P R E P R I N T ICPWS XV Berlin, September 811, 2008

Experimental investigations of superheated and supercooled water (Review of papers of the school of the academician V. P. Skripov)
V. G. Baidakov E-mail: Baidakov@itp.uran.ru The review presents the results of experimental investigations of nucleation in superheated light and heavy water in the range of nucleation rates from 104 to 1029 s-1m-3. A study is performed of the kinetics of crystallization of droplets of superheated water and amorphous water layers. Measurements have been made of the density, sound velocity, dielectric constant of light and heavy water in the vicinity of the phase equilibrium line with deep entry into the region of metastable (superheated) states. The local and integral characteristics of streams of boiling-up water flowing out into the atmosphere through a short channel have been investigated. One can see the determining role of a vapor phase in such a process at a temperature above 0.9Tc , where Tc is the temperature at the critical point.

Introduction Water is the most widespread liquid on our planet. Phase transitions in water are often accompanied by a considerable deviation from equilibrium conditions, with one of the phases being in the metastable state. Examples of metastable states of water are superheated and supercooled water. In nature high water superheats are observed in geysers and active volcanoes and supercoolings in atmospheric phenomena. The development of new technologies is almost always connected with the intensification of processes. If a process is accompanied by a phase transition, an inevitable concomitant of intensification is the metastability of one or several phases. The control of such a process presupposes a sufficient knowledge of the phenomenon of phase metastability. In developing powerful steam turbines it is necessary to reckon with the initiation of a supersaturation surge in the running-water part of the low-pressure stages, and in development of pumps with the phenomenon of liquid cavitation. Steam generators of atomic power plants should have a sufficient margin of stability with respect to boiling crisis, but at the same time operate in a regime of very intense heat exchange.

A supercooled liquid poses its own problems. The interest in nucleation under considerable supercoolings has appreciably increased in connection with problems of obtaining new noncrystalline materials by the methods of rapid melt cooling. Thus, the problems of the kinetics of nucleation under considerable supercoolings border with the technological problems of production and thermal stability of new materials (amorphous films, ultradisperse systems). The existence of metastable states is caused by the activation character of the initial stage of a firstorder phase transition. Homogeneous nucleation determines the upper boundary of the liquid superheat and supercooling. The appearance of a viable new-phase nucleus in a metastable liquid is connected with the performance of the work W* determined by the height of the thermodynamic potential barrier, which is to be overcome for the subsequent irreversible growth of a new phase. The dimensionless complex W* / k B T , where k B is the Boltzmann constant and T is the temperature, is the stability measure of the metastable phase [1]. In homogeneous nucleation the work W* is performed at the cost of fluctuations. In this sense homogeneous nucleation is a fluctuation process. For a nucleus that consists of n 10 2 103 mole-

cules the magnitude of W* / k B T is equal to several tens of unities, and the spontaneous process of nucleation at an appropriate supersaturation proceeds with an appreciable rate J . The work W* may be related to the probability of fluctuation nucleation and the nucleation rate. For the stationary nucleation rate we have [2] J = B exp ( W* / k B T ) . (1) Here is the number of molecules in a unit volume of the metastable phase, B is the kinetic factor determining the rate of the nucleus transition through the critical size. A check of the validity of the main result of the homogeneous nucleation theory (Eq. (1)) presupposes an experimental study of the behavior of J (T , p) in a wide range of temperature T and pressure p . It can be done by using different techniques. As shown below, for water a range of J from 104 to 1029 s-1m-3 can be spanned in such a way. The investigation of liquids in the metastable state is not limited by homogeneous nucleation. The allowance for metastability in engineering practice requires extending the existing tables (banks) of data on thermophysical properties of liquids to the region of metastable states. For solving this problem it was first of all necessary to ascertain the very possibility of measuring quasi-statically (irrespective of the systems history) the properties of a metastable system. On this way V. P. Skripov [3] formulated the notion of a well-defined metastability. This term presupposes a system with unremoved metastability, but relaxed with respect to all other motions. The condition of a well-defined metastable state is fulfillment of the requirement i l 2 / Di t x , (2) where l is the characteristic linear dimension of the system, Di is the kinetic coefficient for relaxation of the i -th type, t x is the characteristic time of

