Unlike in binary systems, when we consider ternary systems, the equilibrium compositions do not lie specifically and uniquely

on a single isobaric equilibrium curve, we know this from the Gibbs phase rule which tells us, there is an additional degree of freedom. The compositions of the other component can only be determined if the temperature, pressure and composition of one component in one phase are set. Hence for plotting the equilibrium data for ternary mixture we use the help of triangular graphs: Residue curves (for batch processes) and Distillation curves (for continuous processes) Residue Curves: Residue curves are used for graphing the nature and compositions of ternary mixtures. A residue curve represents the liquid-residue compositions with time as the result of a simple, one stage batch distillation. The curve is pointed in the direction of increasing time, from a lower-boiling state to a higher-boiling state for the liquid residue. Consider a simple distillation model (Rayleigh batch distillation model) where there are no trays, no packing or reflux (as seen in the figure below)

Fig: simple distillation setup. The results, when plotted on a triangular graph, are called a residue curve because the plot follows the liquid residue composition in the still. Different residue lines result from different starting compositions. A collection of these curves for a given ternary system is called a residue curve map. A residue curve map has the following characteristics: If we assign the direction of the residue curves as being from the starting composition to the ending composition, then the arrow on each curve points from a lower boiling component or azeotrope to a higher boiling component or azeotrope.

The presence of azeotropes can create distillation boundaries which cannot be crossed by a residue curve. These distillation boundaries represent the residue curve on which the light or starting residue composition is a lower boiling pure component or azeotrope and the heavy or ending composition residue is a higher pure component or azeotrope. Any given pure component point or azeotrope will be connected to some but not all other pure component points and azeotropes on the graph. Those that are connected form distillation boundaries. These boundaries are thermodynamic in nature. These distillation boundaries partition the map into distillation regions. The nature of these regions is such that two pure components which lie in different regions cannot be separated using conventional distillation.

Some definitions are in order before we explain how residue curve maps apply to enhanced distillation systems. Node: Residue curves begin and end at nodes. Stable node: The component or azeotrope with the highest boiling point in the region. All the residue curves in the region point to (terminate) at this point. Unstable node: The component or azeotrope with the lowest boiling point in the region. Saddle: Residue curves move toward and then away from saddles. Pure components and azeotropes which have a boiling point between the stable and unstable nodes are saddles. Vapor line: The vapor line is the line formed by those vapor compositions which are in equilibrium with the liquid compositions on the distillation boundaries. In other words, if you take all the compositions on a distillation boundary line as saturated liquid compositions; then determine the composition of the vapors which are in equilibrium with all these points; and plotted all these vapor compositions on the residue curve map, one line would be formed for each distillation boundary. That line is called the vapor line. Vapor boilup curve: The vapor boilup curve is the plot of the vapor compositions in equilibrium with any given residue curve. Binodal plot: This is a constant temperature plot of all saturated liquid compositions. It is used to identify the liquid-liquid region of the mixture. Liquid boiling envelope: This is the constant pressure binodal like plot of the two liquid phase region of a ternary system.

Properties of a residue curve map: Based on experimental evidence, for ternary mixtures with very few exceptions, there are at most three binary azeotropes and restrictions that apply to a ternary system: N1 + S1 = 3 N2 + S2 = B < 3 N3 + S3 = 1 or 0

where, N1 = the number of pure single component nodes. N2 = the number of binary nodes. N3 = the number of ternary nodes. S1 = the number of pure component saddles. S2 = the number of binary saddles. S3 = the number of ternary saddles. and 2N3 2S3 + 2N2 B + N1 = 2 For homogeneous azeotropes the nodes may be either stable (maximum boiling) or unstable (minimum boiling). However, heterogeneous azeotropes can be either unstable nodes or saddles but not stable nodes (i.e. they cannot be maximum boiling). The liquid temperature always increases along residue curves in the heterogeneous region. This property, coupled with fact that all singular points on heterogeneous residue curve maps are restricted to be either nodes or saddles, means that the entire topological methodology for analyzing and constructing homogeneous residue curve maps from boiling temperature data alone extends verbatim to heterogeneous mixtures.

Distillation-Curve Maps: An alternative representation for distillation on a ternary diagram is a distillation curve for continuous, rather than batch, distillation. The curve is most readily determined for total reflux. The sequence of liquid-phase compositions, which corresponds to the operating line at total reflux, is

plotted on a triangular diagram. Distillation curve maps can be arbitrarily directed to increasing or decreasing temperatures. A collection of distillation curves, including the lines for distillation boundaries, is a distillation curve-map. Distillation curve maps have been used extensively by Stichlmair and his associates for the development of feasible distillation sequences. In the maps used by them, arrows on the distillation curves are directed toward the lower-boiling species, rather than the higher boiling species as in residue curve maps. Product Composition Regions Residue-curve maps and distillation-curve maps are used to make preliminary estimates of regions of feasible product compositions for distillation of non-ideal ternary mixtures. The product regions are determined by superimposing a column material balance line on the curve map diagram. If a straight line is drawn that connects distillate and bottoms compositions, that line must pass through the feed composition at some intermediate point to satisfy overall and component material balances. For such a material balance line, the distillate and bottoms compositions must lie on the same distillation (residue) curve. Because of this, the feasible product region can be established like so: Find the limiting distillate composition point for the region. Draw a line from this point, through the feed composition, to the opposite side of the map. This point represents the bottoms composition with the lowest amount of low boiler possible for the limiting distillate composition. Call this material balance line M1. Find the limiting bottoms composition point for the region. Draw a line from this point, through the feed composition, to the opposite side of the map. This point represents the distillate composition with the lowest amount of high boiler possible for the limiting bottoms composition. Call this material balance line M2. Locate and draw the distillate curve which contains the feed composition. Call this curve DF. The areas on the convex side of DF, and lying between M1 and DF and between M2 and DF, are the feasible product regions.

For azeotropic systems, where distillation boundaries are present, a feasible product region can be found for each distillation region.