CEIC3004

RESIDUE CURVE MAPS (RCM)

Tuan Pham
Further reading:
Seader & Henley Section 11.1
Perry Chapter.13
CONTENTS
1

INTRODUCTION
1.1
1.2
1.3

TERNARY AZEOTROPES
RESIDUE CURVES AND RESIDUE CURVES MAPS (RCM)
MAIN FEATURES OF AN RCM

GENERAL RULES FOR CONSTRUCTING AN RCM

CLASSIFICATION OF RCM - DRD (DISTILLATION REGION DIAGRAMS)

WHAT CAN WE DO WITH RCMS?

CONDITIONS OF FEASIBILITY FOR DISTILLATION

APPENDIX 1: CONCENTRATION PROFILE FOR PACKED DISTILLATION COLUMN AT TOTAL

REFLUX
APPENDIX 2: EXTRACTIVE DISTILLATION ON AN RCM
LEADING QUESTIONS
EXERCISES

NOMENCLATURE
A
mass transfer area, m2
BP
boiling point
DRD
Distillation region diagram
kY
mass transfer coefficient,
mole/sm2
Ki
equilibrium ratio, yi/xi
L
total liquid flow in continuous
distillation, mole/s
L'
total liquid remaining in batch
still, mole

V
V'
x
y

RCM
Residue curve map
total vapour flow in continuous distillation,
mole/s
total vapour evaporated from batch still,
mole
mole fraction in liquid
mole fraction in vapour

Subscripts
i, j
component indices

1 Introduction
Residue curve diagrams (RCM) are a type of diagram used to study the distillation of
ternary mixtures, especially those that form azeotropes.
1.1

Ternary azeotropes
An azeotrope is a mixture whose liquid and vapour phases have exactly the same
composition.
Binary azeotropes:

Ternary azeotropes:
With ternary mixture you can get several azeotropes:

Real-life analogue of a ternary saddle azeotrope. Two of the edges (sides) have a
minimum and the third edge (back) has a maximum. The saddle point (minimax) is
shown by the white arrow.
Because 3-D representations are difficult to make, residue curve maps (RCM) are
used instead.
1.2

Residue Curves and Residue Curves Maps (RCM)

When we evaporate a liquid mixture, the composition of the remaining liquid
(residue) will gradually change, with the concentration of the lighter components
gradually decreasing and that of the heavier components increasing.

A residue curve shows how the composition of the residue (liquid mixture remaining
in the still) on a ternary diagram, for a three-component liquid mixture. We now
derive a differential equation that describes this curve.
Over a time interval, dV' moles of vapour evaporates from the
still, of which yidV' is component i. The residual liquid loses dL' moles, of which -d(L'xi) is component i. Material balance
gives
yi dV' = - d(L'xi)
(the two sides of the equation look different because yi is the
mole fraction of i in a puff of vapour, while xi is the mole
fraction in the whole flask, which is assumed well mixed)
and
dV' = -dL'
Equilibrium gives
yi = Kixi
Eliminate dV' and yi from the first equation to get

- Ki xi dL' = - xidL' - L'dxi

Solving for dxi
dxi = (Ki - 1)xi dL'
Similarly for another component j:
dxj = (Ki - 1)xj dL'
Hence the relative change in concentration from one interval to the next is
dxi
K 1 xi
i
dx j K j 1 x j

(1)

or

d ln xi K i 1
(1a)

d ln x j K j 1
This is the differential equation (ODE) that describes the residue curve on the ternary
diagram. From this equation, for any starting composition (initial value), the residue
curve can be calculated and drawn using equations for K-values from thermodynamic
models. The simulation software Aspen Plus has facilities for calculating and plotting
residue curves.

A ternary diagram with families of residue curves drawn on it is called a residue curve
map (RCM). A couple of typical RCMs are shown below:

1.3

Main features of an RCM

Example A
With a non-azeotropic ternary mixture, the lightest
component preferentially evaporates first, therefore
its mole fraction gradually decreases and the
composition moves towards the opposite side of the
triangle. Then the intermediate component (saddle)
evaporates preferentially: the residue curve turns
around and moves towards the apex representing the
heaviest component.