The fact of a very abrupt increase in the nucleation rate J under changes of temperature and pressure established in homogeneous nucleation theory and confirmed by experiment makes it possible to realize the shock regime of phase transition, when boiling or crystallization on heterogeneous centres gives a weak and blurred signal against the background of a powerful burst of evaporation or crystallization caused by homogeneous nucleation. The conception of a system strong response to the boiling-up of a liquid in the shock regime proves to be useful in solving problems characterized by high rates of changes in the liquid state (laser heating, depressurization of a hot liquid, rapid melt cooling, etc.). As any limiting case, this approach has its field of application; in particular, it proves to be very efficient in describing high-speed flows of boiling-up liquids [4]. The paper presents the results of experimental investigations of nucleation, thermophysical properties and processes in superheated and supercooled water. This work was initiated and performed for a number of years under the guidance of the academician V. P. Skripov at first at the Department of Molecular Physics of the Ural Polytechnical Institute, and then at the Institute of Thermal Physics of the Ural Branch of the Russian Academy of Sciences.
Nucleation in Superheated Water

expectation of decay of the metastable phase. Choosing the characteristic time of experiment texp < t x , one can study thermodynamic and kinetic properties of a metastable system in the pure state. The results of investigating thermodynamic properties make it possible to approximate a spinodal, which is determined by the conditions p T (3) = 0. =0, s p v T Here v is volume, s is entropy. The spinodal is not connected directly with nucleation and is the limit of stability of the metastable phase against infinitesimal changes in the state variables.
2

Experimental investigations of the kinetics of stationary nucleation presuppose the determination of the rate J as a function of temperature and pressure. Information on the nucleation rate may be obtained from data on distribution functions and moments of appearance of the first critical nucleus. It requires repeated experiments with one sample or measurements with a system of equivalent samples. In studying the kinetics of spontaneous boilingup of superheated water use was made of the method of measuring the lifetime (quasi-static method) and the method of pulse superheat of a liquid on a thin platinum wire (dynamic method). In the method of measuring the lifetime the liquid under investigation was contained in a thermostatted tube (with volumes V 50 150 mm3) and transferred to the metastable state by a pressure release to a given value of p [5]. Measurements were made of temperature, pressure and the time of the liquid stay in the superheated state. The results of 30100 measurements of were used to determine the mean lifetime related to nucleation by the relation J = ( V ) 1 . The method of measur-

ing the lifetime covers a range of J from 104 to 109 s-1m-3.

lg J 8 1 2 3 4

J = J (T ) does not depend on the degree of asso-

6 5 5 6 7

4 510

520

530

540

550

T, K

Figure 1: Temperature dependence of the nucleation rate in superheated light (1 p = 0.1 MPa, 2 1.0, 3 2.0, 4 3.3) and heavy (5 p = 0.1 MPa, 6 1.1, 7

2.1) water [5, 6]. Investigation of nucleation in superheated light and heavy water in quasi-static conditions [5, 16] has revealed their anomalous behavior, which is manifested in the fact that superheat temperatures achieved in experiments at different pressures have proved to be much lower than theoretical ones, and the character of the dependence J ( p, T ) is different from other, for instance cryogenic, liquids [7]. Light water was superheated in tubes of optical quartz or pyrex glass. Experiments were made in the pressure ranges 0.13.3 MPa (H2O) and 0.12.1 MPa (D2O) at nucleation rates 3 104 5 108 s-1m-3. On experimental isobars (Fig. 1) there are no flattened sections and sections with curvature of different sign characteristic of other liquids [2, 7]. The maximum value of an experimental temperature of superheat in light water at atmospheric pressure is 521.4 K, which is 55 K lower than the theoretical value. For heavy water these values are 531.4 K and 44 K, respectively. With increasing pressure, discrepancies between theory and experiment decrease, which is mainly connected with a decrease in the dimensions of the metastable region. For the elucidation of the reasons for the anomalous water behavior a study was made of nucleation in superheated hydrogen-bonded liquids with different energies of hydrogen bonds and different bond characters (ammonia, Freons F-11, F21, F-113) [8]. The energy of hydrogen bonds in ammonia is comparable with the energy of hydrogen bonds in water. Freon F-21 forms considerably weaker hydrogen bonds. Freons F-11 and F-113 do not form such bonds. It has been found that in all the liquids listed the kind of kinetic curves 3

