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Chapter 5 Fluid Phase Equilibria of Binary Mixtures

Considerable progress (Sadus, 1992) has been achieved in the application of theory to the calculation of binary mixture phase equilibria. The importance of vapourliquid equilibria and liquid-liquid equilibria to many industrial processes provides a considerable incentive to improve the quality of phase equilibria prediction.

Historically, the prediction of phase transitions has relied on empirical methods, but more realistic equations of state (Chapter 3) are being developed that attempt to account for the various aspects of intermolecular interactions. Some of these equations have been applied successfully to the prediction of phase equilibria (Chapter 3). In this Chapter, we will apply the van der Waals, Guggenheim (1965) and Heilig-Franck (1989) equations of state to binary mixtures containing ammonia, water and helium. The unlike interaction parameter for binary mixtures are obtained by comparing experimental critical data with calculations using the equations of state. These interaction parameters and equations of state are used to predict a priori both the vapour-liquid and liquid-liquid equilibria. The predicted critical properties and binodal phase diagrams are compared with experimental data for a wide range of pressure, temperature and composition.

5.1 Classification of Fluid Phase Behaviour of Binary Mixtures Before presenting our results, we first discuss the classification of fluid phase behaviour of binary mixtures. General classification of fluid phase equilibria was given by Van Konynenburg and Scott (1980). Based on the p-T projections of the critical curves and the van der Waals equation of state, Van Konynenburg and Scott (1980) classified the phase behaviour of critical curves in binary mixtures into six types. It is presented in Fig 5.1. Type I and Type II behaviour are very similar. In both cases, a continuous gas-liquid line is observed linking the critical points of the two pure components. The difference between Type I and Type II is obscured by solidification at low temperatures where Type II mixtures exhibit a liquid-liquid critical line. For Type III to Type V mixtures, the critical curve is separated into two or more parts. These branches of the critical curve can no longer be clearly identified as being vapour-liquid or liquid-liquid. A more extensive commentary on the phase behaviour classification of

____________________________________________________________________________________ 120

binary mixtures can be found in several reviews, e.g., Schneider (1978, 1991), Rowlinson and Swinton (1982), McGlashan (1985), Young (1986), Sadus (1992) and De Loos (1994). A brief summary of their classification of the phase diagrams is given here. Each type of phase behaviour will be illustrated with one or more examples of binary mixtures. A detailed overview of experimentally determined critical data for binary systems can be found in the work of Hicks and Young (1975) and Sadus (1992). 5.1.1. Type I phase behaviour

In a Type I system only one critical curve is found, that is the liquid-vapour critical curve. It starts from the critical point of component 1 and runs continuously to the critical point of component 2. Type I behaviour occurs in binary mixtures with components of similar chemical types and/or components with critical properties of comparable magnitude. Typical examples are argon + krypton (Schouten et al., 1975), methane + ethane (Wichterle and Kobayashi, 1972), methane + nitrogen (Stryjek et al., 1974) and carbon dioxide + oxygen (Booth and Carter, 1930; Zenner and Dana, 1963; Muirbrook and Prausnitz, 1965). Carbon dioxide + ethylene (Rowlison et al., 1958) and carbon dioxide + benzene (Hicks and Young, 1975) are also examples of Type I.

5.1.2. Type II phase behaviour Type II behaviour has a continuous liquid-vapour critical curve which links component 1 and component 2, just as in the case of Type I. In addition, at low temperatures Type II mixtures show a liquid-liquid critical line which rapidly rises to high pressures from an upper critical end point (UCEP) on the end of a three-phase liquid-liquid-gas line. If not interrupted by the formation of a solid phase, this liquidliquid critical curve runs to infinite pressures. Generally the liquid-liquid critical curve in Type II behaviour has one of the three shapes shown in Fig. 5.2. In Type IIa, the liquid-liquid critical curve has a negative slope whereas Type IIb has a positive slope in the p-T projection. In Type IIc, the critical curve has a negative slope in the UCEP and changes via a temperature minimum to a liquid critical curve with a positive slope at higher pressures.

____________________________________________________________________________________ 121

Fig. 5.1 Classification of the phase behaviour of binary mixtures with respect to different critical phenomena. The lines denoted 1 and 2 are the vapour pressure curves of the two components which end at a gas-liquid critical point (c). The remaining lines represent critical phenomena with the exception of three-phase equilibria which are denoted by a broken line.

____________________________________________________________________________________ 122

Fig. 5.2 Three possible types of critical curves in Type II mixtures.

Type II behaviour has been one of the most extensively studies. For example , water + phenol (Roth, et al., 1966) and acetic acid + triethylamine (Rowlinson and Swinton, 1982) etc exhibit Type II phase behaviour. Hicks and Young (1975) have compiled the gas-liquid critical properties of about 600, mainly Type II binary mixtures. Brunner (1988a) reported that Type II behaviour was found in binary mixtures of ammonia + the n-alkanes from ethane to octadecane (see section 5.3.1).

5.1.3. Type III phase behaviour There are two distinct critical curves in Type III phase behaviour. One critical curve starts from the critical point of the component with the higher critical temperature and usually extends part of the way to the critical point of the other component, but then turns sharply to high pressure. We call this curve as the first branch. The other critical curve starts from the other component with the lower critical temperature and extends until an UCEP is reached on the end of a three-phase line. We call this curve as the second branch. There are various sub-classes of Type III behaviour, depending on the positions of the main critical locus. Generally, for the first branch there are five possible kinds of Type III behaviour showed in Fig. 5.3. In Type IIIA, the critical curve starts from the

____________________________________________________________________________________ 123

critical point of the component with the higher critical temperature, runs to direction of the critical point of the another component, passes through a pressure maximum and a pressure minimum, and goes to very high pressure. This kind of the critical curve can also be a temperature minimum combined with a pressure minimum and a pressure maximum. For Type IIIB, the critical curve can have a negative slope whereas Type IIIE can have a positive slope without a pressure maximum and/or a temperature minimum in the p-T projection. That is, the critical curve in Type IIIB extends to lower temperature whereas the critical curve in Type IIIE extends directly to greater temperature. In Type IIIC behaviour, the critical curve only has a temperature minimum without a pressure minimum and a pressure maximum. Type IIID is also possible, the critical curve starts from the critical point of the component with the higher critical temperature and near vertically rises to very high pressure.

Fig. 5.3 Four possible types of critical curve in Type III mixtures.

For the curve C and E types of systems, since two-phase equilibria can exist at higher temperatures than the critical temperature of the less volatile component these equilibria are often referred to as gas-gas equilibria (Schneider, 1978). The system with

____________________________________________________________________________________ 124

curve C is said to show gas-gas equilibria of the second kind (called Type IIIb behaviour, the critical line passes through a minimum in temperature) and curve E is called gas-gas equilibria of the first kind (Type IIIa behaviour, no minimum critical temperature). Temkin (1959) proposed two simple criteria to predict gas-gas immiscibility of the first kind that are based on the relative magnitude of the van der Waals equation of state parameters. In terms of the critical volume (Vc) and temperature (Tc) of the components, the criteria that must be satisfied to observe Type IIIa behaviour are

c c V11 0 .42V22

(5.1)

c c c c T11V11 < 0.052T 22V 22

(5.2)

where component 2 is the component with the higher critical temperature. Ethane + methanol (Brunner, 1985) is a typical Type III mixture which has a pressure maximum and a pressure minimum in its critical curve that goes to infinite pressure (Fig. 5.3 curve A). A binary mixture that corresponds to curve B in Fig. 5.3 is ethane + nitromethane (Alwani and Schneider, 1976). Binary systems helium + xenon (De Swaan Arons and Diepen, 1966), water + neon (Mather et al., 1993) and water + helium (Sretenskaja et al., 1995) are said to show gas-gas equilibria of the first kind (Fig. 5.3 curve E) and binary mixtures that display gas-gas immiscibility of the second kind (Fig. 5.3 curve C) are water + argon (Tsiklis and Prokhorov, 1966; Lentz and Franck, 1969; Wu et al., 1990), xenon (Franck et al., 1974) or krypton (Mather et al., 1993) and ammonia + methane, argon or nitrogen (Brunner, 1988b). Helium + methane (Sinor et al., 1966, Streett, 1969) was said to corresponds to curve D. Rowlinson and Swinton (1982) illustrated four possible kinds of Type III behaviour similar with Fig. 5.3. Young (1986) showed another four possibilities for Type III behaviour. The three phase line could be at higher or lower pressures that the vapour pressure curve of the pure component. Each of these two cases could have the upper critical end point at a higher or lower temperature than the critical point.

____________________________________________________________________________________ 125

5.1.4 Type IV phase behaviour

In Type IV the three-phase (liquid-liquid-vapour) equilibrium consist of two branches. The low -temperature branch shows an upper critical end point (UCEP) and is comparable with the liquid-liquid-vapour equilibrium found in Type II systems. The high-temperature branch shows a lower critical end point (LCEP) and also an upper critical end point (UCEP) and is comparable with the liquid-liquid-vapour equilibrium found in Type V systems. There are three distinct critical curves in Type IV phase behaviour. One is the liquid-liquid critical line which starts at the UCEP of the lowtemperature branch and moves directly to high pressure. The second line starts at the critical point of the component with lower critical temperature and ends at the UCEP of high-temperature branch. The third line starts at the critical point of the component with higher critical temperature and ends in the LCEP of the high-temperature branch. The systems methane + 1-hexene (Davenport et al., 1966) and carbon dioxide + n-tridecane (Van der Steen, 1989) are examples of the system showing Type IV fluid phase behaviour. 5.1.5. Type V phase behaviour

Type V is similar with Type IV but without the liquid-liquid critical line and three phase (liquid-liquid-vapour) line at lower temperature. Characteristic for this type of phase behaviour is a three-phase equilibrium with a LCEP and an UCEP, and a discontinuous critical curve. The first branch of the critical curve connects the critical point of the more volatile component with the UCEP. The second branch runs from the LCEP to the critical point of the less volatile component. An example of Type V system is methane + n-hexane (Davenport and Rowlinson, 1963).

