States of a supersaturated solution in limited-size systems

Fedoseev, V. B.; Fedoseeva, E. N.

doi:10.1134/s0021364013070059

Cited by 19 publications

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“…The method used in this work is based on the microscopic observation of an ensemble of evaporat ing droplets of a solution of nonvolatile compounds and was described in [8,9]. The ensemble of droplets of a diluted solution was deposited by an atomizer on the slide of an MBS 1 microscope.…”

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Solution-crystal-solution oscillatory phase transitions in the KCl-NaCl-H2O system

Fedoseev

Maksimov

2015

Jetp Lett.

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390Microscopic studies of size effects at phase transi tions revealed unusual kinetic features. Under almost stationary conditions, in an ensemble of droplets of an aqueous solution of a mixture of nonvolatile com pounds, multiple repeated processes of evaporationcondensation of droplets of the solution with the for mation of a crystal and subsequent condensation of water on the crystal, which completely recovered the dimensions of droplets, were observed. Solutioncrystal oscillations occurred with a frequency of sev eral oscillations per minute. They were not interrupted until stationary conditions were maintained.The most well known observations of an oscilla tory regime at a phase transition are Liesegang rings described at the end of the 19th century [1]. The first theoretical interpretation of this phenomenon was proposed by Ostwald. The formation of Liesegang ring type structures is usually irreversible in both time and space. A periodic phase transition was described for a lattice model [2]. However, this two dimensional mathematical model is inapplicable to the description of a heterogeneous three component system and can not describe mass transfer between three phases.Pulsations of the temperature and pressure at the evaporation of sessile droplets were described in [3]. The effect appeared in multicomponent, unlimitedly mutual soluble mixtures of volatile components (water-ethanol-methanol). A theoretical interpreta tion proposed by the authors of that work is based on the description of a diffusive water flux through the interface between phases at a given temperature drop with the imposition of a pulsation. The chemical ¶ See the supplemental materials to this article at the website www.jetpletters.ac.ru potentials of the components of the imperfect solution are determined by the concentrations of all sub stances. This relation (equations of state) usually has a quite complex form. Diffuse fluxes generated by the difference between chemical potentials in a real solu tion also depend on the concentrations of all compo nents. This possibly explains why oscillations were observed experimentally only in multicomponent sys tems.The oscillatory regime of nucleation of droplets was observed in counterpropagating fluxes of vapors and falling droplets [4]. In this case, oscillations occur not with individual droplets, but at the condensation of supersaturated vapor.Oscillations described in [3,4] have a common nature with phenomena observed in our experiments. Oscillations occur owing to diffusive fluxes at the interface between phases, where one of the phases is far from the state of an ideal solution.Phase transitions discussed in this work occur under almost stationary conditions and are accompa nied by reversible condensation: evaporation of the liquid phase with simultaneous condensation-solu tion of the crystal phase. The mass of the system changes significantly at multiple transitions from the "crystal" state to the "crystal + solution" state and back in observed oscillations. As far as we know, such a ...

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Solution-crystal-solution oscillatory phase transitions in the KCl-NaCl-H2O system

Fedoseev

Maksimov

2015

Jetp Lett.

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“…Растворимость NaCl в рассматриваемых условиях практически не зависит от температуры [10], поэтому в качестве дополнительного приближения примем, что концентрация раствора в объеме капли в присутствии кристалла сопоставима с концентрацией x s насыщенного раствора и постоянна x = x s = const при L = 0. Это приближение пренебрегает массопереносом внутри капли и тем, что концентрация насыщенного раствора при малых объемах зависит от радиуса капли [8].…”

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“…При испарении зарождение кристаллической фазы происходит при достижении некоторого пересыщения (x > x s ). Степень пересыщения обычно имеет стохастический характер и зависит от размера капли [8].…”

Section: особенности испарения и роста капель раствора содержащих крunclassified

“…После этого при испарении радиус кривизны R d возрастает до ∞ при L ≈ const, и на поверхности кристалла образуется пленка раствора. Если давление во внешней сре-Осциллирующие фазовые переходы раствор -газ и раствор -кристалл 205 де ниже, чем давление в точке B, испарение будет продолжаться с понижением давления пара над каплей (точка С на рисунке 5) путем образования островковых пленок и повышения концентрации в них за счет повышения растворимости, описанного в [8]. Состояние несферических капель (точка С на рисунке 5) показано схематически.…”

Section: особенности испарения и роста капель раствора содержащих крunclassified

“…Возможность достижения необходимого пересыщения показана экспериментально в [7]. В [8] описаны некоторые термодинамические аспекты, связанные с энергией образования и размерами критического зародыша новой фазы при уменьшении объема системы.…”

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States of a supersaturated solution in limited-size systems

Cited by 19 publications

References 10 publications

Solution-crystal-solution oscillatory phase transitions in the KCl-NaCl-H2O system

Solution-crystal-solution oscillatory phase transitions in the KCl-NaCl-H2O system

Solution – gas and solution – crystal oscillatory phase transitions in the drops of aqueous solutions with one crystallizable component

Formation of BI- and Polymodal Distributions and the Non-Ostwald Behavior of Disperse Systems

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