THE JOURNAL OF CHEMICAL PHYSICS 122, 064507 2005

Stability limits in binary uids mixtures

Attila R. Imre
KFKI Atomic Energy Research Institute, H-1525 Budapest, P.O. Box 49, Hungary

Thomas Kraskaa
Department of Physical Chemistry, University Cologne, Luxemburger Strasse 116, D-50939 Kln, Germany

Received 7 September 2004; accepted 17 November 2004; published online 2 February 2005 The stability limits in binary uid mixtures are investigated on the basis of the global phase diagram approach employing a model for the attracting hard-sphere uid. In addition to the diffusion spinodals the mechanical spinodals are included. As a result one nds topologically different types of the diffusion spinodals while only one shape exists for the mechanical spinodals which are present in the region of liquid-vapor equilibria only. The diffusion spinodals represent the underlying properties of the phase behavior. The types of stable phase behavior therefore resemble that of the spinodal behavior. The different shapes of the spinodals can be important for nonequilibrium processes in nature and technology. 2005 American Institute of Physics. DOI: 10.1063/1.1847651
I. INTRODUCTION

Besides the stable homogeneous liquid and gas phases uids can also exist under metastable condition.1 The borderline between stable and metastable states at positive pressure is the coexistence or saturation curve. A part of the metastable region of the liquid phase is located at negative pressures14 Fig. 1 . The metastable region is limited by another curve called spinodal separating the metastable states from the unstable region in which states cannot exist. As a limit of the metastable region the spinodal also reaches negative pressure on the liquid side. Hence, if a liquid is isotropically stretched it is transferred into a metastable state either at positive or negative pressure. By overheating only the metastable region at positive pressure can be reached. In experiments one can usually not reach the spinodal but a socalled attainable stability limits, also called homogeneous nucleation limit.1,5 The presence of a heterogeneous nucleus such as an impurity lowers the critical work of the formation of a vapor nucleus and therefore leads to a phase separation at lower supersaturation. A vapor can be transferred into a metastable state by undercooling or pressurizing. The metastable region of the vapor phase also has a limiting spinodal which is entirely located at positive pressures. The vapor and the liquid spinodal meet continuously at the critical point in the p and T projections. This is the only point in the phase diagram where the spinodal touches the stable region. Hence, it is the only point at which the diverging density uctuations at the spinodal reach the stable region of the phase diagram. All other points of the spinodal are screened from the stable gas- or liquid-phase regions by metastable regions as shown in Fig. 1. In the pressure-temperature pT projection the two branches of the spinodal meet in a cusp at the critical point. Some similarities exist for the behavior close to a critical point and close to a spinodal such as the diverging compressa

Electronic mail: t.kraska@uni-koeln.de

ibility and isobaric heat capacity. However, other properties such as the exponents of the powers laws differ when approaching the critical point and the spinodal.5 For pure substances two topologically different liquidvapor spinodal types are discussed which are marked as type A and B in Fig. 1 a .4 The difference between types A and B is the existence of a minimum in type B. Since the experimental determination of the spinodals is difcult and only possible by extrapolation,6 the spinodals of real materials are not well known. The three best known systems are water and the two isotopes of the helium. The spinodals of the helium 3 and helium 4 are type B and type A, respectively, while for water it is still under discussion whether it is type A or B.1,4,7,8 In binary liquid mixtures not only liquid-vapor LV but also liquid-liquid LL phase transition can take place. Therefore, it is also possible to reach a metastable liquid state by crossing the LL coexistence curve. The limit of such metastable liquid is a LL spinodal. When reaching the LL spinodal the system immediately splits into two liquid phases with different compositions. Although experimentally the spinodal cannot be reached or jumped over, due to the slow kinetics of phase separation, in some systems one can observe the so-called spinodal decomposition. Such jump can be done by changing the temperature in a very fast manner or changing the pressure which can be faster and easier for LL phase separation than for LV phase separations.9 A jump into the nonstable region can lead to two different structures which are nucleation-and-growth type or spinodal type. The nucleation-and-growth type of phase separation happens in the metastable region and forms islands of the new phase in the mother phase. At the spinodal the phase separation is spontaneous and happens immediately within the whole body of liquid leading to two bicontinuous, spongelike phase.1 Although these structures disappear quickly, it is possible to follow LV phase separations using very fast photographic technique.10 In case of LL phase separations
2005 American Institute of Physics