5.1.6 Type VI phase behaviour

Type VI has a three phase (liquid-liquid-vapour) equilibrium with a LCEP and an UCEP. The LCEP and UCEP are connected by a liquid -liquid critical curve which shows a pressure maximum. Another possibility is the existence of a second liquidliquid critical curve at high pressure with a pressure minimum, shown in Fig. 5.1. This phenomenon is called high pressure immiscibility. Also the low-pressure immiscibility

____________________________________________________________________________________ 126

region and the high-pressure immiscibility region can be combined in one uninterrupted liquid-liquid region. This type of phase behaviour is also characterised by a continuous liquid-vapour critical locus between the critical point of the two pure components. A common example of Type VI phase behaviour can be found in the system water + 2butoxyethanol (Schneider, 1963). In reality, it should be accepted that many mixtures will not fall neatly into one of these categories. This is particularly the case for mixtures exhibiting transitional behaviour between phase behaviour types. There are also some other classifications of binary phase behaviour suggested. Walas (1985) listed seven types of vapour-liquid behaviour according to azeotropic condition. For practical reasons, this classification is less widely used than that of Van Konynenburg and Scott (1980).

5.2 Parameters for Equations of State The Heilig-Franck equation of state uses the Carnahan-Starling (Carnahan and Starling, 1972) representation of repulsive forces between hard-spheres and a squarewell representation for attractive forces. For the reader's convenience, we recall the equation here (further details can be found in Chapter 3).

p=

RT (1 + y + y 2 y 3 ) RTB + 2 3 V (1 y) V (C / B )V

(5.3)

Heilig and Franck (1989) used the following temperature-dependence (Christoforakos and Franck, 1986) for the y term

bc y= 4V

T c T

(5.4)

However, in our work y was made independent of temperature by using z = 0. The B and C terms in Eq.(5.3) represent the attractive contributions from the second and third virial coefficients, respectively, of a hard-sphere fluid interacting via a square-well potential. The second and third virial coefficients for the square-well potential can be

solved exactly (Hirschfelder et al., 1954) for both pure fluid and binary mixtures. The

____________________________________________________________________________________ 127

equations for the virial coefficients used in our work, are given elsewhere (Hirschfelder et al., 1954, Heilig and Franck, 1989, 1990). The square-well potential is characterised by three parameters reflecting intermolecular separation (), intermolecular attraction (/RT) and the relative width of the well ( ). The parameter has a simple relationship to the covolume (b = 2 N3 /3) of the fluid. For a chosen value of , the y and /RT terms for a pure fluid can be obtained by applying the following critical conditions to Eq.(5.3).

p =0 V T

(5.5)

2p 2 =0 V T
The variation of y and /RT with respect to is illustrated in Fig. 5.4.

(5.6)

The critical

compressibility for the Heilig-Franck equation also varies with as is illustrated in Fig. 5.4. Both yc and Zc pass through a minimum whereas the depth of the square well (

/RT c) becomes progressively more shallow as the width () of the well is increased. The data in Fig. 5.4 can be fitted accurately to a polynomial equation. of the polynomial equation are summarised in Table 5.1. The unlike interaction parameters are obtained from ( 11 + 22 ) 2 The coefficients

12 =

(5.7)

12 = 11 22

(5.8)

An adjustable parameter was not required in Eq.(5.8).

It was also that assumed that

= 11 = 22 .

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Table 5.1. Polynomial coefficients with respect to which can be used to calculate the values of Zc, /RT c and yc (obtained by solving the critical conditions of a pure fluid using the Heilig-Franck equation of state with different values)

Degree 0 1 2 3 4 5 6 7 8

Zc 0.351232 -0.00232678 0.00341457 -0.00106934 -0.000111972 0.00101833 5.8582 10-5 -3.86712 10-5 -2.44199 10-5

/RT c 0.618314 -0.436265 0.221563 -0.109645 0.0598004 -0.0344097 -0.0197011 -0.0113773 0.00672555

yc 0.120572 -0.00313519 0.00443753 -0.00149962 -3.43611 10-6 6.64929 10-6 8.13316 10-5 -3.86712 10-5

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3.0 2.5

/RTc

2.0 1.5 1.0 0.5 0.0 1.0 1.5 2.0

2.5

3.0

0.15 0.14

c y

0.13 0.12 0.11 1.0 1.5 2.0

2.5

3.0

0.37

0.36

c Z
0.35 0.34 1.0 1.5 2.0

2.5

3.0

Fig. 5.4.

Variation of /RTc, yc and the critical compressibility factor (ZC ) obtained The

by solving the critical conditions of one-component fluid at different values of . line of best fit was obtained by using the polynomial data in Table 5.1.

____________________________________________________________________________________ 130

____________________________________________________________________________________ 131

5.3 Critical High Pressure Liquid-Liquid Phase Behaviour of Binary Mixtures Containing Ammonia The mixtures containing an alkane and a polar compound are of scientific and industrial interest. They have high evaporation enthalpy, and high critical temperature and pressure. They are models for the thermodynamic treatment of mixtures of components with different polarity, and thus show interesting properties such as positive azeotropy, liquid-liquid phase separation, and large positive excess molar Gibbs energies. Ammonia is a strongly polar fluid that forms hydrogen bonds and is classified along with sulfur dioxide as a solvent with properties similar to those of water. Brunner (1988a and 1988b) has investigated the critical high pressure phase behaviour of binary mixtures containing ammonia and either simple gases or n-alkanes. These mixtures exhibit a limited degree of miscibility manifested by either Type II or Type III behaviour in accordance with the classification scheme of van Konynenbury and Scott (1980). Although some experimental binodal curves (Tsiklis and Rott, 1967) are available, no experimental data were reported for ammonia containing mixtures. So, this section will only deal with critical properties. In this part, the critical properties of binary mixtures of ammonia + n-alkanes and some simple gases will be discussed. The experimental critical curves will be compared with calculations using the van der Waals, Guggenheim (1965) and Helig-Franck (Heilig and Franck, 1989) equations of state.

5.3.1 Ammonia and n -Alkanes Mixtures Brunner (1988a) reported the phase behaviour of binary mixtures of ammonia + the n-alkanes from ethane to octadecane. All the n-alkanes + ammonia mixtures investigated with an alkane carbon number of i = 2 to 18 have an uninterrupted critical curve and a continuous vapour-liquid critical transition occurs between the critical points of the components. At low temperatures, three-phase liquid-liquid-vapour coexistence was detected ending at a liquid-liquid upper critical end point (UCEP). As the temperature increases, a liquid-liquid-critical curve rises rapidly from this point in the direction of high pressures. That is, a locus of upper critical solution temperatures (UCSTs) extends to very high pressures from the UCEP. The phase behaviour of all

____________________________________________________________________________________ 132

these mixtures corresponds to type II phase behaviour according to classification scheme of van Konynenburg and Scott (1980). The comparison of experiment with calculations using the Heilig-Franck, Guggenheim and van der Waals equations of state for the critical liquid-liquid equilibria of the ammonia + n-alkane mixtures is presented in Fig. 5.5 and Fig. 5.6.
30

25

9 10 11 12

14

16

18

20

p/MPa

15

10

CP(NH3 )

0 300 320 340 360 380 400 420

T/K
Fig. 5.5 Comparison of calculations using the Heilig-Franck (__ ) and Guggenheim (

---) equations of state with experiment (; Brunner, 1988a) for the UCST locus of binary ammonia + CnH2n+2 (where n = 2-18) mixtures. The liquid-liquid-vapour line

__ (---) and the vapour-pressure curve ( ) ending at the critical point () of ammonia are l also shown.

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30

25

9 10 11 12

14

16 18

20

p/MPa

15
CP(NH3 )

10

0 300 320 340 360 380 400 420

T/K
Fig. 5.6 Comparison of calculations using the van der Waals (__ ) equation of state with experiment (; Brunner, 1988a) for the UCST locus of binary ammonia + CnH 2n+2 (where n = 2-18) mixtures. The liquid-liquid-vapour line (---) and the vapour-pressure curve (__ ) ending at the critical point (l) of ammonia are also shown.

The exact co-ordinates of the UCEP of a Type II binary mixture cannot be a priori determined by theory. Consequently, the calculations were terminated at the experimental UCEP. The calcula tions were repeated with different values of the adjustable parameters and until the calculated critical locus coincided with the experimental data over the entire pressure range. Values of the best fit interaction parameters for different equations of state are given in Table 5.2. The critical volumes were obtained either from a compilation by Ambrose (1980) or estimated by extrapolation. Calculations for mixtures containing alkanes larger than octadecane were

____________________________________________________________________________________ 134

not attempted because of the unacceptably large uncertainty in the pure component critical properties caused by decomposition. TABLE 5.2. Values of the interaction parameters for the binary ammonia + either nalkane or gas mixtures. = 1.26684 in Heilig-Franck equation of state. _____________________________________________________________________ van der Waals 0.640 0.702 0.704 0.697 0.690 0.680 0.673 0.668 0.663 0.658 0.654 0.650 0.642 0.628 0.625 0.590 0.370 0.550 0.520 0.600 0.595 0.870 0.930 0.920 0.900 0.890 0.880 0.870 0.860 0.850 0.840 0.830 0.821 0.816 0.803 0.800 0.900 1.000 0.900 0.840 0.860 0.930 Guggenheim 0.830 0.819 0.800 0.783 0.780 0.772 0.765 0.758 0.758 0.758 0.758 0.758 0.753 0.744 0.734 1.100 1.790 0.793 0.755 0.840 0.723 0.930 1.005 1.005 0.960 0.870 0.850 0.835 0.825 0.805 0.788 0.772 0.762 0.752 0.752 0.752 0.885 1.030 0.910 0.830 0.840 0.950 Heilig-Franck 0.850 0.840 0.826 0.808 0.792 0.775 0.759 0.745 0.733 0.723 0.715 0.707 0.699 0.689 0.682 1.110 1.900 0.820 0.779 0.870 0.766 0.930 1.005 1.049 1.062 1.067 1.100 1.126 1.144 1.155 1.162 1.160 1.163 1.141 1.133 1.123 0.898 1.020 0.910 0.830 0.840 1.000 ________________ ________________ ________________ n-alkane/gas Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane Tetradecane Hexadecane Octadecane Hydrogen Helium Nitrogen Argon Carbon monoxide Sulphur hexafluoride

