List of Figures

Figure No. Figure Name Page No.

1 Residue curve map for a ternary non-azeotropic

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mixture

2 Residue curve patterns near pure component

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vertices

3 Residue curve patterns near binary azeotropes 9

4 Residue curve patterns near ternary azeotropes 9

5 Residue curve map for a ternary homogeneous 10

nonazeotropic mixture

6 Residue curve map for a system with two binary 11

azeotropes

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 CONTENTS
1. Introduction 6

2. Characteristics of a Residue curve 7

2.1. Stability of a Residue curves 8

3. Examples of Residue curves 10

3.1. Simple Residue Curve 10
3.2. System of Octane, Ethyl Benzene and 2-EthoxyEthanol 11

4. References 12

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1. Introduction
The most basic form of distillation, called simple distillation, is a process in which a
multicomponent liquid mixture is slowly boiled in an open pot and the vapours are
continuously removed as they form. At any instant in time the vapour is in equilibrium
with the liquid remaining in the still. Because the vapour is always richer in the more
volatile components than the liquid, the liquid composition changes continuously with
time, becoming more and more concentrated in the less volatile species [4].

A simple distillation residue curve is a graph showing how the composition of the liquid
residue in the pot changes over time. A residue curve map is a collection of residue
curves originating from different initial compositions. Residue curve maps contain the
same information as phase diagrams, but present it in a way that is more useful for
understanding how to create a distillation sequence to separate a mixture [4].

Residue curves can only originate from, terminate at, or be deflected by the pure
components and azeotropes in a mixture. Pure components and azeotropes that residue
curves move away from are called unstable nodes (UN), those where residue curves
terminate are called stable nodes (SN), and those that deflect residue curves are called
saddles (S). The simplest residue curve map for a ternary mixture is shown in Figure 1.

Figure 1: Residue curve map for a ternary non-azeotropic mixture [4]

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 All ternary nonazeotropic mixtures, including ideal and constant relative volatility
mixtures, are qualitatively represented by this map. All of the residue curves originate
at the light (lowest boiling) pure component, move toward the intermediate boiling
component, and end at the heavy (highest boiling) pure component [4].
Residue curves point in the direction of increasing temperature and must always move
in such a way that the mixture boiling temperature continuously increases along every
curve. From this property and the direction of the arrows in Figure 1, the light
component is an unstable node; the intermediate component, which deflects the residue
curves, is a saddle; and the heavy component is a stable node [4].

2. Characteristics of a Residue curve

A residue curve map has the following characteristics:

i. 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
form a lower boiling component or azeotrope to a higher boiling component or
azeotrope [3].

ii. 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 [3].

iii. 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 [3].

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2.1 Stability of a Residue curve

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 terminate at this point.
Unstable node: The compound or azeotrope with lowest boiling point in
the region. All the residue curves originate from this point.
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 [3].

Figure 2: Residue curve patterns near pure component vertices [2]

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 Figure 3: Residue curve patterns near binary azeotropes [2]

Figure 4: Residue curve patterns near ternary azeotropes [2]

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3. Examples of Residue curves

3.1 Non-azeotropic mixture

A rough sketch of residue curve map for ternary homogeneous mixture of

component A, B and C. Pure component boiling points for component A, B and
C are 55 C, 69 C and 81 C, respectively. There is no binary or ternary
azeotrope.

Figure 5: Residue curve map for a ternary homogeneous nonazeotropic mixture

Unstable node: The point representing the pure component A (55 oC)

Saddle point: The point representing the pure component B (69 oC).

Stable node: The point representing the pure component C (81 oC).

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3.2 System of Octane, Ethyl Benzene and 2-EthoxyEthanol

A residue curves map for a system containing octane, ethylbenzene and 2-

ethoxyethanol with boiling point 398.8 K, 409.2 K and 408.1 K respectively. 2-
ethoxyethanol makes binary azeotrope with octane and ethylbenzene at 389.1 K
and 400.1 K respectively [1].

Figure 6: Residue curve map for a system with two binary azeotropes [1]

In this case, the curved line DE is the simple distillation boundary called
separatrice which divides the diagram into regions with distinct pairs of
starting and terminal points.
In region ADECA, the unstable node is point D and the stable node is point
C with point A as the saddle point.
In region DBED, the unstable node is point D but the stable node is point B
with point E as the saddle point.
In this case, a pure octane product is not possible.

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4. References
1. Seader, J. D., Warren D. Seider, and Daniel R. Lewin. Product and Process Design
Principles: Synthesis, Analysis and Evaluation. Wiley, 2004.
2. Seader, Junior D., Ernest J. Henley, and D. Keith Roper. "Separation process
principles." (1998).
3. Raut, N. B. "Optimization of design and operation in reactive distillation." (1908).
4. Doherty, Michael F., and Jeffrey P. Knapp. "Distillation, azeotropic, and
extractive." Kirk-Othmer Encyclopedia of Chemical Technology (1993).