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FIG. 1. Schematic sketch of the vapor-liquid phase diagram of a pure substance in a pT projection and b p projection. a Dotted, vapor pressure curves; dashed, different types of spinodals; and lled circle, liquid-vapor critical point. b Solid, coexistence curve; long dashed, mechanical spinodal; and short dashed, isotherm.

pressure.14,2125 For this kind of extrapolation the knowledge of the spinodals is crucial, because extrapolating beyond the spinodal would yield articial results.25 While there are several investigations of the stability limits in pure substances experimentally and theoretically5,26 there is yet no thorough investigation on the stability limits in binary uid mixtures. For such study the systematic behavior of the global phase diagram approach is very useful. The global phase behavior of binary uid mixtures has been investigated over the last decades in a general fashion2732 as well as applied to specic problems and phenomena in phase behavior.3336 In such investigations usually only the stable parts of the phase diagram are considered. In some cases nonstable parts are included such as metastable and unstable parts of a critical curve.31,36,37 Although there are studies about the LV spinodal of pure liquids and some more about the LL spinodal of binary liquids, the relative position and topology of LL and LV spinodals in binary mixtures has been rarely studied.1,38,39 In this work we study systematically the spinodals exemplary for attracting hard-sphere uid binary mixtures.
II. METHOD

the two different topologies, nucleation-and-growth type, and spinodal decomposition type can be long lasting, especially when very high molecular weight components are involved. There are processes such as membrane production or phase separation in polymer blends in which the partly phaseseparated liquid is further cooled down until one or both phases solidify. In this way the initial structure can be frozen, leading to different mechanical behavior of the solid. Hence, the morphology and properties of the composite material strongly depends on the type of the phase transition. Therefore, the knowledge of the location of the spinodal is crucial for the understanding and prediction of the properties of new materials. Furthermore, there are a lot of important liquid mixtures including binary ones which can be temporarily in metastable condition at which the physical and chemical properties can change very fast. Stretched binary liquids at absolute negative pressure can easily split into two liquid phases which can cause changes in the viscosity and several other properties abruptly. Prominent examples for multicomponents uid are biological uids such as blood or sap, crude oil or aqueous solutions in soil. Blood or other body uids can be in metastable state locally when they are exposed to medical ultrasound see Ref. 4 and references therein . Sap is under moderate negative pressure down to 4 bar in the xylem,11 crude oil can experience negative pressure during ow or sudden decompression,12 while aqueous solutions can be under deep negative pressure 100 MPa in the capillaries of the soil.13,14 Miscibility measurements as well as other measurements of other properties under metastable conditions are very difcult.1520 Therefore, methods have been developed in which properties measured at positive pressure are extrapolated into the region of negative

The conditions for the stability of phases can be obtained from the second law of thermodynamics saying that a closed system is stable if the entropy is at its maximum value. From the second-order variation of the entropy with respect to the volume, the condition for the mechanical stability limit, the mechanical spinodal, can be obtained:1,38,40 p V pV = 0.
T

A phase is mechanically stable for pV 0 and mechanically unstable for pV 0. This is the case for pure substances and, in principle, also for mixtures. Integration of Eq. 1 gives 2 A / V2 T A2V = 0. The mechanical spinodal is therefore given on the liquid side by the minima and on the gas side by the maxima of an isothermal van der Waals loop Fig. 1 b . As the maximum and the minimum approach each other with increasing temperature and eventually coincide, the spinodal goes through the critical point Fig. 1 b . In binary uid mixture phase separation usually leads to two phases with different mole fraction with exception of azeotropy. The second-order variation of the entropy with respect to the mole fraction in a closed system gives the thermodynamic condition of the diffusion spinodal in mixtures:1,38,40
2

Gm x2

G2x = 0.
p,T

In analogy to the extrema of the van der Waals loop for the mechanical spinodal the diffusion spinodal is given by the extrema of the chemical potentials of the two compounds as function of the mole fraction. At the diffusion spinodal the mole fraction exhibits diverging uctuations. In pure substances only LV equilibria exist. In mixtures there is the possibility either for LL or LV phase separations. Although thermodynamically there is no difference between these two

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cases, i.e., Eq. 2 always holds, experimentally the difference can be crucial. While in LL phase transitions the volume of the new phases is in the same order of magnitude as that of the original supersaturated phase, in case of LV transition the volume of the vapor phase can be orders of magnitudes larger. While Eq. 1 can be easily applied to an equation of state, Eq. 2 has to be rewritten in terms of the Helmholtz energy A by Jacobi transformation: G2x = A2x
2 AVx = 0. A2V