ciativity of a substance and is close to those observed for ordinary liquids [2, 7]. The sections of the kinetic curves corresponding to spontaneous boiling-up within 0.21.5 K coincide with those calculated by the homogeneous nucleation theory. Thus, the ability of a substance to form hydrogen bonds is not a sufficient condition for the anomalous behavior of the stability of a superheated liquid, as it is in the case of water. Water is very aggressive and destroys the surfaces of practically all glasses, including pyrex and quartz. Surface defects may be variously shaped and, accordingly, may variously reduce the work of nucleus formation. In a capillary of molybdenum glass, which is the least tolerant of water, n-hexane was superheated at atmospheric pressure. A superheat temperature Ts = 453.4 K was obtained. The theoretical value of Ts is equal to 453.9 K. Then the kinetics of spontaneous boiling-up of superheated water was studied in this capillary. In the course of an experiment the capillary surface was destroyed. The experiment was stopped when the capillary surface became mat. The average size of defects was 5 107 m. Nevertheless, for water the superheat temperature achieved was Ts = 521 K, the same as in quartz and pyrex capillaries with a smooth surface. The radius of a water critical bubble at this temperature is equal to 1.4 108 m. At last n-hexane was superheated in the capillary again and, as before, the temperature obtained was Ts = 453.4 K, to which corresponds a criticalbubble radius of 5.8 10 9 m. If the reason for the premature boiling-up of water were surface defects, it would be impossible to superheat n-hexane above 428 K. Therefore, it is not defects that cause the premature boiling-up of water. To achieve high nucleation rates in superheated water, use was made of pulse methods [9]. In heating a liquid at a rate of 105108 K/s a thin platinum wire was used as a heater and temperature-sensitive element. The wire was included in a special metering circuit and heated by a current pulse. When the liquid in the wall boundary layer was heated to a certain temperature Ts , its explosive boiling-up was observed. An electric signal of explosive boiling-up, based on the solution of the corresponding thermophysical problem, made it possible to determine the nucleation rate. The temperature of the wire heater surface was determined in synchrony with it. This method allowed one measuring the water superheat temperature in the range of nucleation rates from 10191029 s-1m-3.

In experiments on pulse water superheat on a thin platinum wire it has been established that the shock boiling-up regime, when the determining
lg J 26
-1 -2 -3 -4 -5

can observe a change in the slope of the dependence Ts ( p) ( J = const ) in passing from positive to negative pressures [13] (Fig. 3). It is
T, K C

600

16

500 -1 -2 -3 400
565 575 585 T, K

-10

10

20 p, MPa

Figure 2: Temperature dependence of the nucleation rate in superheated water at atmospheric pressure. Data of dynamic experiments: 1 [12], 2 [9], 3 [9], 4 [10], 5 [11]. The solid line shows calculation by homogeneous nucleation theory.

contribution to evaporation is made by centres of fluctuation nature, is realized at heating rates above 107 K/s [10-12]. In experiments with other liquids a heating rate of 105 K/s will suffice to achieve the shock regime [9]. In the case of pulse water superheat the agreement between theory and experiment improves with increasing pressure in the liquid and recorded nucleation rate (Fig. 2). In the region of negative pressures water also behaves anomalously with respect to superheat [13]. A negative pressure in water was created when a short compression wave ( 3 s ) was reflected from a free liquid surface. The compression wave was formed by a duralumin membrane during a discharge of a low-inductance capacitor onto a flat coil pressed to the membrane. A platinum wire heated by a current pulse was immersed in the liquid. The pressure pulse and the heating pulse were reconciled in time in such a way as to make the moment of the liquid boiling-up on the wire coincide with the passage through it of the maximum negative-pressure pulse. Nucleation rates of 1024 1026 s-1m-3 were realized in the experiments. Experimental investigations of limiting superheats of organic liquids in the region of positive and negative pressures have shown that the limiting superheat boundary passes continuously from the region of positive into the region of negative pressures and is close to that calculated by homogeneous nucleation theory [14]. In the case of water one 4

