Ternary System Example

Two further examples of type I ternary systems are shown in Figure 19 which presents calculated and observed selectivities. For successful extraction, selectivity is often a more important index than the distribution coefficient. Calculations are shown for the case where binary data alone are used and where binary data are used together with a single ternary tie line. It is evident that calculated selectivities are substantially improved by including limited ternary tie-line data in data reduction. 

When the relationship between the distribution coefficient of a solute and solvent composition, or the corrected retention volume and solvent composition, was evaluated for aqueous solvent mixtures, it was found that the simple relationship identified by Purnell and Laub and Katz et al. no longer applied. The suspected cause for the failure was the strong association between the solvent and water. As a consequence, the mixture was not binary in nature but, in fact, a ternary system. An aqueous solution of methanol, for example, contained methanol, water and methanol associated with water. It follows that the prediction of the net distribution coefficient or net retention volume for a ternary system would require the use of three distribution coefficients one representing the distribution of the solute between the stationary phase and water, one representing that between the stationary phase and methanol and one between the stationary phase and the methanol/water associate. Unfortunately, as the relative amount of association varies with the initial... 

The system H2S-CH4-H20 is an example of a ternary system forming a continuous range of mixed hydrates of Structure I. For this system Noaker and Katz22 studied the H2S/CH4 ratio of the gas in equilibrium with aqueous liquid and hydrate. From the variation of this ratio with total pressure at constant temperature it follows that complete miscibility must occur in the solid phase. 

Numerous ternary systems are known for II-VI structures incorporating elements from other groups of the Periodic Table. One example is the Zn-Fe-S system Zn(II) and Fe(II) may substimte each other in chalcogenide structures as both are divalent and have similar radii. The cubic polymorphs of ZnS and FeS have almost identical lattice constant a = 5.3 A) and form solid solutions in the entire range of composition. The optical band gap of these alloys varies (rather anomalously) within the limits of the ZnS (3.6 eV) and FeS (0.95 eV) values. The properties of Zn Fei-xS are well suited for thin film heterojunction-based solar cells as well as for photoluminescent and electroluminescent devices. 

For three-component (C = 3) or ternary systems the Gibbs phase rule reads Ph + F = C + 2 = 5. In the simplest case the components of the system are three elements, but a ternary system may for example also have three oxides or fluorides as components. As a rule of thumb the number of independent components in a system can be determined by the number of elements in the system. If the oxidation state of all elements are equal in all phases, the number of components is reduced by 1. The Gibbs phase rule implies that five phases will coexist in invariant phase equilibria, four in univariant and three in divariant phase equilibria. With only a single phase present F = 4, and the equilibrium state of a ternary system can only be represented graphically by reducing the number of intensive variables. 

Let us now consider two real ternary systems to illustrate the complexity of ternary phase diagrams in some detail. While the first is a system in which the solid state situation is rather simple and attention is primarily given to the liquidus surfaces, the solid state is the focus of the second example. 

The Al-Zn-Si is another example of simple ternary system its isothermal section at 307°C is shown in Fig. 2.27 together with its boundary binaries. Si, in the solid state, is practically insoluble in A1 or in Zn and in their binary solutions. In the... 

More complex situations were shown in Figs. 2.26 and 2.27, where some typical examples of isobarothermal sections of ternary alloy phase diagrams were presented. In the case of ternary systems, several binary and ternary stoichiometric (Fig. 2.28) phases and/or different types of variable composition phases (Fig. 2.29) may be found. We may differentiate between these phases by using terms such as point compounds (or point phases, that is, phases represented in the composition triangle, or more generally in the composition simplex by points), Tine phases , field phases , etc. 

Many different types of phase behaviour are encountered in ternary systems that consist of water and two solid solutes. For example, the system KNO3—NaNC>3— H20 which does not form hydrates or combine chemically at 323 K is shown in Figure 15.6, which is taken from Mullin 3 . Point A represents the solubility of KNO3 in water at 323 K (46.2 kg/100 kg solution), C the solubility of NaN(>3 (53.2 kg/100 kg solution), AB is the composition of saturated ternary solutions in equilibrium with solid KNO3 and BC... 

Figures 8 and 9 show, by way of examples, the I.B. spectra of the ternary systems toluene-HCl-GaCls and m-xylene-HCl-GaCla. The pronounced changes can be interpreted if the formation of a proton addition complex is assumed. A detailed discussion of the I.B. spectra...

Fig. 10.1 Different types of liquid-liquid systems, (a), (b) Solubility as function of temperature for binary systems (c), (d) ternary systems. (Dashed lines are examples of tie lines, which connect the two phases in equilibrium located at the binodal.)...

The behaviour of ternary systems consisting of two polymers and a solvent depends largely on the nature of interactions between components (1-4). Two types of limiting behaviour can be observed. The first one occurs in non-polar systems, where polymer-polymer interactions are very low. In such systems a liquid-liquid phase separation is usually observed each liquid phase contains almost the total quantity of one polymer species. The second type of behaviour often occurs in aqueous polymer solutions. The polar or ionic water-soluble polymers can interact to form macromolecular aggregates, occasionally insoluble, called "polymer complexes". Examples are polyanion-polycation couples stabilized through electrostatic interactions, or polyacid-polybase couples stabilized through hydrogen bonds. 

The most significant advantage of these more quantitative methods is that, in a binary system, only one sample is needed to determine the position of both phase boimdaries in a two-phase field. Further, if the alloy lies in the two-phase field over a wide range of temperatures, it is feasible that only one alloy need be used to fix the phase boundaries over this range of temperature. In a ternary system the analogous position is found with three-phase fields and, as these also define the limiting tie-lines of the three sets of two-phase fields, substantial information can be gained from the accurate determination of only one alloy. More recently transmission electron microscopy (TEM) has been used which is particularly valuable when microstructures are very fine as, for example, found in yTiAl alloys (Chen et al. 1994). 

There are other factors to be considered. In a number of systems ternary phases exist whose stability indicates that there are additional, and as yet unknown, factors at work. For example, in the Ni-Al-Ta system r, which has the NisTi structure, only exists as a stable phase in ternary alloys, although it can only be fully ordered in the binary system where it is metastable. However, the phase competes successfully with equilibrium binary phases that have a substantial extension into the ternary system. The existence of the ly-phase, therefore, is almost certainly due to... 

The discussion above centred around diagrams where die axes were composition or temperature. It is quite possible to use other variables in mapping routines, for example, activity/chemical potential and pressure. Furdier, it is possible to consider mapping other features, for example, the liquid invariant lines in a ternary system (Fig. 9.21). In such cases the positions of the lines are defined by other criteria than described above and new search routines are required. 

Figure 3-21 Calculated diffusion profiles for a diffusion couple in a ternary system. The diffusivity matrix is given in Equation 3-102a. The fraction of Si02 is calculated as 1 - MgO - AI2O3. Si02 shows clear uphill diffusion. A component with initially uniform concentration (such as Si02 in this example) almost always shows uphill diffusion in a multi-component system.

Although the activity obtained by the MA route was not the highest in this case, the effectiveness of MA was still much higher than that of conventional catalyst. In some cases, MA is more effective than rapid solidification for making supersaturated precursors. An example is the Al-Co-Cu ternary system (11). The ranking of effectiveness of these methods may in general depend on the alloy system. 

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