The abbreviations of the derivatives in general are given41 by n+k A / Vn xk T AnVkx. All other natural variables of the functions are kept constant at differentiation. The Helmholtz energy can be calculated from the equation of state by integration as for the residual part: Ares = presdV. 4

FIG. 2. a Type I phase behavior in a pressure-temperature projection for = 0, = 0.2, and = 0.1. Solid curve, binary vapor-liquid critical curve; long-dashed curves, diffusion spinodal isopleths; short-dashed curves, mechanical spinodal isopleths; dotted line, pseudocritical curve; and dotdashed, pure substance vapor pressure curves. b The same phase diagram in pressure-mole fraction diagram. The numbers mark different T / Tc1 values.

After adding the ideal mixing term one can compute the mechanical and the diffusion spinodal for a given equation of state. The calculations here are performed for the attracting hard-sphere uid modeled by the Carnahan-Starling-van der Waals equation of state:42 RT 1 + y + y 2 y 3 a p= 2. 3 Vm 1y Vm 5

a=
i j

xix jaij ,

b=
i j

xix jbij .

10

Here a is the attraction parameter and y = b / 4Vm the packing fraction with the covolume parameter b. The choice of this equation is twofold: rst it is a simple and good description the attracting hard-sphere model uid, second the global phase behavior of this equation is very well investigated.32,43,44 The latter point makes it possible to locate easily the different types of stable phase behavior in terms of the global parameters , , and . These global parameters are reduced differences of the equation of state parameters a and b, = b22 b11 , b22 + b11 a11 2 b11 , a11 2 b11 6

III. RESULTS

The diffusion and the mechanical spinodals are calculated by the computer algebra program MAPLE Ref. 45 with a code developed for this investigation. Although the mechanical spinodal is hidden behind the diffusion spinodal in mixtures, its location in phase space can be important because it inuences the magnitude of the density uctuation in the system at a metastable state point. A third type of spinodal, the isentropic spinodal, is not considered here. In an recent investigation of pure substances26 the isentropic spinodal has been located far below the mechanical spinodal and therefore its inuence on the metastable region is expected to be negligible.
A. Type I phase behavior

a22 2 b22 = a22 2 + b22

a22 a12 a11 + 2 2 2 b11b22 b11 b . = 22 a22 a11 + 2 2 b22 b11

The parameters of the mixture are calculated from the corresponding parameters of the pure substances aii, bii and the cross-interaction parameters a12, b12 by the one-uid mixing theory with quadratic mixing rule

In order to analyze the spinodal behavior we start with the simplest possible binary system, the type I system in the classication of van Konynenburg and Scott.27,28 In such systems the critical points of the pure substances are connected by a continuous binary liquid-gas critical curve. Besides this critical curve there are no further critical curves. Such system can be obtained with the parameter set = 0.2, = 0.1, and = 0.0 as shown in Fig. 2. One can see in Fig. 2 b that in the limits of the pure substances the mechanical and the diffusion spinodal approach each other. In case of equal covolumes = 0.0 the cusps of the mechanical spinodal in the pT projection form a straight line connecting the critical points of the pure substances Fig. 2 a , dotted line . In the px projection shown in Fig. 2 b it appears as a continuous curve.

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J. Chem. Phys. 122, 064507 2005

FIG. 3. Schematic vapor-liquid phase diagram with the coexistence curve solid , the mechanical spinodal short dashed , and the diffusion spinodal long dashed . The arrows symbolize a jump into the two-phase region from the vapor or the liquid phase. In all cases rst the diffusion spinodal is reached. The pressure-temperature diagram on the left side corresponds to one of the pure substances with x = 0. Here the vapor pressure curve solid curve of the pure substance and the mechanical spinodals short dashed are plotted.