____________________________________________________________________________________ 135

The van der Waals equation of state is capable of qualitatively predicting the phase behaviour of mixtures. The results presented in Fig.5.6 indicate that the agreement between theory and experiment is unsatisfactory. As the carbon number of n alkanes is increased, the calculated trajectory of the critical curve just qualitatively coincide with experimental data. This can be attributed to the failure of the van der Waals hard-sphere repulsive term at high temperatures. It is evident from Fig. 5.5 t at the agreement between theory and experiment for h Heilig-Franck equation of state is generally very good. In most cases, the critical locus can be accurately calculated from the UCEP to high pressures. The ammonia + ethane and ammonia + octadecane mixtures are exceptions. For the experimental results of ammonia + ethane and ammonia + octadecane, the liquid-liquid critical curve passes through a temperature minimum and rapidly climbs to high pressures. For the calculation results, in both cases, the high pressure critical locus curves towards the UCEP. This curvature is only partly reproduced by the calculations for the ammonia + ethane mixture whereas no curvature was apparent in the calculated critical locus of ammonia + octadecane. Nonetheless, good agreement was still obtained for the high pressure equilibria of both mixtures. The Heilig-Franck equation of state (Heilig and Franck, 1989) is essentially a "hard-sphere + attractive term" equation of state. It can be expected to apply adequately to either relatively small molecules or molecules with a high degree of spherical symmetry. In view of this, the results presented in Fig.5.5 are quite impressive. The larger n-alkane molecules are demonstrably non-spherical and there is up to a 15-fold difference in size (as judged by the ratio of critical volumes) between ammonia and the n-alkanes. The results predicted by Guggenheim equation of state (Fig.5.5) show that, when pressure is greater than 10 MPa the agreement between calculation and experiment is good. For lower pressure part (p < 10 MPa ), the calculated curves can predict experimental data with reasonable results in most cases. However, very good agreement for ammonia + butane and ammonia + pentane are obtained. The very good agreement between theory and experiment relies on the a posteriori evaluation of combining rule parameters (Table 5.2). It is of interest to

compare the variation of these combining rule parameters with the ratio of critical volumes of the two components. The graphical results are shown in Fig. 5.7. The parameter is often interpreted as reflecting the strength ( > 1) or weakness ( < 1) of

____________________________________________________________________________________ 136

unlike intermolecular interaction. For Heilig-Franck equation of state, it is apparent from Fig. 5.7 that the magnitude of declines systematically as the size difference between the component molecules increases. This trend is consistent with the interpretation of declining strength of intermolecular interaction between progressively dissimilar molecules. For Guggenheim equation of state, as the size difference between the component molecules is not much (<= 8), the tendency of the magnitude of is similar with that of the Heilig-Franck equation of state. However, as the size difference between the component molecules increases (>8), the tendency of the magnitude of is close to the van der Waals equation of state. This is another way to explain the results showed in Fig.5.5. As expected, the value obtained by van der Waals equation of state is lower and this indicates that the van der Waals equation can not accurately reflect the unlike intermolecular interaction. Consequently, this is another evidence that the van der Waals equation can only be used qualitatively to predict critical properties.

____________________________________________________________________________________ 137

0.86 0.84 0.82 0.80 0.78 0.76

Guggenheim

0.74 0.72 0.70 0.68 0.66

van der Waals Heilig-Franck

0.64 0.62 1 2 3 4 5 6
c

9
c

10 11 12 13 14 15 16

V (alkane)/V (NH3)
Fig. 5.7. Variation of using the Guggenheim (+), Heilig-Franck () and van der

Waals () equations of state with respect to the ratio of critical volumes of the ammonia + n-alkane mixtures.

____________________________________________________________________________________ 138

The parameter can be interpreted as reflecting the interaction separation between dissimilar molecules. Generally, values of < 1 are reported for either nonpolar or slightly polar Type II and Type III binary mixtures. This indicates that the separation for dissimilar molecular interaction is less than a simple average of the hardsphere radii. Fig.5.8 shows that the parameters calculated by the Guggenheim and van der Waals equations of state have the similar tendency as the size difference between the component molecules increases. This may be explained by that these two equations of state have the same attractive term. Obviously (Fig.5.5 and Fig.5.6), this attractive term is less accurate than that of Heilig-Franck equation in predicting the critical properties for ammonia + n-alkane binary mixtures. For the Heilig-Franck equation of state, it is of interest to observe that > 1 for all of the Type II ammonia + n-alkane mixtures. This may reflect the degree of repulsion between the ammonia and n-alkane molecules. The parameters from Heilig-Franck equation in Fig. 5.8 shows that the parameter passes through a maximum value and then declines for the higher molecular weight n-alkanes. This could possibly reflect the greater conformational flexibility of the higher molecular weight alkanes to adopt a space saving orientation and a relative decline in the importance of the ammonia dipole moment. However, it must be noted that the interpretation of the both the and parameters should be treated as conjecture because the use of combining rule parameters can also be partly attributed to weaknesses in the theoretical model. A discrepancy of 6-8% is typically reported (Sadus and Young, 1985) in the interaction parameters obtain from gas-liquid critical transitions compared with values from the analysis of upper critical solution temperatures. A discrepancy of 0.01 in the parameter will affect the accuracy of the predicted gas-liquid critical temperature by approximately 1 K. Consequently, the interaction parameters reported in Table 5.1

could probably be used to predict the gas-liquid critical transitions of these fluids with a reasonable degree of accuracy. Furthermore, the data are valuable for the prediction of critical equilibria in ternary mixtures. It has been demonstrated (Sadus, 1992) that the critical transitions of ternary mixtures can often be accurately predicted by using only the critical properties of the component fluids and the interaction parameters for the three binary sub-systems.

____________________________________________________________________________________ 139

1.20 1.10 1.00

0.90 0.80 0.70 0 1.20 1.10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Guggenheim

Heilig-Franck
1.00

0.90 0.80 0.70 0

1.20 1.10 1.00

9 10 11 12 13 14 15 16

0.90

van der Waals

0.80 0.70 0 1 2 3 4 5
c

9 10 11 12 13 14 15 16
c

V (alkane)/V (NH3)
Fig. 5.8. Variation of using the Guggenheim ( Heilig-Franck () and van +), der Waals () equations of state with respect to the ratio of critical volumes of the ammonia + n-alkane mixtures.

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5.3.2 Ammonia and Simple Gas Mixtures

Brunner (1988b) reported the critical phase behaviour for binary mixtures of ammonia + a simple gas. According to the classification scheme of van Konynenburg and Scott (Fig. 5.1), these mixtures exhibit Type III behaviour. A continuous gas-liquid critical transition is not observed between the critical points of the components of a Type III system. Instead, two distinct critical branches can be identified commencing from the pure component critical points. At low temperatures, a line of gas-liquid critical transitions is terminated by an UCEP at the end of a three-phase liquid-liquidvapour coexistence curve. The critical curve commencing at the critical point of the least volatile component typically extends partly to lower temperatures before abruptly rising to very high pressures. A continual transition between "gas-liquid" and "liquidliquid" transitions can be inferred along this locus. The comparison of theory with experiment for the main Type III critical locus of ammonia + either hydrogen, helium, nitrogen, argon, carbon monoxide, sulphur hexafluoride or methane is presented in Fig. 5.9 (Heilig-Franck and Guggenheim equations of state) and Fig. 5.10 (van der Waals equation of state). The calculated critical properties from the van der Waals, Guggenheim and Heilig-Franck equations of state are in exceptionally good agreement with the available experimental data. Although the tendency of predicted curves by van der Waals equation of state is slightly different from the Heilig-Franck and Guggenheim equations of state, especially for ammonia + methane. In the absence of experimental data, it is difficult to conclude which trend is more accurate unless more experimental data in the higher pressure range (above 100 MPa) are available. In common with the analysis of Type III behaviour, the agreement between theory and experiment was maximised by the trial and error determination of the best fit values of the and combining rule parameters (Table 5.2). When Heilig-Franck equation of state was used, values of < 1 were obtained for most mixtures which contrasts with > 1 for all of the Type II systems. The parameters are very similar for three equations of state for ammonia + simple gases mixtures. The parameters obtained by Heilig-Franck and Guggenheim equations of state show the expected dependence on the relative size difference between the component molecules with the exception of the anomalously high values associated

____________________________________________________________________________________ 141

with either the ammonia + hydrogen or ammonia + helium systems. Again, the parameters obtained by the van der Waals equation of state are very low.

200 180 160 140 120

CH 4 CO Ar N2 H2 SF6 He

p /MPa

100 80 60 40 20
CP(NH3)

0 300 320 340 360 380 400 420 440 460

T/K
Fig. 5.9. Comparison of the experiment (; Brunner, 1988b) with calculations using

the Heilig-Franck () and Guggenheim ( equations of state for the critical locus of ---) __ Type III ammonia + gas mixtures. The vapour-pressure curve ( ) ending at the critical point (l) of ammonia is also shown.

____________________________________________________________________________________ 142

200 180 160 140 120

CH4 CO Ar N2 H2 SF6 He

p /MPa

100 80 60 40 20
CP(NH3)

0 300 320 340 360 380 400 420 440 460

T/K
Fig. 5.10. Comparison of the experiment (; Brunner, 1988b) with calculations using

the van der Waals () equation of state for the critical locus of Type III ammonia + gas mixtures. The vapour-pressure curve (__ ) ending at the critical point (l) of ammonia is also shown.

The critical curves of the binary ammonia + either hydrogen, nitrogen, argon, methane or carbon monoxide mixtures all commence at the critical point of ammonia. As the pressure increases, the critical curves pass through a temperature minimum and then rise steeply towards high pressures as the temperature increases. In contrast, the critical transitions of the ammonia + helium system occur at temperatures and pressures greater than the critical point of ammonia. The branch of the critical curve originating from the critical point of ammonia immediately tends towards higher temperatures and pressures. This behaviour is an example of so called "gas-gas" immiscibility of the first

____________________________________________________________________________________ 143

kind (Schneider, 1978) which is typical of helium containing mixtures. The ammonia + sulphur hexafluoride mixture is the only system to display a pressure-temperature minimum in the critical locus. At very high pressures, the critical curve of mixtures with a temperature minimum sometimes extends to temperatures above the critical temperature of the least volatile component. This phenomenon is described as "gas-gas" immiscibility of the second kind (Schneider, 1978). There are no experimental data at pressures above 100 MPa; however, the calculated critical curve (Fig. 5.9 and Fig. 5.10) indicates a region of "gas-gas" immiscibility at pressures above 170 MPa.

