vitrification and increase of basicity in between ice Ih crystals in rapidly frozen dilute NaCl aqueous solutions

Link between molecular mobility and order parameter during liquid–liquid transition of a molecular liquid

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