VL spinodal . The liquid part can be approached only coming for the liquid side and vice versa as indicated by the arrows in Fig. 3. When jumping into the two-phase region by pressure increase from the vapor phase or pressure decrease from the liquid phase one eventually reaches the diffusion spinodal. Figure 3 also shows that a spinodal can be located in the one-phase region in such diagram, for example, the gas-phase spinodal in the liquid phase region. This may appear unusual but makes sense because the spinodals belong to the mother phase on the other side of the corresponding branch of the coexistence curve. The limit of both, the diffusion and the mechanical spinodal for vanishing mole fraction is the pressure of mechanical spinodal of the pure substance at given temperature. This is shown in the left diagram in Fig. 3. The fact that the spinodals can be located outside the vapor-liquid coexistence region is inseparably related to this limiting behavior.
B. Type II phase behavior

Along this curve also A3V = 0 holds, which corresponds to the pure substance critical condition. Therefore it is occasionally called pseudocritical curve. It is a straight line in the pT projection because the critical conditions for pure substances A2V = A3V = 0 give Tc = 0.3773 a / Rb and pc = 0.070669 a / b2 for the CarnahanStarlingvan der Waals equation. Here Tc and pc both depend linearly on the attraction parameter a x which is the only mole fraction dependence in case of equal sized molecules. Therefore the pseudocritical curve is a linear interpolation of the pure critical points in the pT projection. It should be emphasized that the pseudocritical curve is by no means a real critical curve. The binary critical curve is rather located on the surface to the diffusion spinodal surface in pTx space. In Fig. 2 one can see that for a jump from the stable gas phase into the nonstable region one rst reaches the diffusion spinodal. The mechanical spinodal is located behind the diffusion spinodal. It follows that the vapor-liquid phase transition in binary mixtures is dominated by concentration uctuations and the system is decomposed already before at the diffusion spinodal. The same can be observed for a jump from the liquid phase into the two-phase region. This is in agreement with inspection of Eq. 3 which shows that rst G2x and than A2V vanishes.46 For a mechanically stable phase A2V is positive and because of the square the complete sec2 ond term of Eq. 3 AVx / A2V is positive. It follows that for vanishing G2x the rst of term Eq. 3 A2x has to be positive as well. At the mechanical spinodal A2V vanishes and hence G2x diverges to minus innity. Therefore, vanishing G2x requires positive A2V and hence rst the diffusion spinodal and then the mechanical spinodal is reached. In Fig. 3 a schematic sketch of an isothermal vapor-liquid equilibrium including the spinodals is shown. The chosen temperature is between the critical temperatures of the pure substances. The diffusion spinodal long dashed touches the binodal solid at the binary critical point. The mechanical spinodal short dashed is in this case present only in the lower part of the phase equilibrium. Half of the diffusion spinodal belongs to the liquid phase LV spinodal; from the bottom-left corner to the critical point ; the other half belongs to the vapor phase

After having analyzed a type I liquid-vapor system the next step is to turn to a system with a liquid-liquid immiscibility. Type II is such system. In Fig. 4 different projections of a type II system as calculated with Eq. 5 for the global parameters = 0, = 0.396, and = 0.005 are plotted. In Fig. 4 a the pT projection of the binary critical curve is shown. One can see a type I VL critical curve and in addition a LL critical curve at low temperatures. At high pressure the LL critical curve goes to innite pressure within a uid model, however, it is terminated by solidication in real systems. In some cases this LL branch of the critical curve behaves monotonously in the pT projection, in other cases it can exhibit a temperature minimum.36 At low pressure the LL-critical curve goes trough a minimum to a cusp in the pT projection. This cusp is the stability limit of the critical curve G4x = 0 and hence the remaining branch of the LL-critical curve going to negative pressure is an unstable critical curve. While a normal phase becomes unstable at G2x = 0 a critical phase becomes unstable at G4x = 0. Somewhere, typically below and close to the vapor pressure curve of the more volatile substance a critical endpoint separates the stable and the metastable branch of the LL-critical curve. In the px projections in Figs. 4 a and 4 c as well as in the pTx diagram in Fig. 4 e one can recognize that the cusp of the LL-critical curve in the pT projection is actually a continuous curve. Figure 4 e also shows that in case of type II the diffusion spinodals have an additional branch going to high pressure. Together with the spinodal branches known from type I the diffusion spinodal isopleths form a &-like shape in the constant mole fraction section. Further analysis shows that the high pressure spinodal is also present in type I systems but located at negative absolute temperature which is of course outside the physical meaningful range in these systems. When varying the molecular parameters the high pressure branch of the spinodals can move to positive temperature which results in the appearance of the LL-critical curve. This appearance corresponds to the hypothetical transition from type I to type II which is called zero-Kelvin transition.47 At this transition the system has a LL critical curve at zero