5.4 Phase Behaviour of Water + 5 Noble Gases The phase behaviour of water + noble gas mixtures is interesting because we can observe the effects of interactions between a small dipolar molecule (water) with a series of different spherical entities (He to Xe) that increase in size. The phase behaviour of the water + argon mixture has been the most widely investigated. Tsiklis and Prokhorov (1966) reported measurements of the critical curve for this mixture. These data were supplemented by measurements of both critical properties and binodal curves at high temperatures and pressures reported by Lentz and Franck (1969) and later in an improved way by Wu et al. (1990). Similar measurements for the water + xenon system have been reported (Franck et al., 1974). Mather et al. (1993) measured the binodal curves for both the water + krypton and water + neon mixtures over a wide range of temperatures and pressures. They also used the Heilig-Franck (Heilig and

Franck, 1989, 1990) equation of state to calculate a critical curve for these mixtures that was in good agreement with the experimental phase-envelope. Sretenskaja et al. (1995) completed the experimental investigation of the water + stable noble gas mixtures by measuring the critical curve, binodal curves and supercritical molar volumes for the water + helium mixture. The critical properties of the water + noble gas systems are characteristic of Type III phase behaviour according to classification scheme of van Konynenburg and Scott (1980). Type III behaviour is often associated with so called "gas-gas" immiscibility (Schneider, 1978) whereby phase-coexistence is observed at temperatures greater than the critical temperature of either binary mixture component. Some degree of "gas-gas" immiscibility is observed for all of the water + noble gas mixtures. "Gasgas" immiscibility of the first kind (Type IIIa behaviour) was reported for the water +

____________________________________________________________________________________ 144

helium and water + neon mixtures. In these mixtures, the entire p-T projection of the critical curve commencing from the critical point of water extends to temperatures above the critical temperature of water. xenon systems display In contrast, the water + argon, krypton and "gas-gas" immiscibility of the second kind (Type IIIb

behaviour). The p-T projection of the critical curve for these mixtures initially passes through a pressure-temperature minimum before extending to temperatures and pressures that are higher than the corresponding critical properties of water. Therefore, the water + noble gas family of mixtures exhibits a transition between Type IIIa and Type IIIb behaviour. This is the only known homologous series of binary mixtures to exhibit such a transition. In this section, the critical properties and high pressure binodal curves of binary mixtures of water + helium, neon, argon, krypton and xenon are discussed. The experimental binodal equilibria and critical curves are compared with calculations using the van der Waals, Guggenheim (1965) and Heilig-Franck (Heilig and Franck, 1989) equations of state. 5.4.1 Critical Curves

The experimental data for mixtures containing helium (Sretenskaja et al., 1995), neon (Mather et al., 1993), argon (Wu et al., 1990), krypton (Mather et al., 1993) and xenon (Franck et al., 1974) were obtained from the literature. The critical properties of the water + neon and water + krypton systems have not been measured directly. In these cases the position of the calculated critical curve was determined by examining isopleth measurements (Mather et al., 1993). The calculated critical curves for the water + noble gas mixtures are compared with experimental data in Fig. 5.11 and Fig. 5.12. For all mixtures, the critical curves are calculated using the simple van der Waals (Fig. 5.11), Guggenheim (Fig. 5.12) and Heilig-Franck (Fig. 5.12) equations of state. The adjustable parameters ( and for the van der Waals and Guggenheim equations of state, , and for the Heilig-Franck equation of state) used to maximise agreement between theory and experiment for the critical properties of the binary mixtures are summarised in Table 5.3. These parameters were used for all subsequent binodal curve calculations.

____________________________________________________________________________________ 145

Table 5.3. Adjustable parameters obtained by optimising the agreement between theory and experiment for the critical pressure-temperature behaviour of binary water + noble gas mixtures.

______________________________________________________________________ van der Waals Gas He Ne Ar Kr Xe 0.800 0.120 0.400 0.430 0.500 1.062 1.070 0.937 0.920 0.900 Guggenheim 1.000 0.560 0.663 0.635 0.680 0.760 1.000 0.920 0.898 0.895 1.000 0.712 0.679 0.640 0.670 Heilig-Franck 0.740 1.000 0.913 0.880 0.873 1.27 1.06 1.27 1.27 1.45 ________________ ________________ _________________________

The comparison of experiment with theory presented in Fig. 5.11 indicates that the van der Waals equation is generally unable to predict accurately critical phenomena in water + noble gas mixtures. The inadequate agreement between theory and experiment can be attributed primarily to the failure of the van der Waals hard-sphere repulsive term at high pressures and high densities. This limitation is well known and it has also been documented (Sadus, 1992) for other equations of state that use the van der Waals repulsive term. The inadequacy of the van der Waals equation of state is also reflected in the unrealistically small values of (Table 5.3) required to optimise agreement of theory with experiment. However, in contrast to the calculations for the other mixtures, the van der Waals equation can be used to calculate accurately the critical curve for helium + water (Fig. 5.11) with a physically realistic value (Table 5.3). The comparison of theory with experiment in Fig. 5.12 indicates that the critical properties of the water + noble gas mixtures can be calculated accurately with either the Guggenheim or Heilig-Franck equations of state. The improvement in the accuracy of theory compared with the van der Waals calculations (Fig. 5.11) can be attributed to the improved accuracy of hard-sphere repulsive term used in the Heilig-Franck and Guggenheim equations of state. The water + helium mixture is a notable exception.

____________________________________________________________________________________ 146

Both the Guggenheim and Heilig-Franck equations of state fail (Sretenskaja et al., 1995) to predict adequately the critical behaviour of this system. In contrast, the

calculations using the van der Waals equation (Fig. 5.11) are in very good agreement with experiment. This good result is an anomaly and it does not apply to the other water + noble gas mixtures.

300

250

Xe
200

Ar

Kr

He

Ne

p/MPa

150

100

50

CP(H2O)
0 600 620 640 660 680 700 720 740

T/K
Fig. 5.11. Comparison of experiment (O) with calculations using the van der Waals

equation of state (___) for the critical curves of water + 5 noble gases.

____________________________________________________________________________________ 147

300

250

Xe
200

Ar

Kr

He

Ne

p/MPa

150

100

50

CP(H2O)
0 600 620 640 660 680 700 720 740

T/K
Fig. 5.12. Comparison of experiment (O) with theory for the critical curves of water + 5 noble gases in the p projection using the Heilig-Franck ( ) and Guggenheim (---) -T equations of state.

____________________________________________________________________________________ 148

1.2 1.0 0.8

Guggenheim

0.6 0.4 0.2 0.0 0.04 1.2 1.0 0.8 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20

Heilig-Franck

0.6 0.4 0.2 0.0 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20

1.2 1.0 0.8

van der Waals

0.6 0.4 0.2 0.0 0.04 0.06 0.08

c

0.10

0.12

0.14
c

0.16

0.18

0.20

V (noble gas)/V (H2O)

Fig. 5.13. Variation of using the Guggenheim (+ ), Heilig-Franck () and van der Waals () equations of state with respect to the ratio of critical volumes of the water + noble gas mixtures. Bold symbols indicate for water + helium mixture.

____________________________________________________________________________________ 149

1.2 1.1 1.0

Guggenheim

0.9 0.8 0.7 0.6 0.04 1.2 1.1 1.0 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20

0.9 0.8 0.7 0.6 0.04 0.06 0.08 0.10 0.12 0.14

Heilig-Franck

0.16

0.18

0.20

1.2 1.1 1.0

van der Waals

0.9 0.8 0.7 0.6 0.04 0.06 0.08

c

0.10

0.12

0.14
c

0.16

0.18

0.20

V (noble gas)/V (H2O)

Fig. 5.14. Variation of using the Guggenheim (+ ), Heilig-Franck () and van der Waals () equations of state with respect to the ratio of critical volumes of the water + noble gas mixtures. Bold symbols indicate for water + helium mixture.

____________________________________________________________________________________ 150

The adjustable parameters required to optimise agreement of theory with experimental critical data are summarised in Table 5.3. Fig. 5.13 and 5.14 give the variation of and using equations of state with respect to the ratio of critical volumes of the water + noble gas mixtures. Except for the water + helium system, there is fairly close agreement between the values of and obtained from either the Guggenheim and Heilig-Franck equations of state. The tendency of the variation of using these three equations of state is much of the same (Fig. 5.14). However, the tendency of the variation of using these three equations of state (Fig. 5.13) is of different nature. For van der Waals equation of state, the value of (Fig. 5.14) is close to that of the other two equations, but the value of (Fig. 5.13) is much lower than that of the other two equations. This may be explained by that the van der Waals equation of state cannot accurately reflect the unlike intermolecular interaction. The use of adjustable combining rule parameters partly reflects the failure of theory to adequately a priori predict the phase behaviour of the mixture. In particular, the adjustable parameters are dependent on the equation of state. However, there is evidence (Sadus, 1992, 1994) that they also reflect the strength of unlike interactions. Generally, a small value indicates weak unlike interaction whereas values of at or close to unity indicate strong interaction between dissimilar molecules.

5.4.2 Water + Helium The water + helium mixture is of particular interest because, according to the theory proposed by Temkin (1959), it should exhibit so called "gas-gas" immiscibility of the first kind (Type IIIa). The high pressure phase behaviour of systems containing helium is also of potential interest to the study of the atmospheric behaviour of the outer planets (Stevenson, 1982). Some solubility data are available (Gerth, 1983) for helium in water at high pressure and some preliminary results for the water + helium mixtures was reported by Franck (1987). More recently, Sretenskaja et al. (1995) reported a comprehensive description of the high pressure phase behaviour including both the critical curve and binodal curves for the binary water + helium mixture. They showed the experimental pressure-temperature isopleths at several compositions and the coordinates of the critical curve at pressures up to 180 MPa. Experimental data are also presented for the supercritical molar volumes of the binary mixture.