Figure 3: Boundary of limiting superheats of water and solutions of acetone with water: 1 water, 2 water + 5 % acetone, 3 water + 15 % acetone. Solid line line of liquidvapor phase equilibrium, critical point, dashed line -- calculation by homogeneous nucleation theory for J = 1024 s-1m-3 (water) [15].

shown that additions of ethanol to water smooth out the dependence Ts ( p) , increasing the cavitation strength of water at high negative pressures. On dissolving acetone in water the temperature of the water superheat decreases. So does the slope of the curves Ts ( p ) in the region of negative pressures.
T, K

500

400

-1 -2 -3

-10

-5

p, MPa 10

Figure 4: Boundary of limiting superheats of acetone and water solutions in acetone: 1 acetone, 2 acetone + 10 % water, 3 acetone + 30 % water. Solid line line of liquidacetone vapor phase equilibrium, critical point, dashed line - calculation by homogeneous nucleation theory for J = 1024 s-1m-3 (acetone) [15].

For pure acetone a smooth extension of the curve Ts ( p ) from the region of positive into the

region of negative pressures is observed (Fig. 4). However, at stretches exceeding 4.0 MPa the experimental curve deviates from the theoretical line. Additions of water into acetone flatten the dependence Ts ( p ) , increasing the temperature of the acetone limiting superheat at high negative pressures. The dependence Ts ( p) becomes similar to the dependence Ts ( p) for normal liquids and agrees well with homogeneous nucleation theory. The courses of the curves Ts ( p) described are observed up to a volume concentration of water of about 60 %, which is close to the azeotropic composition of a solution [15].
Spontaneous Crystallization of Supercooled Water

the nucleation rate increased 10 times when the temperature decreased by 0.8 K. The effective value of the surface tension calculated from experimental data is l = 28.7 mN/m2, and the value of the preexponential factor B = 1037 1 s-1m-3 is close to the theoretical evaluation by (1) for homogeneous nucleation ( B = 1036 s-1m-3). Experiments in the regime of continuous cooling [17] give additional arguments in favor of the homogeneous mechanism of crystal nucleation of supercooled water. The half-width of the temperature distribution of crystallization events has proved to be equal to 0.85 0.10 , which is in good agreement with the expected value T1/ 2 = 0.8 for homogeneous nucleation. In conditions of high viscosity of the metastable phase the time of establishment of a stationary concentration of nuclei becomes longer. The process of non-stationary nucleation may be characterized by the stationary nucleation rate J and the lag time 0 . Non-stationary nucleation shows up in the crystallization of amorphous layers of water. The crystallization of such layers proceeds during continuous heating or an isothermal allowance after a stepwise rise in the temperature. Amorphous layers of light and heavy water 50500 m thick were obtained by condensation of vapor in vacuum on a copper substrate cooled by liquid nitrogen [18]. The condensation rate was 50500 m/hour. Crystallization was detected by the method of differential-thermal analysis. In experiments with amorphous layer of light and heavy water for the same heating rate the position of the abrupt temperature jump pointing to the sample crystallization was independent within 0.5 K of both the thickness of the sample and the condensation rate in the process of its preparation. In heating amorphous layers of water at a rate of 0.25 K/s crystallization took place at T* 166 [18]. Experimental data on the sample heating rate T and the crystallization temperature corresponding to it T* , and also the fraction X = 0.1 of the crystallized substance referred to it, made it possible to evaluate the activation energy, E . On calculating it one can evaluate the stationary nucleation rate J , the lag time 0 at different crystallization temperatures of amorphous layers [16, 19]. Fig. 5 gives temperature dependences of the stationary nucleation rate for supercooled and heavy water under crystallization of amorphous layers (dots on the low-temperature branch of the dome of J (T ) ).