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branch of the LL-critical curve, the maximum at higher pressure is a stable VL critical point, and the minimum is a point on the unstable branch of the LL-critical curve. These three points are marked by symbols in Fig. 4 b and by a dotdashed line in Fig. 4 d . At slightly higher temperature below T / Tc1 = 1.07 the maximum and minimum corresponding to the unstable and metastable LL-critical points meet and the diffusion spinodal exhibits a saddle point. This saddle point corresponds to the cusp of the LL-critical curve in the pT projection with G4x = 0 connecting the metastable and unstable branch of the critical curve. In Fig. 4 c spinodals at lower temperature are shown. The spinodals are similar as for T / Tc1 = 1 Fig. 4 a but exhibit a pronounced maximum at high pressure corresponding to a stable LL-critical point. For T / Tc1 = 0.5 the extrema are marked by symbols in Fig. 4 c and as well as by a dot-dashed line in Fig. 4 d .
C. Type V phase behavior

FIG. 4. Type II spinodal isotherms calculated for = 0, = 0.396, and = 0.005. a High temperature isotherms; b enlargement of the region near the critical point of the more volatile substance; c low temperature isotherms; and d pT projection. Legend as for Fig. 3. The numbers mark different T / Tc1 values. The dot-dashed lines at T / Tc1 = 0.5 and 1.03 in d correspond to the diffusion spinodal isotherms plotted as bold dashed curves in b and c . e Three dimensiona1 plot: bold solid curve, critical curve; light solid curves, diffusion spinodal isopleths; and dashed curves, mechanical spinodal isopleths.

Kelvin, an approach which neglects of course the solidication. In the isothermal sections at high temperature such as T / Tc1 = 2.0 the diffusion spinodals behave as in type I systems shown in Fig. 4 a . With decreasing temperature the spinodals in the isothermal section undergo a topological transition. At T / Tc1 = 1.03 close to the critical temperature of the more volatile substance Fig. 4 b , the looplike topology of the LV diffusion spinodals has changed to a curve with two maxima and one minimum. These extrema of the isothermal diffusion spinodal are points on the critical curves: the maximum at lower pressure is a critical point on the metastable

Type V phase behavior consists of a LV-critical curve which is interrupted by a LLV three-phase curve as shown schematically in Fig. 5 d . The calculations for = 0, = 0.5, and = 0.2 shown in Fig. 5 a indicate that the spinodals at high temperature are similar to the ones of type I. At T / Tc1 = 1 the diffusion spinodal has a topologically similar shape as at higher temperature but the maximum is more pronounced. Therefore, the mechanical spinodal is at much lower pressure than the diffusion spinodal compared to the type I phase diagram described above. This distance between mechanical and diffusion spinodal, which is also present for the type II phase diagram, appears to be typical for LL equilibria. The appearance of such LL type diffusion spinodal corresponds to the LL type critical curve of type V at T / Tc1 1. The maximum is maintained with decreasing temperature. Furthermore, an additional minimum at high mole fraction becomes visible, for example, at T / Tc1 = 0.8 in Fig. 5 c . These two extrema coincide in a saddle point at negative pressure corresponding to a cusp in the critical curve G4x = 0 in the pT projection at which the metastable and unstable branches meet. In Fig. 5 d the situation corresponding to T / Tc1 = 0.8 is shown schematically. In Fig. 5 b the region close to the critical point of the more volatile substance is enlarged. At T / Tc1 = 1.01 one can recognize one minimum corresponding to the unstable branch of the critical curve and a maximum corresponding to the very short LV-critical branch connected to the critical point of the more volatile substance Fig. 5 d . At T / Tc1 = 1.03 these two extrema have vanished and hence the cusp of the critical curve is located between T / Tc1 = 1.01 marked by a dot-dashed line in Fig. 5 d and T / Tc1 = 1.03.
D. Type III phase behavior

In type III systems the LV-critical curve starting at the critical point of the less volatile substance is continuously connected to the LL-critical curve going to high pressure. The critical curve is monotonously going to high pressure, i.e., there is no pressure minimum or maximum.32 Figure 6 a shows the spinodals of such system = 0, = 0.45, and = 0.1 which are at high temperature as T / Tc1 = 2.0 also

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J. Chem. Phys. 122, 064507 2005