____________________________________________________________________________________ 151

In the water + helium system, critical points commence from the critical point of water and extend directly to higher temperatures and pressures (Sretenskaja et al., 1995), see Fig. 5.11 and Fig. 5.12. This phenomenon is characteristic of "gas-gas" immiscibility of the first kind (Type IIIa). Sretenskaja et al. (1995) compared theory and experiment for the critical curve but no calculations were attempted for the binodal curves. In this work, the experimental binodal equilibria are compared with calculations using equations of state. The hard-sphere repulsive term of the Heilig-Franck and Guggenheim equations is expected to be of similar accuracy for water + helium mixture. The difference between these equations of state is primarily confined to different assumptions regarding attractive interactions. The calculations of the binodal curves of water + helium were repeated with the van der Waals equation which has a different repulsive term than either of the other two equations of state but the same attractive term as the Guggenheim equation. The adjustable parameters in Table 5.3 were used without modification for the calculation of all the binodal curves. The predicted binodal curves at several different pressures between 75 MPa and 200 MPa are compared with experimental data in Fig. 5.15. Irrespective of the pressure, reasonably good agreement of theory with experiment is obtained. At pressures < 100 MPa, the results for the Heilig-Franck and Guggenheim equations are very similar and more accurate than the calculations for the van der Waals equation of state. equation is more accurate at higher pressures. However, the van der Waals

____________________________________________________________________________________ 152
750 p = 75MPa 700 650 700 650 750 p = 100MPa

T/K

600 550 500 0.0 0.2 0.4 0.6 0.8 1.0

T/K
600 550 500 0.0 0.2 0.4 0.6 0.8 1.0

x (water)

x (water)

750 p = 175MPa 700 650

750 p = 200MPa 700 650

T/K

600 550 500 0.0 0.2 0.4 0.6 0.8 1.0

T/K
600 550 500 0.0 0.2 0.4 0.6 0.8 1.0

x (water)

x (water)

Fig. 5.15. Comparison of experiment (O) with theory for the binodal curves of water + helium in the T-x projection using the Heilig-Franck (), Guggenheim ( - -) and van der Waals (.
. .

) equations of state.

The calculated critical points are identified ().

5.4.3 Water + Neon Water + neon is another mixture which exhibits "gas-gas" immiscibility of the first kind (Type IIIa). Mather et al. (1993) reported the high-pressure phase behaviour of mixture containing water and neon. The critical locus of water + neon was not experimentally determined. However, it was deduced by identifying the phase envelope of the various ( T) isopleths. The binodal curves of water + neon predicted using the p, van der Waals, Guggenheim and Heilig-Franck equations are compared with

____________________________________________________________________________________ 153

experiment in Fig. 5.16. The agreement of theory with experiment is adequate.

It is

interesting to note that there is very little difference between the calculations using either the Guggenheim or Heilig-Franck equations of state. In contrast, calculations using the van der Waals equation of state are less accurate.
700 p = 100MPa 690 680

T/K
670 660 650 0.3 700 p = 150MPa 690 680 0.4 0.5 0.6 0.7 0.8 0.9

x (water)

T/K
670 660 650 0.3 0.4 0.5 0.6 0.7 0.8 0.9

x (water)

Fig. 5.16. Comparison of experiment (O) with theory, for the binodal curves of water + neon in the T-x projection using the Heilig-Franck (__ ), Guggenheim (- - -) and van der Waals ( . . . . ) equations of state. The calculated critical points are identified ().

5.4.4 Water + Argon The liquid-liquid phase equilibria of water + argon has been investigated by Wu et al. (1990). They reported binodal equilibria at pressures between 50 MPa and 250

____________________________________________________________________________________ 154

MPa. These data are compared with our calculations in Fig. 5.17. The results from either the Guggenheim and Heilig-Franck equations of state are almost

indistinguishable and the predictions are reasonably accurate. The van der Waals equation of state predicts a considerably more narrow er two-phase coexistence region than either the Heilig-Franck or Guggenheim equations.
660 p = 50MPa 640 620 640 620 660 p = 100MPa

T/K

600 580 560 0.0 660 p = 200MPa 640 620 0.2 0.4 0.6 0.8 1.0

T/K
600 580 560 0.0 660 p = 250MPa 640 620 0.2 0.4 0.6 0.8 1.0

x(water)

x(water)

T/K

600 580 560 0.0 0.2 0.4 0.6 0.8 1.0

T/K
600 580 560 0.0 0.2 0.4 0.6 0.8 1.0

x(water)

x(water)

Fig. 5.17. Comparison of experiment (O) with theory, for the binodal curves of water + argon in the T-x projection using the Heilig-Franck (__ ) and Guggenheim ( - -) and -

van der Waals ( . . . .) equations of state. The calculated critical points are identified ().

____________________________________________________________________________________ 155

5.4.5 Water + Krypton

The high-pressure phase behaviour of mixtures water + krypton was reported by Mather et al. (1993). The critical locus of water + krypton was also deduced by identifying the phase envelope of the various (p, T) isopleths. The critical curves (Fig. 5.11 and Fig. 5.12) pass through a pressure-temperature minimum and exhibits "gasgas" immiscibility of the second kind (Type IIIb behaviour). The calculated binodal curves are compared with experimental data in Fig. 5.18. There is a noticeable deterioration in the quality of the agreement of theory with experiment for water + krypton mixture. This can be partly attributed to the reduced reliability of the combining rule parameters for this system.

5.4.6 Water + Xenon

For the system water + xenon, the two-phase boundary surface and the critical curve have been determined experimentally by Franck et al. (1974). Inspection of Fig. 5.11 and Fig. 5.12 indicates that although the calculated critical curve of water + xenon passes through a pressure-temperature minimum and belongs to "gas-gas" immiscibility of the second kind (Type IIIb), theory does not accurately predict the position of the critical pressure-temperature minimum for the water + xenon mixture. All three different equations of state predict the binodal curve of the water + xenon mixture (Fig. 5.19) with a similar degree of accuracy.

Finally, it should be emphasised that the comparison of theory and experiment for the binodal curves (Figures 5.15 - 5.19) represent genuine predictions using the unlike interaction parameters (Table 5.3) obtained form analysing the critical curve (Fig. 5.11 and Fig. 5.12). The agreement with experiment could be improved by directly fitting theory to the binodal curve. However, in view of the non-classical nature of phase equilibria in the vicinity of the critical point, it would be preferable to fit the coexistence curve using an equation of state which incorporated classical/non-classical crossover behaviour (De Pablo and Prausnitz, 1989). Nonetheless, the prediction of the coexistence curves using the Guggenheim and Heilig-Franck equations of state are reasonably accurate.

____________________________________________________________________________________ 156
650 p = 100MPa 640

T/K

630

620

610 0.2 0.4 0.6 0.8 1.0

x (water)

650 p = 150MPa 640

T/K

630

620

610 0.2 0.4 0.6 0.8 1.0

x (water)

Fig. 5.18. Comparison of experiment (O) with theory, for the binodal curves of water + krypton in the T projection using the Heilig-Franck (__ ) and Guggenheim ( - -) and -x van der Waals ( . . . .) equations of state. The calculated critical points are identified ().

____________________________________________________________________________________ 157
630 p = 60MPa 600 570

T/K
540 510 480 0.0 630 p = 100MPa 600 570 0.2 0.4 0.6 0.8 1.0

x(water)

T/K
540 510 480 0.0 630 p = 130MPa 600 570 0.2 0.4 0.6 0.8 1.0

x(water)

T/K
540 510 480 0.0 0.2 0.4 0.6 0.8 1.0

x(water)

Fig. 5.19. Comparison of experiment (O) with theory, for the binodal curves of water + xenon in the T-x projection using the Heilig-Franck () and Guggenheim (- - -) and van der Waals ( . . . .) equations of state. The calculated critical points are identified ().

____________________________________________________________________________________ 158

5.5 Vapour-Liquid and Liquid -Liquid Phase Equilibria of Binary mixtures containing Helium Mixtures of helium + a non-polar component are rare examples of non-polar systems exhibiting both vapour-liquid and liquid-liquid phase transitions. They are also relatively free from theoretical complications with the possible exception of quantum effects at low temperatures. The mixtures exhibit Type III behaviour in accordance with the phase behaviour classification scheme of van Konynenburg and Scott (1980). Experimental high pressure and critical data are available for the helium + argon (Streett, 1969, Streett and Hill, 1971, Streett and Erickson, 1972), xenon (De Swaan Arons and Diepen, 1966), hydrogen (Streett et al., 1964, Streett, 1973), nitrogen (Streett, 1967, Streett and Erickson, 1972, Streett and Hill, 1976), ethylene (Tsiklis, 1953) and propane (Tsiklis, 1955) mixtures. The helium + noble gas mixtures are the simplest possible binary mixtures and as such they represent a suitable test for hard sphere + attractive term equations of state. In this chapter, the results of the phase diagrams of binary mixture containing helium with Guggenheim and Heilig-Franck equation of state are discussed. It is well documented (Sadus, 1992a) that the accurate prediction of binary mixtures requires accurate information concerning the strength of the unlike interaction parameters. For relatively simple cases (Sadus, 1989, 1992b), reliable a priori estimates of the and parameters are possible. However, the interaction parameters for liquidliquid equilibria are generally obtained from experimental data. In this work, we have obtained the values of , and by optimising the agreement between theory and experiment for the p-T projection of the critical curve. The optimal agreement was obtained by trial and error adjustment of the interaction parameters and repeated calculation of the critical curve as described elsewhere (Sadus, 1992a).

5.5.1 Critical Properties of Binary Helium + Gas Mixtures The critical data are compared in Fig. 5.20 with calculations of the critical curve using the van der Waals, Guggenheim and Heilig-Franck equations of state. The unlike interaction parameters required for the van der Waals, Guggenheim and Heilig-Franck equations of state are obtained by fitting theory with experiment for the critical curves of eight helium + gas mixtures and the results a included in Table 5.4. The critical re

____________________________________________________________________________________ 159

curves and the interaction parameters for the helium + neon (Heck and Barrick, 1967) and helium + methane (Sinor et al., 1966, Streett et al., 1972) systems were estimated by assuming that the experimental critical pressure coincided with the maximum pressure of the phase envelope. It should be stressed that in reality, the critical pressure can occur below the pressure maximum. The comparison of theory with experiment indicates good agreement for the p-T projection of the critical curve. It is almost impossible to distinguish between the critical curve calculated using either the van der Waals, Guggenheim or Heilig-Franck equations of state.

Table 5.4. Combining rule parameters for binary helium + gas mixtures obtain ed by optimising agreement between theory and experiment for the p-T projection of the critical locus.

