Supercritical anomalies in liquid ODIC-forming cyclooctanol under the strong electric field

Drozd-Rzoska, Aleksandra; Rzoska, Sylwester J.; Szpakiewicz-Szatan, Aleksander; Starzonek, Szymon; Łoś, Jerzy; Orzechowski, Kazimierz

doi:10.1016/j.molliq.2021.117849

Cited by 9 publications

(18 citation statements)

References 48 publications

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“…In contrast to high-pressure phase of ethanol and β-phase of methanol , dielectric constant of cyclooctanol does not decrease, but slightly increases during freezing of liquid phase 43 . This is accompanied with slight decrease (less than one order) of characteristic frequency of relaxational process 44 . So, this indicates that in contrast to methanol and ethanol, rotation of cyclooctanol molecule in plastic crystal phase is practically free.…”

Section: Discussionmentioning

confidence: 92%

“…It is interesting to compare dielectric response of hindered plastic crystals of ethanol and methanol to that of classical example of plastic crystal monoalcoholcyclooctanol (with entropy of fusion as low as 6.98 J/(K mole) 40 ). Its dielectric properties were investigated in number of works (see e. g. the works [41][42][43][44] ). In contrast to high-pressure phase of ethanol and β-phase of methanol , dielectric constant of cyclooctanol does not decrease, but slightly increases during freezing of liquid phase 43 .…”

Section: Discussionmentioning

confidence: 99%

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Dielectric constant of disordered phases of the smallest monoalcohols : evidence for the hindered plastic crystal phase

Kondrin,

Pronin,

Lebed

et al. 2021

Preprint

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With gradual temperature increase in premelting regions of solid phase of methanol and high pressure phase of ethanol, and using novel procedure of separation of electrode polarization effects, we are able to register the contribution of relaxation process to low-frequency dielectric constant. This contribution is about half the liquid's dielectric constant near temperature of solidification , and is almost an order of magnitude higher than reported earlier for ambient pressure phase of methanol. As opposed to dielectric constant of water at ambient pressure, which does not change much during crystallization, our finding indicates the hindrance of molecule rotation in orientationally disordered phases of monoalcohols. Similar dielectric responses of ambient pressure methanol and high-pressure phase of ethanol imply existence of hindered plastic crystal phase of ethanol (not observed at low pressures). We also have found some dynamic disorder in nominally fully ordered phase of these monoalcohols (α-phase of methanol and low-pressure phase of ethanol), the contribution of this disorder being dependent on external conditions (e.g. temperature), and increasing at approaching the order-disorder transition. On the other hand, the amplitude of dielectric responce in hindered plastic crystal phases is almost independent of temperature.

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Section: Discussionmentioning

confidence: 92%

Section: Discussionmentioning

confidence: 99%

Dielectric constant of disordered phases of the smallest monoalcohols : evidence for the hindered plastic crystal phase

Kondrin,

Pronin,

Lebed

et al. 2021

Preprint

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“…Only recently, the model deriving Eq. ( 4 ) and covering the isotropic liquid phase of liquid crystals and also plastic crystals has been proposed [ 21 ].…”

Section: Critical Phenomena Dielectric Properties and Their Link To B...mentioning

confidence: 99%

Criticality-related fundamental bases for new generations of gas–liquid, liquid–liquid, and liquid (LE) extraction technologies

Rzoska

Drozd-Rzoska

2022

Eur. Phys. J. E

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The report presents experimental results, which can be considered as the reference for innovative generations of supercritical fluids (SCF), liquid–liquid (LL), and liquid (L) extraction technologies. They are related to implementations of Critical Phenomena Physics, for such applications not considered so far. For the gas–liquid critical point, the shift SuperCritical Fluids (SCF) ⇒ SubCritical Fluids, due to the additional exogenic impact of ultrasounds, is indicated. For LL technology, the possibility of increasing process effectiveness when operating near the critical consolute under pressure is indicated. Finally, the discovery of long-range precritical-type changes of dielectric constant in linseed oil, standing even 50 K above the melting temperature, is presented. It suggests that extraction processes linking ‘SCF’ and ‘L’ technologies features and exploring the natural carrier, such as linseed oil, are possible. The report recalls the fundamental base for extraction processes via Kirkwood and Noyes–Whitney relations and presents their implementations to ‘critical conditions,’ including pressure. Graphical abstract

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“…Such a simple description may extend even to a few tens of Kelvins for the mean-field type behavior [17][18][19]. It is worth to recall the case of weakly discontinuous phase transitions, where the singularity is hidden below a discontinuous phase transition temperature (𝑇 𝑚 ), but strong pretransitional anomalies still occurs [16][17][18][19][20][21][22]. One may evoke the pseudospinodal behavior in near-critical liquids or the isotropic mesophase transitions in liquid crystalline (LC) [17][18][19][20] and plastic crystalline (PC) systems [21,22].…”

Section: Introductionmentioning

confidence: 99%

“…They are characterized by discontinuity metric 𝑇 * = 𝑇 𝑚 − 𝑇 𝑠 : ranging from 𝑇 * = 1 − 2 𝐾 for the isotropic liquidnematic transition [17][18][19] to even 𝑇 * ~30𝐾 for transitions in highly ordered mesophases such a smectic E (SmE in LCs) [20] or orientationally disordered crystals (ODIC in PCs) [21,22]. Notably, that the weak discontinuity 𝑇 * = 1 − 2 𝐾, can yield significant uncertainty in describing pretransitional effects if only the nonlinear fitting is required [16].…”

Section: Introductionmentioning

confidence: 99%

New paradigm for configurational entropy in glass-forming systems

Drozd-Rzoska

Rzoska

Starzonek

2022

Sci Rep

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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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Supercritical anomalies in liquid ODIC-forming cyclooctanol under the strong electric field

Cited by 9 publications

References 48 publications

Dielectric constant of disordered phases of the smallest monoalcohols : evidence for the hindered plastic crystal phase

Dielectric constant of disordered phases of the smallest monoalcohols : evidence for the hindered plastic crystal phase

Criticality-related fundamental bases for new generations of gas–liquid, liquid–liquid, and liquid (LE) extraction technologies

New paradigm for configurational entropy in glass-forming systems

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