FIG. 6. Type III phase behavior calculated for = 0, = 0.45, and = 0.1. a Diffusion and mechanical spinodal isotherms in the low pressure region. b Diffusion spinodal isotherms in the high pressure region. Legend as for Fig. 3. The numbers mark different T / Tc1 values.

below with a maximum. Since these extrema correspond to LL-critical points the LL-critical curve exhibits a critical temperature minimum between T / Tc1 = 1.28 and T / Tc1 = 1.29. The topology of this transition resembles that of the binodals at a critical temperature minimum.48
E. Type IIIm phase behavior

FIG. 5. Type V phase behavior calculated for = 0, = 0.5, and = 0.2. a High temperature diffusion and mechanical spinodal isotherms. b Enlargement of the region near the critical point of the more volatile substance. The bold dashed curve calculated for T / Tc1 = 1.01 shows the existence of three extrema of the diffusion spinodal isotherm together with a maximum at higher pressure not shown in this scale . c Low temperature diffusion and mechanical spinodal isotherms. The minimum of the diffusion spinodal isotherms close to x = 1 corresponds to the unstable branch of the critical curve. Legend as for Fig. 3. The numbers mark different T / Tc1 values. d Schematic sketch of the pT diagram of this system. The dot-dashed lines mark the isothermal sections shown in b and c .

Type IIIm phase behavior is similar to that of type III but the critical curve exhibits a pressure minimum and a maximum in Fig. 7 b . In Fig. 7 a some diffusion spinodal isotherms are shown for a type IIIm phase diagram near the region of the critical point of the more volatile substance = 0, = 0.4, and = 0.05 . At T / Tc1 = 1.05 and T / Tc1 = 1.1 one can recognize two maxima and one minimum which are marked by symbols for T / Tc1 = 1.1. The maximum at low pressure and the minimum has vanished for T / Tc1 = 1.2

similar to those of type I. With decreasing temperature, but still above the critical temperature of the less volatile substance, the diffusion spinodal forms a pronounced maximum at high pressure corresponding to a LL-critical point. The continuous appearance of the LL type spinodal represents the continuous transition from LV to LL phase equilibria. At T / Tc1 = 1 the spinodals reach the critical point of the less volatile substance in a cusp as for the other types of phase behavior mentioned above. This diffusion spinodal is not continuously connected to the less volatile substance. It rather diverges to innite pressure coming from both pure substances. Figure 6 b shows how the spinodals behave at high pressure. At T / Tc1 = 1.28 the spinodals go to high pressure as for T / Tc1 = 1, while at T / Tc1 = 1.29 they consist of two parts, one at high pressure with a minimum and one

FIG. 7. a Type IIIm phase behavior calculated for = 0, = 0.4, and = 0.05. The three squares mark the extrema of the diffusion spinodal isotherm at T / Tc1 = 1.1. Legend as for Fig. 3. The numbers mark different T / Tc1 values. b Corresponding pT diagram. Solid curves, critical curves; and dashed curves, vapor pressure curves of the pure substances. The isotherm at T / Tc1 = 1.1 marks a section shown in a .

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FIG. 8. Type VII phase behavior calculated for = 0, = 0.42, and = 0.019. a High temperature diffusion spinodal isotherms. The numbers mark different T / Tc1 values. b Low temperature diffusion spinodal isotherms. Legend as for Fig. 3.

which means that the cusp formed by the unstable critical curve and the short critical curve connected to the critical point of the more volatile substance is passed. The maximum at high pressure corresponds to the stable LL-critical curve.
F. Types VI and VII phase behavior

FIG. 9. a Diffusion spinodals for a phase diagram in the shield region calculated for = 0, = 0.02, and = 0.35. b Corresponding pT diagram. Symbols, binary critical points forming the critical curves; and dashed curves, vapor pressure curves of the pure substances. The isotherms at T / Tc1 = 0.8, 0.85, and 0.9 mark the sections shown in a .