______________________________________________________________________ van der Waals 1.05 0.68 0.26 0.75 0.64 0.40 0.20 0.08 0.90 1.02 1.09 1.04 1.03 1.06 1.10 1.16 1.55 1.50 1.40 1.07 1.37 1.30 1.25 1.23 Guggenheim 0.70 1.02 1.07 1.06 1.03 1.05 1.06 1.06 1.10 1.35 1.27 1.50 1.55 1.65 1.60 1.50 Heilig-Franck 1.62 1.55 1.59 1.08 1.38 1.30 1.28 1.50 0.80 1.02 1.08 1.07 1.03 1.05 1.06 1.09 Gas Neon Argon Xenon Hydrogen Nitrogen Methane Ethylene Propane

____________________________________________________________________________________ 160

400
C2H 4 Xe C3H 8 CH4 H2 N2 Ar

350

300

250

p/MPa

200

150

100

50

0 0 50 100 150 200 250 300 350 400 450

Ne

T/K
Fig. 5.20. Comparison of the experimental critical curves () of binary helium + gas mixtures with calculations using the Guggenheim (), Heilig-Franck (----) and van der Waals ( L) equations of state. experimental data (). Also shown are critical properties estimated from

____________________________________________________________________________________ 161

There is a logical continuity between the critical curves of binary systems exhibiting fluid-fluid equilibria and those of more conventional systems (Streett, 1967). This is shown in the p-T diagram of Fig. 5.20. With increasing critical temperature of the second component, the critical curve rises more steeply from the pure component critical point, and appears to be essentially vertical around the helium + methane system. For the helium + ethylene, helium + xenon and helium + propane systems, the critical mixture curves clearly leave the critical point of the second component with a positive slope. The critical curves of the helium + hydrogen, helium + nitrogen and helium + argon are nearly vertical at the highest pressure reached. This evidence strongly suggests that these critical curves will have a positive slope at higher pressures, thus defining a region of liquid-liquid equilibria. The helium + neon system probably also exhibits this behaviour although the experimental critical curve is unavailable. As we discussed, it is apparent from Fig. 5.20, that the critical locus of the helium + gas systems all commence at the critical point of the gas component and thereafter, rise rapidly to very high pressures and exhibit Type III behaviour. However, there is a subtle and interesting distinction between the different critical curves. The critical curves of helium + the gases methane, ethylene, propane and xenon, occur at temperatures and pressures above the critical point of the gas. This phenomenon is characteristic of so-called gas-gas immiscibility (Schneider, 1978) of the first kind (Type IIIa behaviour). In contrast, the critical curve for the remaining mixtures extends initially to temperatures below that of the gas. For the helium + nitrogen mixture, the experimental data indicate a region of gas-gas immiscibility of the second kind (Type IIIb behaviour) at very high pressures. There are insufficient experimental data to

assign Type IIIb behaviour to the other mixtures and the calculated critical properties always occur at temperatures below the critical temperature of the gas. The phenomenon of gas-gas immiscibility of the first kind is rare and it is almost confined exclusively to mixtures containing helium. The neon + water mixture

(Mather et al., 1993) is the only other reported Type IIIa mixture. Examining Temkin's (1959) criteria, the criteria have mixed success in predicting gas-gas immiscibility of the first kind for the helium + gas mixtures. Type IIIa behaviour is not predicted for the
c c helium + propane mixture (Temkin's (1959) criteria V11 0 .42V22 is not satisfied)

whereas the phenomenon is incorrectly predicted for both the helium + argon and

____________________________________________________________________________________ 162

helium + nitrogen mixtures.

However, Type IIIa behaviour is correctly predicted for

mixtures of helium + xenon, methane and ethylene. Fig. 5.21 and 5.22 show the variation of and using equations of state with respect to the ratio of critical volumes of the helium + gas mixtures. The tendency of the values of and obtained from the three equations of state are very similar. Consistent with water + noble gases mixtures, there is fairly close agreement between the values of and obtai ed from either the Gugeenheim and Heilig-Franck equations of state. For n van der Waals equation of state, although the value of is close to that of the other two equations, the value of is much lower than that of the other two equations.

5.5.2 Helium + Neon The p-x vapour-liquid phase envelopes for the helium + neon mixture have been measured (Heck and Barrick, 1967) at several different temperatures. These experimental data are compared with the predictions of the van der Waals, Guggenheim and Heilig-Franck equations of state. The results are showed graphically in Fig. 5.23 and Fig. 5.24. The mole fraction helium is plotted vs. total pressure. At any temperature and pressure, the portion of the isotherm with lower helium compositions is the liquid phase, and the portion of the isotherm with higher helium compositions is the vapour phase. By using the Guggenheim and Heilig-Franck equations of state (Fig. 5.23), reasonably good agreement between theory and experiment is obtained at all temperatures. However, when the van der Waals equation of state was used to calculate the binodal curves, only the qualitative agreement (Fig. 5.24) was obtained between theory and experiment. At pressures > 5 MPa, there is a noticeable difference in the position of the critical p-x locus predicted by the Guggenheim and Heilig-Franck equations of state. At low temperatures, the Heilig-Franck equation of state is slightly more accurate than the Guggenheim equation. Phase separation at high pressures is also predicted at unrealistically low temperatures (Fig. 5.20). This may be caused by errors in the unlike combining rule parameters obtained by comparing theory with the estimated critical points at low pressures.

____________________________________________________________________________________ 163

1.80

1.35

0.90

Guggenheim

0.45

0.00 0.5
1.80

1.0

1.5

2.0

2.5

3.0

3.5

4.0

1.35

0.90

Heilig-Franck

0.45

0.00 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

1.80

1.35

0.90

van der Waals

0.45

0.00 0.5 1.0 1.5

c

2.0

2.5
c

3.0

3.5

4.0

V (gas)/V (He)
Figure 5.21. Variation of using the Guggenheim ( Heilig-Franck () and van der +), Waals () equations of state with respect to the ratio of critical volumes of the helium + gas mixtures.

____________________________________________________________________________________ 164

1.20 1.10 1.00

0.90 0.80 0.70 0.60 0.5

1.20 1.10 1.00

Guggenheim

1.0

1.5

2.0

2.5

3.0

3.5

4.0

0.90 0.80 0.70 0.60 0.5 1.0 1.5 2.0 2.5 3.0

Heilig-Franck

3.5

4.0

1.20 1.10 1.00

0.90 0.80 0.70 0.60 0.5 1.0 1.5

c

van der Waals

2.0

2.5
c

3.0

3.5

4.0

V (gas)/V (He)
Figure 5.22. Variation of using the Guggenheim (+), Heilig-Franck () and van der Waals () equations of state with respect to the ratio of critical volumes of the helium + gas mixtures.

____________________________________________________________________________________ 165

30

25

29.91 K

20

p/MPa

15

32.89 K

10

35.9 K

38.88 K

5
41.9 K

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.23. Comparison of experimental vapour-liquid equilibrium data () for the helium + neon mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold. Critical

points estimated from experimental data are illustrated ().

____________________________________________________________________________________ 166

30

25

20

29.91 K

p/MPa

15

32.89 K

10
35.9 K

b
38.88 K

5
41.9 K

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.24. Comparison of experimental vapour-liquid equilibrium data () for the helium + neon mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold. Critical points estimated from experimental data are illustrated ().

____________________________________________________________________________________ 167

5.5.3 Helium + Argon

Considerable experimental high pressure data are available for the helium + argon mixture (Streett, 1969, Streett and Hill, 1971, Streett and Erickson, 1972). The equations of state predictions for vapour-liquid equilibria of the helium + argon mixture are compared with experiment in Fig. 5.25 and Fig. 5.26. For the experimental and calculated isotherms, the portion of the isotherm with lower helium compositions is the liquid phase, and the portion of the isotherm with higher helium compositions is the vapour phase. When the temperature is 147.29 K, the isotherm exhibits liquid-liquid equilibria and the portion of the isotherm with lower compositions is the dense phase. At pressures < 70 MPa (Fig. 5.25), there is satisfactory agreement of theory with experimental vapour-liquid equilibria data in the p-x projection. The predictions of both equations of state are of similar accuracy. However, the transition between vapourliquid and liquid-liquid equilibria is not predicted accurately. There are some obvious reasons. The critical points shown in Fig. 5.25 have been estimated from plots of the experimental data on p-x, T-x, and p-T diagrams (Streett, 1969). The adjustable parameters in Table 5.4 were used without modification for the calculation of all the binodal curves. Although the calculated critical curves of p-T diagram (Fig. 5.20) showed very good agreement with the estimated experimental critical points, the calculated critical curves in p-x diagram do not agree very well with the estimated experimental critical data. This may lead to some errors which can not be overcome unless more adjustable parameters are introduced.

____________________________________________________________________________________ 168

130.08K

130.08K

70
91.34K 144.4K 144.4K

60

50

p/MPa

30

20
147. 73 K

10

0 0.0 0.2 0.4 0.6 0.8 1.0

Fig. 5.25. Comparison of experimental vapour-liquid equilibrium data () for the helium + argon mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold and the

estimated experimental critical points are identified ().

147.2

40

9K

x (He)

91.34K

____________________________________________________________________________________ 169

70
b 130.08K
130.08K 144.4K 91.34K 144.4K 91.34K

60

50

40

p/MPa

30

20
7.7 3K

10

0 0.0 0.2 0.4 0.6 0.8 1.0

14

x (He)
Fig. 5.26. Comparison of experimental vapour-liquid equilibrium data () for the helium + argon mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold and the estimated experimental critical points are identified ().

147 .29K

____________________________________________________________________________________ 170

The very high pressure (up to 1000 MPa) liquid-liquid phase coexistence of helium + argon at different temperatures is examined in Fig. 5.27 and Fig. 5.28. For the curves at temperatures 98.02 K, 120.01 K and 139.39 K, vapour-liquid equilibria are showed with fair agreement between experimental and calculated results. For the rest of temperatures, the liquid-liquid phase equilibria exhibit qualitatively agreement with experimental data. The agreement of theory with experiment is only satisfactory at moderately high pressures (< 400 MPa). discrepancy between the predicted At very high pressures there is a substantial and experimental critical composition.