Considerable supercoolings are realized in small liquid drops [16]. Water drops from 500 to 20 m in diameter in oil were located on the junction of a differential thermocouple. Every drop was melted down and crystallized several tens of times. Measurements at the same temperature were made on 510 drops similar in size. The distribution of crystallization events of isolated drops was studied in repeated experiments under isothermal conditions and continuous supercooling [16].
J, s m
-1 -3

1 1020 2

1015

1010

105

160

200

240 T, K

Figure 5: Temperature dependence of the nucleation rate of crystals in light (1) and heavy (2) water. Dots on the low-temperature branch of the curve data on crystallization of amorphous layers [18, 19], on the high temperature-branch crystallization of droplets [17]. Solid line calculation by homogeneous nucleation theory.

Experimental results obtained in isothermal conditions for light and heavy water are presented in Fig. 5. For light water they cover a range of nucleation rates of 5 orders in the interval of supercoolings from 33.9 to 37.8 K [17]. In this interval 5

Thermophysical Properties and the Spinodal of Superheated Water

The thermodynamic interpretation of first-order phase transitions assumes that the thermodynamic potentials of each of the phases exist on either side of the phase-equilibrium line, and this line is in no way distinguished for the potentials of each of the phases. At the same time the appearance of a growth channel for pre-critical nuclei in the metastable phase makes the analyticity of a thermodynamic potential on the phase-equilibrium line nonobvious. The uncertainty arises because the system is essentially relaxing. Evaluations show that at W* / k BT > 18 the uncertainty is small as compared with the level of thermal fluctuations, which allows one to speak about the uniqueness of extension of the substance properties deep beyond the phase equilibrium line into the metastable region [20]. The method of a piezometer of variable volume in glass cells has been used to measure the density of superheated light and heavy water [21, 22]. Experimental data have been obtained in the range of temperatures (0.7 0.95)Tc and pressures from the saturation line to those close to the boundary of spontaneous boiling-up.
V 10
3

are essentially nonlinear, isochores are close to straight lines in the metastable region up to the critical point. The sound velocity ( f = 1 3 MHz) in superheated ordinary and heavy water was measured by the pulse method [23]. A liquid was superheated in a glass acoustic cell of volume 3 cm3. Measurements were made along isotherms. The entry into a metastable region was realized by a pressure release. The depth of the entry into a metastable region was limited by the action of the radiation background and easily activated boiling sites. A water superheat was accompanied by a decrease in the sound velocity (an increase in the adiabatic compressibility). Values of the sound velocity on the binodal and the line of attainable superheat ( J = 105 s-1m-3, T = const ) differ on average by 812 %. The static dielectric constant of superheated water was measured by the relative noncontact bridge method [24]. The glass measuring cell was relieved of pressure. Measurements were made in the range from 423 to 573 K along isotherms with an interval of 10 K. Within the measurement error the static dielectric constant of superheated water remains unchanged along the isotherms. Experimental data on thermodynamic properties of water in the stable and the metastable states make it possible to approximate the spinodal. An empirical equation of state is set up with the use of p , , T data and data on the sound velocity or isochoric heat capacity. The spinodal is found by its simultaneous solution with Equation (3).
p, MPa C 20 ps -1 -2

3 -1

m .kg

ps 11 pn 9 8 10

1.4

1.3
6 5 4

1.2

3 2 1

10

1.1

p, MPa

Figure 6: Water isotherms: 1 T = 452.2 K, 2 474.2, 3 493.6, 4 507.8, 5 520.8, 6 533.4, 7 542.7, 8 552.6, 9 560.6, 10 567.9, 11 572.5. ps saturation line, pn line of attainable superheats

400

500

600

T, K

-10

[21]. Fig. 6 presents water isotherms. From experimental data follows the smoothness of extension of isotherms, isochores, isobars from the stable into the metastable region and the absence of singularities, at least for the first two derivatives of the thermodynamic potential, on the phase-equilibrium line. As distinct from isotherms and isobars, which 6