The high temperature part of the type VII hase behavior shown in Fig. 8 a for = 0, = 0.42, and = 0.019 resembles that of type V discussed above. In addition type VII systems have a LL closed loop critical curve. Type VI phase behavior is similar to type VII but with a continuous LVcritical curve as in type I. Therefore, it is not discussed here separately. It has been shown32 and conrmed several times44,49 that Eq. 5 is able to generate such closed loop phase behavior, however, at very low temperature. Experimentally LL closed loop phase behavior have been found for water containing systems.50,51 Figure 8 b shows the spinodals corresponding to a LL equilibria at low temperature calculated with Eq. 5 . One can see a sequence of LL diffusion spinodals forming the closed-loop dome. At these temperatures the mechanical spinodal is at very large negative pressure not shown here which indicates that this diffusion spinodal is LL type, being far away from the mechanical spinodal.
G. Phase behavior in the shield region

x = 0 and x = 1. At higher pressure a spinodal related to a LL equilibria with a LL-critical point at the minimum exists. With decreasing temperature these three spinodals intersect in two steps. First the LV spinodal at low mole fraction intersects with the LL spinodal as one can see in Fig. 9 a for T / Tc1 = 0.85. For lower temperatures the VL spinodal at high mole fractions joins the remaining part of the LV spinodal at low mole fraction. These two branches do not form a cusp at T / Tc1 = 0.85 as Fig. 9 a suggests. Actually both have a continuous maximum being LV-critical points. At T / Tc1 = 0.8 the system has already passed the second transition. One diffusion spinodal connects the pure substance spinodals continuously while the diffusion spinodals starting at the pure substance spinodal at low pressure go to very high pressure at about x = 0.18 and x = 0.82. The remaining island of the diffusion spinodal between x = 0.4 and 0.6 around p / pc1 = 0.5 is related to partly unstable critical curves G4x 0 as one can see in Fig. 9 b .

IV. CONCLUSIONS

The shield region is a small area in the global phase diagram which exhibits several complex phase diagrams including four-phase equilibria. Here, we have investigated the diffusion spinodals for a system which very close to the symmetric systems at = 0.0. The chosen parameters are = 0, = 0.02, and = 0.35. The diffusion spinodals and the pT projection of this system are shown in Fig. 9 a . Each reduced temperature, for which a diffusion spinodal is calculated in Fig. 9 a is marked by a thin line in Fig. 9 b . The square symbols in Fig. 9 a correspond to the same symbols in Fig. 9 b . At T / Tc1 = 0.9 we nd two spinodals corresponding to LV equilibria ending at the pure substance spinodals at

The spinodals represent the underlying property of a phase diagram. They form planes in pTx space which are envelops of the critical curves. There are a limited number of spinodal shapes such as the LV-type spinodal, the continuous LL spinodal of types II, V, or III or the diverging spinodal of type III at low temperature. The different types of phase behavior as known from the classication of van Konynenburg and Scott further differentiate similar types of spinodal topologies. As expected, the mechanical spinodal shape marked as type B in pure substances Fig. 1 has not been found with the attracting hard-sphere model uid. In case of a LV equilibrium a mechanical spinodal is located near the diffusion spinodal. In case of a LL equilibrium the mechanical spinodal is typically far away from the diffusion spinodal. For type II or III phase behavior the reason for the large

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distance to the mechanical spinodal can be deducted from the pressure-volume sections. A mechanical spinodal requires a van der Waals loop in the pressure-density diagram which is not present at high pressure in these phase diagram types. At low pressure the diffusion spinodal exhibits a pronounced maximum which causes the distance to the mechanical spinodal. The unusual shape of the diffusion spinodal of type II or type IIIm systems in the vicinity of the critical temperature of the more volatile substance is of interest for processes including a supercritical solvent such as carbon dioxide. Carbon dioxide-solute systems are often type II, IV, or III and process conditions a usually slightly above the critical temperature of carbon dioxide. The spinodal isotherm at T / Tc1 = 1.03 in Fig. 4 b showing a type II system has already two maxima and one minimum. However, only one maximum is related to a stable LV-critical point. In Fig. 5 b showing a type V system at T / Tc1 = 1.01 the second maximum has emerged to high pressure and is here a stable LL-critical point. Such type of topology can be found in mixtures of carbon dioxide with certain organic solvents which exhibit a LL immiscibility on top of the LV equilibria. In case of the gas antisolvent crystallization such LL decomposition leads to undesired large agglomerated paracetamol particles rather than ne ones as discussed recently.52 The location of the diffusion spinodal is expected to affect the precipitation process in such cases.
ACKNOWLEDGMENTS

This work was partially supported by the Hungarian Research Fund OTKA under Contract No. T 043042, by a bilateral program of the German Science Foundation DFG and the Hungarian Academy of Science HAS , Grant No. 436 UNG 113/150/n-1. A.R.I. was also supported by the Bolyai Research Fellowship.
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