Consequently, the predicted coexistence curves are shifted to lower compositions. There is a noticeable difference in Fig. 5.27 and Fig. 5.28. The predicted curves in Fig. 5.28 are in better agreement with experiment than those in Fig. 5.27 in the pressure range 100 MPa to 700 MPa. In other words, the van der Waals equation of state can predict better than the Guggenheim and Heilig-Franck equations of state in this pressure range. This result is similar to that of water + helium binary mixture (see 5.4.2 for details). The isobaric T-x behaviour for liquid-liquid equilibria at pressures between 10 MPa and 400 MPa is examined in Fig. 5.29. In contrast to the predicted isothermal behaviour, the equation of state calculations at isobaric conditions are in exceptionally good agreement with experiment for the entire composition range. As expected, when pressure is greater than 100 MPa (200 MPa and 400 MPa in Fig. 5.29), better agreement can be obtained by using the van der Waals equation of state.

____________________________________________________________________________________ 171

1000
190K

900 800 700 600

180K

170K

159.9K

p/MPa

500 400 300

150.02K

139.39K

120.01K

200 100 0 0.0 0.2 0.4 0.6 0.8 1.0

98.02K

x(He)
Fig. 5.27. Comparison of the experimental isothermal pressure-composition behaviour ( ) of the helium + argon mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold. Direct experimental critical point measurements (l) or critical points estimated from experimental data () are also identified.

____________________________________________________________________________________ 172

1000
190K

900 800 700 600

180K

170K

159.9K

p/MPa

500 400 300

150.02K

139.39K

120.01K

200 100 0 0.0 0.2 0.4 0.6 0.8 1.0

98.02K

x(He)
Fig. 5.28. Comparison of the experimental isothermal pressure-composition behaviour ( ) of the helium + argon mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold. Direct experimental critical point measurements (l) or critical points estimated from experimental data () are also identified.

____________________________________________________________________________________ 173
150 140 130 p = 10 MPa 150 140 130 p = 60 MPa

T/K

120 110 100 90 0.0 180 170 160 150 0.2 0.4 0.6 0.8 1.0

T/K

120 110 100 90 0.0 180 170 160 150 0.2 0.4 0.6 0.8 1.0

x (He)
p = 200 MPa

x (He)
p = 400 MPa

T/K

130 120 110 100 90 0.0 0.2 0.4 0.6 0.8 1.0

T/K

140

140 130 120 110 100 90 0.0 0.2 0.4 0.6 0.8 1.0

x (He)

x (He)

Fig. 5.29. ) of

Comparison of experimental isobaric temperature-composition behaviour

the helium + argon mixtures with predictions using the Guggenheim (),

Heilig-Franck (----) and van der Waals ( L) equations of state. The experimental ( l) and calculated () critical points are identified.

____________________________________________________________________________________ 174

5.5.4 Helium + Xenon

De Swaan Arons and Diepen (1966) measured liquid-liquid equilibria for the helium + xenon mixture. Their experimental data at several different temperatures are compared with equation of state predictions in Fig. 5.30. The predicted liquid-liquid equilibria are in reasonably good agreement with experiment. However, for the curves predicted by the Guggenheim and Heilig-Franck equations of state, a deterioration in the quality of prediction occurs at helium-rich compositions. This can be attributed partly to the inability of theory to adequately account for the considerable size difference between the component molecules. 5.5.5 Helium + Hydrogen

Helium-hydrogen mixtures are composed of the two elements with the simplest atomic and molecular structures. The liquid-vapour phase equilibrium of the heliumhydrogen system is of interest for a number of reasons. High-pressure gaseous helium is often used in the transfer of liquid hydrogen from storage tanks. The possibility of using helium-hydrogen mixtures in bubble chambers to study the interaction of elementary particles with helium nuclei has also been suggested (Roellig and Giese, 1962). Further, the liquid-vapour equilibrium of the two elements with the lowest critical temperatures is of particular interest from a theoretical point of view. The isothermal p-x vapourliquid coexistence curves at several different temperatures have been reported (Streett et al., 1964) for the helium + hydrogen mixture. These data are compared with equation of state predictions from Fig. 5.31 to Fig. 5.35. The closed loops in Fig. 5.31 and Fig. 5.32 represent temperatures for which the critical point occurs at a pressure below 4 MPa. These loops show a region of retrograde condensation of the first type, which is that portion of the loop lying to the right of a vertical line through the critical point. The region in which the liquid lines crosse is one of retrograde condensation of the second type. In Fig. 5.31 and Fig. 5.32, the temperature of all curves is below the critical temperature of hydrogen. It is apparent from Fig. 5.31 that either the Guggenheim or Heilig-Franck equations of state can predict accurately the vapour-liquid coexistence of this mixture. However, the van der Waals equation of state can only predict qualitatively the vapour-liquid coexistence of this mixture and fails to predict the closed loops (Fig. 5.32). Although the van der Waals equation gave some worse results, very

____________________________________________________________________________________ 175

impressive agreement predicted by the Guggenheim and Heilig-Franck equations of state with experiment (Streett et al., 1964) is also obtained for the isobaric temperaturecomposition phase coexistence at low pressures (Fig. 5.33). The helium + hydrogen mixture also exhibits liquid-liquid separation at very high pressures and the results was reported by Streett (1973). The experimental isothermal liquid-liquid coexistence data are compared with equation of state calculations in Fig. 5.34 and Fig. 5.35. At pressures > 50 MPa there is a significant discrepancy between the predicted and experimental critical composition. Nonetheless, there is generally satisfactory agreement between theory and experiment at temperatures < 80 K and pressures < 600 MPa. When temperature is equal to 70.3K, the curve (in Fig. 5.35) predicted by the van der Waals equation of state is in better agreement with experiment than the Guggenheim and Heilig-Franck equations of state (in Fig. 5.34).

____________________________________________________________________________________ 176
310 p = 30.3975 MPa 310 p = 50.6225 MPa

300

300

T/K

290

T/K
290 280 0.0
320

280 0.2 0.4 0.6 0.8 1.0 320 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
p = 81.06 MPa

x (He)
p = 101.325 MPa

310

310

T/K
0.0 0.2 0.4 0.6 0.8 1.0

T/K

300

300

290

290

280

280 0.0 330 320 310 0.2 0.4 0.6 0.8 1.0

x (He)
330 320 310 p = 131.7225 MPa

x (He)
p = 162.12 MPa

T/K

300 290 280 0.0 0.2 0.4 0.6 0.8 1.0

T/K
300 290 280 0.0 0.2 0.4 0.6 0.8 1.0

x (He)

x (He)

Fig. 5.30. Comparison of experimental liquid-liquid equilibrium data () for the helium + xenon mixtures with predictions using the Guggenheim (), Heilig-Franck (----) and van der Waals ( L) equations of state. The experimental (l) and calculated () critical points are identified.

____________________________________________________________________________________ 177

4
20.40K 17.07K 23.0K 26.0K 29.0K 29.0K 26.0K 23.0K

p/MPa

0 0.0 0.2 0.4 0.6 0.8 1.0

31 . 9K

31.5K

31K

30.6K

x (He)
Fig. 5.31. Comparison of experimental vapour-liquid equilibrium data () for the helium + hydrogen mixtures with predictions using the Guggenheim () and HeiligFranck (----) equations of state. The calculated critical curve is illustrated in bold. Direct experimental critical point measurements (l) or critical points estimated from experimental data () are also identified.

____________________________________________________________________________________ 178

4
17.07K 20.40K 23.0K 26.0K 29.0K 26.0K 20.40K 17.07K 23.0K

b
0.8

p/MPa

0 0.0 0.2 0.4 0.6 1.0

b 30.6K

x (He)
Fig. 5.32. Comparison of experimental vapour-liquid equilibrium data () for the helium + hydrogen mixtures with predictions using the van der Waals ( ) equation of state. The calculated critical curve is illustrated in bold. Direct experimental critical point measurements (l) or critical points estimated from experimental data () are also identified.

____________________________________________________________________________________ 179
35 p = 3.447 MPa

30

T/K

25

20

15 0.0 35 0.2 0.4 0.6 0.8 1.0

x (He)
p = 20.0 MPa

30

T/K

25

20

15 0.0 100 0.2 0.4 0.6 0.8 1.0

x (He)
p = 500.0 MPa

80

T/K
60 40 0.0 0.2 0.4 0.6 0.8 1.0

x (He)

Fig. 5.33.

Comparison of experimental isobaric temperature-composition behaviour (

) of the helium + hydrogen mixtures with predictions using the Guggenheim (), Heilig-Franck (----) and van der Waals ( L) equations of state. The experimental (l) and calculated () critical points are identified.

____________________________________________________________________________________ 180

900
93K

800

700

84.82K

600

77.61K

p/MPa

500

70.3K

400
61.5K

300

200
38.88K

100

29K

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.34. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + hydrogen mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold and the experimental critical points are identified (l).

____________________________________________________________________________________ 181

900
93K

800

700

84.82K

600

77.61K

p/MPa

500

70.3K

400

61.5K

300

200
38.88K

100

29K

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.35. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + hydrogen mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold and the experimental critical points are identified (l).

____________________________________________________________________________________ 182

5.5.6 Helium + Nitrogen

The phase behaviour of helium + simple diatomic mixtures are represented by systems containing either hydrogen or nitrogen. Streett (1967) reported equilibrium phase compositions for the helium-nitrogen system. Inspection of Fig. 5.20, the critical curve of helium + nitrogen moves first to lower temperatures but passes through a temperature minimum (Streett (1967) reported at 119.89 K and 58.6 MPa) and thereafter moves into regions of higher temperature with increasing pressure. The isotherms below this temperature are open ended at the highest pressures reached and apparently cannot be closed (Fig. 5.36 and Fig. 5.37), regardless of the pressure, unless the critical curve changes direction again and moves to lower temperatures at much higher pressures. At temperatures between 119.89 K and the critical temperature of nitrogen (126.2 K) each isotherm should also form a closed loop, on which the maximum point is a critical point, theories fail to predict this region. When the temperature > 119.89 K, the isotherm should have a second branch at higher pressures, however, on which the minimum point is a critical point. This second branch can be seen in Fig. 5.36 and Fig. 5.37. There is generally only qualitative agreement between theory and experiment at all temperatures. In particular, theory fails to account for the coexistence isotherms at very high pressures. The experimental (Streett and Hill, 1976) isobaric T-x behaviour of liquid-liquid coexistence for the helium + nitrogen mixture is compared with equation of state predictions in Fig. 5.38. Irrespective of the pressure, there is good agreement between theory and experiment for the entire composition range.