Figure 7: Spinodal of superheated liquid water: solid line by the empirical equation of state [21], 1 by Frth equation [20], 2 by Gimpan equation [20]. ps satu-

ration line, critical point. The validity of the international equation of state for water has been confirmed [21, 22] (in an accessible region of metastable states) for the

subregion 1 [25]. The results of several means of finding the water spinodal are compared in Fig. 7. Data obtained by the empirical and by the international equation of state are closely analogous and on the scale of Fig. 7 coincide.
Flows of Boiling-up Water

T > 0.9Tc (flow-rate crisis) [28]. The jet shape

beyond the channel changes essentially depending on the value of the liquid superheat. The bar form of the jet gives way to the conic, parabolic (with a large angle of opening at the outlet section), gas one (at T / Tc > 1 ). Water at T / Tc < 0.9 is characterized by anomalously high nucleation rates as compared with most organic liquids. This affects the jet form. In experiments with water a complete jet opening ( 1800 ) was observed even at T / Tc 0.75 , whereas in n-pentane it happened only at T / Tc 0.9 . The flow instability shows up at high liquid superheats. A jet may be entrapped by the wall of the channel superimposed flange and spread out in the plane perpendicular to the direction of its motion [29] (the Coanda effect [30]). The force of the jet recoil R acting on a chamber with a liquid increases with saturation pressure in the chamber, but on attaining conditions of explosive boiling-up and a jet collapse (spread along the surface of the operating chamber) the value of R decreases (Fig. 8).
R, N

Jets of a boiling-up liquid may originate in an emergency in various thermal-power and chemical machines. The consequences of an accident with local depressurization of a high-pressure pipeline (vessel) are affected by diverse factors, for instance, the flow rate of a heat-transfer agent, the jet form and its dynamic reaction to the construction elements. An experimental study of jets of boiling-up water has been made on a setup of short-term action, which ensures a stationary regime of an outflow from a high-pressure chamber into the atmosphere for 510 s [26]. The initial state ( p0 , T0 ) of water in the chamber varied along the saturation line from T = 200 0 to temperatures close to Tc and isobars. Considerable water superheats in a flow were ensured by the use of short channels d / l 1 ( d is the diameter of a cylindrical channel, l is its length), in which high rates of pressure decrease are realized (of the order of 106 MPa/s). The main results of these investigations are reduced to the following. A thermodynamically nonequilibrium flow of a boiling-up liquid is realized in a short channel. Owing to the delay in boiling-up and the short time of the liquid stay within the channel the mass flow rate during the outflow into the atmosphere may be twice the equilibrium flow rate [27]. For a wide range of superheated states T 0.9Tc , 0 < p < ps the liquid in the channel remains practically in a one-phase state. Here for describing the outflow use may be made of the approximation of the ideal incompressible liquid, and the flow rate may be calculated by the Bernoulli formula. Homogeneous nucleation theory predicts quite low values of the nucleation rate at low and moderate superheats ( J 1 ) and an extremely high intensity and rate of increase in J for positive pressures at temperatures T > 0.9Tc . The high intensity, and above all, the extremely strong dependence of J on p and T lead to an abrupt increase in the local vapor content in the flow and a rapid decrease in the velocity of propagation of small perturbations upstream to values of the order of the outflow velocity. This results in a crisis of the outflow regime. It leads to a channel choking and an abrupt decrease in the liquid flow rate at 7

1.5

1.0

0.5

0.0

8 , MPa

Figure 8: Dependence of the reactive force of a superheated-water jet on the initial pressure corresponding to the saturation line [29]. Solid line calculation for the hydraulic regime of outflow of a onephase (non-boiling-up) liquid.

In the process of observing jets of boiling-up water not only were characteristic jet shapes under certain superheats established, but considerable fluctuations of the flow parameters were noted as well. In particular, noticeable fluctuations were observed in the angle of opening of the jet cone and the local density of the outgoing two-phase medium. The method of photometry of laser radiation was used to study spectral characteristics of the fluctuation phenomena in different regimes of boiling-up of water jets. For the bar shape of a jet (with boiling-up on isolated centres in the flow) the frequency distribution of the intensity of fluctuations

corresponded to white noise. For the conic jet shape (intense volume boiling-up on heterogeneous centres) in a region of low frequencies the spectral density of the power of fluctuations had a dependence inversely proportional to frequency (flicker or 1/ f noise). When the homogeneous mechanism of evaporation was realized in a water jet ( T / Tc 0.9 ), the frequency interval of flicker noise widened [29].
Conclusion

layers of light and heavy water there forms a mixture of hexagonal and cubic ice.
lg30 J 20 10 0 -10 -20 1 3'' 100 200 300 400 T, K 500 600 0 -1 -2 3' 3 2
3 T .10 , MPa
-1 -3