____________________________________________________________________________________ 183

1000 900

138.00K

154K

130.00K

800 700 600

124.05K

117.13K

p/MPa

500 400
100.61K

300 200 100 0 0.0 0.2 0.4 0.6 0.8 1.0

77.48K

x (He)
Fig. 5.36. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + nitrogen mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold. Direct experimental critical point measurements (l) or critical points estimated

from experimental data () are also identified.

____________________________________________________________________________________ 184

1000 900

138.00K

154K

130.00K

800 700 600

124.05K

117.13K

p/MPa

500 400
100.61K

300 200 100 0 0.0 0.2 0.4 0.6 0.8 1.0

77.48K

x (He)
Fig. 5.37. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + nitrogen mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold. Direct

experimental critical point measurements (l) or critical points estimated from experimental data () are also identified.

____________________________________________________________________________________ 185
140 130 120 p = 82.78 MPa 140 130 120 p = 137.90 MPa

T/K

100 90 80 70 0.0 140 130 120 0.2 0.4 0.6 0.8 1.0

T/K

110

110 100 90 80 70 0.0 140 130 120 0.2 0.4 0.6 0.8 1.0

x (He)
p = 206.80 MPa

x (He)
p = 262.03 MPa

T/K

100 90 80 70 0.0 140 130 120 0.2 0.4 0.6 0.8 1.0

T/K

110

110 100 90 80 70 0.0 140 130 120 0.2 0.4 0.6 0.8 1.0

x (He)
p = 344.91 MPa

x (He)
p = 413.71 MPa

T/K

100 90 80 70 0.0 0.2 0.4 0.6 0.8 1.0

T/K

110

110 100 90 80 70 0.0 0.2 0.4 0.6 0.8 1.0

x (He)

x (He)

Fig. 5.38. Comparison of experimental liquid-liquid equilibrium data () for the helium + nitrogen mixtures with predictions using the Guggenheim (), Heilig-Franck (----) and van der Waals equations of state. The experimental ( and calculated () critical l) points are identified.

____________________________________________________________________________________ 186

5.5.7 Helium + Methane

Experimental measurements for helium + a non-polar polyatomic molecule are limited to mixtures containing a hydrocarbon gas. The helium + methane mixture represents the simplest possible helium + hydrocarbon combination. Sinor et al. (1966) measured the isothermal p-x vapour-liquid coexistence of the helium + methane mixtures at several temperatures. It is apparent from Fig. 5.39 and Fig. 5.40 that reasonably accurate predictions for these experimental data are obtainable with either the van der Waals, Guggenheim or Heilig-Franck equations of state. Streett et al. (1972) reported liquid-liquid separation for this system under isothermal conditions. Their data

are compared with equation of state predictions in Fig. 5.41 and Fig. 5.42. The isotherms in Fig. 5.41 and Fig. 5.42 can be viewed as contour lines in the surfaces representing equilibrium between methane-rich and helium-rich phases. These two surfaces have common boundaries in the methane vapour-pressure curve and the mixture critical line. The left branch of each isotherm lies in the methane-rich surface and the right branch in the helium-rich surface. These surfaces join smoothly along the critical line, which is the locus of minimum in the p-x isotherms (Fig. 5.41 and Fig. 5.42). In common with the other helium mixtures, the agreement between theory and experiment deteriorates progressively at very high pressures.

5.5.8 Helium + Ethylene and Helium + Propane

Experimental liquid-liquid coexistence data are available for the helium + ethylene (Tsiklis, 1953) and helium + propane (Tsiklis, 1955) mixtures. The predicted

liquid-liquid coexistence of helium + ethylene is compared with experiment in Fig. 5.43. The agreement with theory at different pressures is satisfactory at most compositions. In contrast, the isobaric T-x liquid-liquid coexistence predicted for the At high pressure, the Heilig-Franck equation is marginally more

helium + propane mixture (Fig. 5.44) occurs over a narrower range of composition than the experimental data.

accurate than the van der Waals and Guggenheim equations of state. The deterioration in the quality of prediction for this mixture can be attributed partly to the significantly non-spherical geometry of the propane molecule.

____________________________________________________________________________________ 187

153.15K 173.15K

188.15K

188.15K

173.15K

153.15K

12

p/MPa

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.39. Comparison of experimental vapour-liquid equilibrium data () for the helium + methane mixtures with predictions using the Guggenheim () and HeiligFranck (----) equations of state. The calculated critical curve is illustrated in bold.

133.15K 113.15K 93.15K

16

____________________________________________________________________________________ 188

133.15K 153.15K

173.15K

188.15K

16

188.15K

173.15K

153.15K

12

p/MPa

0 0.0 0.2 0.4 0.6 0.8 1.0

x (He)
Fig. 5.40. Comparison of experimental vapour-liquid equilibrium data () for the helium + methane mixtures with predictions using the van der Waals ( ) equation of state. The calculated critical curve is illustrated in bold.

133.15K

113.15K 93.15K

____________________________________________________________________________________ 189
256.49K

1100
244.24K

290K 273K

1000
210.62K

900 800 700

180.08K 198.33K

p/MPa

600 500
159.84K

400 300 200 100 0 0.0 0.2 0.4 0.6 0.8 1.0
130.16K

x (He)
Fig. 5.41. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + methane mixtures with predictions using the Guggenheim () and Heilig-Franck (----) equations of state. The calculated critical curve is illustrated in bold and the experimental critical points are identified (l).

____________________________________________________________________________________ 190

256.49K

1100 1000 900 800 700

180.08K 198.33K 244.24K 210.62K

290K

273K

p/MPa

600 500
159.84K

400 300 200 100 0 0.0 0.2 0.4 0.6 0.8 1.0
130.16K

x (He)
Fig. 5.42. Comparison of experimental isothermal pressure-composition behaviour (

) of the helium + methane mixtures with predictions using the van der Waals () equation of state. The calculated critical curve is illustrated in bold and the experimental critical points are identified (l).

____________________________________________________________________________________ 191
340 p = 196.132 MPa

320

T/K
300 280 0.2 380 360 340 0.4 0.6 0.8 1.0

x (He)
p = 392.26 MPa

T/K
320 300 280 0.2 400 380 360 0.4 0.6 0.8 1.0

x (He)
p = 588.397 MPa

T/K

340 320 300 280 0.2 0.4 0.6 0.8 1.0

x (He)

Fig. 5.43. Comparison of experimental liquid-liquid equilibrium data () for the helium + ethylene mixtures with predictions using the Guggenheim (), Heilig-Franck (----) and van der Waals ( L) equations of state. The experimental (l) and calculated critical points () are illustrated.

____________________________________________________________________________________ 192
410 p = 98.066 MPa 410 p = 196.132 MPa

400

400

T/K

390

T/K
0.60 0.80 1.00

390

380

380

370 0.40
430 420 410

370 0.40
430 420 410

0.60

0.80

1.00

x (He)
p = 294.198 MPa

x (He)
p = 392.26 MPa

T/K

400 390 380 370 0.40

T/K
0.60 0.80 1.00

400 390 380 370 0.40

0.60

0.80

1.00

x (He)

x (He)

Fig. 5.44. Comparison of experimental liquid-liquid equilibrium data () for the helium + propane mixtures with predictions using the Guggenheim (), Heilig-Franck (----) and van der Waals ( L) equations of state. The experimental ( ) and calculated () l critical points are identified.

Considering all results, it should be emphasised that the comparison of the theory and experiment for the binodal curves (Fig. 5.15 - Fig. 5.19, Fig. 5.23 - Fig. 5.44) represent genuine predictions using the unlike interaction parameters (Table 5.3 and Table 5.4) obtained from analysing the critical curves (Fig. 5.11, Fig. 5.12, Fig. 5.20). The agreement with experiment could be improved by directly fitting theory to the binodal curve. However, in view of the non-classical nature of phase equilibria in the vicinity of the critical point, it would be preferable to fit the coexistence curve using an equation of state which incorporated classical/non-classical crossover behaviour (De

____________________________________________________________________________________ 193

Pablo and Prausnitz, 1989). Nonetheless, the prediction of the coexistence curves using the Guggenheim and Heilig-Franck equations of state are reasonably accurate. Another interesting aspect of the comparison of experiment with theory is that the consistently good results obtained using the relatively simple Guggenheim equation. In most cases, it is almost impossible to distinguish between the results obtained for either the Guggenheim or Heilig-Franck equations. We may anticipate that the temperature-dependence (Christoforakos and Franck, 1986) of the Heilig-Franck equation may improve the prediction of phase coexistence in dipolar mixtures. However, the results show very little quantitative difference in the accuracy of either the Guggenheim and Heilig-Franck equations of state. The accurate evaluation of the unlike interaction parameters appears to be the crucial influence which determines the quality of equation of state predictions. For Type III systems, the analysis of the p-T behaviour of the critical curve appears to yield combining rule parameters which are satisfactory for both vapour-liquid and liquid-liquid equilibria. In contrast to other mixtures (e.g., Type II systems), the high-temperature critical curve of Type III mixtures are characterised by a continuous transition between vapour-liquid and liquid-liquid

equilibria which may partly explain the similar accuracy of the unlike interaction parameters for both phenomena.

References Alwani, Z. and Schneider, G. M. (1976). Fluid Mixtures at high pressure. Phase Separation and Critical Phenomena in Binary Mixtures of a polar component with Supercritical Carbon Dioxide, Ethane and Ethene up to 1000 bar. Ber. Bunsenges. Phys. Chem., 80, 1310-1315. Ambrose, D. (1980). Vapour-Liquid Critical Properties of Pure Substances. National Physical Laboratory Report, Teddington, U.K. Booth, H. S. and Carter, J. M. (1930). The Critical Constants of Carbon DioxideOxygen mixtures. J. Phys. Chem., 34, 2801-2825. Brunner, E. (1985). Fluid Mixtures at High Pressures II. Phase Separations and Critical Phenomena of (ethane + an n-alkanol) and of (ethane + methanol) and of (propane + methanol). J. Chem. Thermodynamics, 17, 871-885.

____________________________________________________________________________________ 194

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