2 Stable states Tsp 1

Water is a peculiar liquid in many respects. Metastable water is not an exception. Unlike all liquids investigated at present, water cannot be superheated in quasi-static experiments to the point of spontaneous boiling-up, in dynamic experiments the value of the water superheat decreases abruptly in passing from the region of positive into the region of negative pressures. At the same time in experiments on water supercooling in drops and warming of amorphous layers crystallization proceeds quite analogously to other molecular liquids. It may be suggested that in superheated water there are some specific centres which initiate water boiling-up, but they do not affect its stability against crystallization. Experimental investigations of thermophysical properties of superheated water do not reveal any peculiarities in their behavior. However, it should be borne in mind that by now measurements of properties of metastable water have been made in a very narrow range of state variables. In quasi-static experiments a deep entry into the metastable region of water was hindered by a great number of easily activated boiling sites. Dynamic experiments cannot as yet ensure an acceptable accuracy of measurement of thermophysical properties of metastable liquids. For slightly metastable states of superheated water no problems arise in describing its thermophysical properties. They differ little from properties on the saturation line. But a problem will arise at the approach of the spinodal, when isothermal compressibility, thermal expansion and isobaric heat capacity tend to infinity. Water in the supercooled state has been studied less thoroughly than in the superheated one. Experimental data mainly refer to pressures close to atmospheric. Ice exists in different crystalline forms, and the water phase diagram has an elaborate form if one does not restrict oneself to the region of low pressures ( p < 200 MPa). The polymorphism of ice may manifest itself at a low pressure too. It has been found that during crystallization of amorphous 8

Figure 9: Temperature ranges of states of stable, superheated and supercooled water at atmospheric pressure. Stationary homogeneous nucleation rate during crystallization (1) and boiling-up (2). Inverse isothermal compressibility for stable and metastable states of water (3) in the absence of the spinodal in a supercooled liquid (3) and in the case of its presence according to [33] (3), Tsp

the temperature of the spinodal of a superheated liquid. Indicated in Fig. 9 are temperature ranges of supercooled, stable and superheated water at atmospheric pressure [31]. Ibidem one can see curves representing the temperature dependence of the logarithm of the homogeneous nucleation rate for crystallization (curve 1) and boiling-up (curve 2). The maximum rate of formation of vapor nuclei is attained at the approach of the spinodal determined by condition (3). Fig. 9 also shows how the inverse isothermal compressibility 1 = v(p / v) changes with temperature (curve T 3). An arrow shows the temperature of the spinodal of superheated water. In considering the kinetics of crystallization of supercooled water and representing the domelike curve 1 for the crystallization rate we left aside the question of the spinodal of supercooled liquid. If such a spinodal exists, it means that, at least, a part of curve 1 (on the left) does not conform to the actual possibility of nucleation in a homogeneous system. The decrease of the inverse isothermal compressibility of water with a temperature decrease below 319 K is interpreted by the authors [32, 33] as a trace of thermodynamic singularity at 228 K (curve 3). However, it does not agree with the liquid capacity for much greater supercoolings

established by experiment. There is another viewpoint on the stability of a supercooled liquid [34], according to which the region of metastable states of a one-component liquid does not pass into a labile region with decreasing temperature. A supercooled liquid has no spinodal determined by condition (3). V. P. Skripov thought that at T = 228 there was no divergence of T , c p of supercooled water, but there was a sufficiently blurred and small normal maximum. The dashed line 3 (Fig. 9) corresponds to this point of view. The work has been done with a financial support of a project by the Programme of integrated investigations of the Ural and Far Eastern Branches of the Russian Academy of Sciences, grant of the President of Russia Leading Scientific Schools 2999.2008.8.
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