Example B
With a mixture containing two low-boiling
azeotropes, the components/azeotropes can be
ordered according to BP from lowest to highest:
Azeo1, Light or Azeo 2, Intermediate, Heavy.
The RCM is divided into two distillation regions by
a separatrix. The triangular region behaves like the
simple ternary system above.
In the quadrilateral region, the residue curve may
head first towards the first saddle point (the light
component) or the second saddle point (low-boiling
azeo 2), depending on the original composition.
Example C
With a mixture containing three low-boiling
azeotropes, there will be a low-boiling ternary
azeotrope. Three separatrices divide the diagram
into distillation regions.
Azeo 4 will have the lowest BP. Each binary
azeotrope will have lower BP than the two pure
components.
In each quadrilateral region, the residue curves will
start by moving directly away from the lowestboiling, then turn away from the nearest
intermediate-boiling (saddle) towards the highest
boiling.

2 General rules for constructing an RCM

From the above examples we can derive some general rules as follows:
1.

A residue curve starts near a low-boiling node (also called unstable node), move
directly away from it, then curve away from the nearest intermediate boiling node
(saddle ) and end up at the high-boiling node (also called stable node).

2.

When a ternary mixture forms azeotropes, the residue curves are divided into bundles,
each of which consisting of all the residue curves that start and end at the same nodes.

3.

The region defined by each bundle of residue curves is called a distillation regions.

4.

Distillation regions are separated by separatrices.

5.

Residue curves may not cross separatrices.

6.

Each distillation region has two end nodes (low and high boiling component or
azeotrope) and one or more saddles (intermediate boiling component or azeotropes).

7.

From the above, two distillation regions must not share both end nodes (low-boiling and
high-boiling nodes), although they may share one of the two.

3 Classification of RCM - DRD (Distillation Region Diagrams)

RCMs can be classified according to the number of binary azeotropes they form, the
presence or absence of a ternary azeotrope, and the boiling point order of the
components and azeotropes. Depending on these characteristics, they fall into one of
125 different distillation region diagrams (DRD). (Perry Chapter 13). A DRD is a
qualitative (topologically equivalent) RCM, with curved boundaries replaced by
straight segments.
Each DRD is characterised by one or more numbers consisting of 3 to 7 digits. These
digits represent the sequence (in increasing order) of the boiling points of the
components and azeotropes, which are given the following ID numbers:
1: lightest component
3: intermediate component
5: heaviest component
2: azeotrope formed by 1 and 3 if any
4: azeotrope formed by 3 and 5 if any
6: azeotrope formed by 1 and 5 if any
7: ternary azeotrope if any.

For example, (6135) indicates that there is one binary azeotrope (6) formed by the
heaviest (5) and lightest (1) components, and this azeotrope's BP is lower than those
of the pure components.
Thus, from this set of number the DRD can be drawn, with the appropriate arrows on
the distillation boundaries (each arrow moves from a low BP node to a high BP node).
For example, let's see how the DRD for 132567 may be drawn (see figure).

First, remove the non-existent azeotrope, leaving only 2, 6 and 7 (Fig. a).

Then, put in the arrowhead on the line sections, pointing towards the higher boiling
nodes (Fig. b).

Next, notice that there are two low-boiling nodes, which all arrows point away from
(nodes 1 and 3). Thus we must have at least two bundles of residue curves, or two
distillation regions. By drawing a few trial residue curves starting from near nodes 1 and
3, we can see that they form bundles that define distinct regions (Fig. c).

Finally, we separate the bundles by joining 2 to 7 and 6 to 7 to form separatrices, thus

distinguishing the distillation regions (Fig. d).

You may check that no other separatrix can be drawn. For example, if you draw another
separatrix joining 1 to 7, you will obtain two bundles of curves (i.e. two distillation

regions) both starting at 1 and ending at 7 (e.g. 1-2-7 and 1-6-7), which is not allowed
by definition.

A few of the 125 DRDs are shown below.

4 What can we do with RCMs?

RCMs are easy to obtain - all that's needed is a hot plate and some analytical
instrument. (You can also use a computer program such as Aspen Plus - but make sure
the thermodynamic model/equation is suitable for the system considered.)
RCMs are the only way to detect saddle (intermediate boiling) ternary azeotropes.
Although RCMs are obtained from batch distillation, they are identical to the liquid
concentration profiles in ideal packed columns operating at total reflux (see
Appendix), and closely resemble the liquid compositional profile of continuous
columns operating at total reflux. Even if the column does not operate at total reflux,
the separatrices still closely resemble distillation boundaries in continuous distillation
(lines that the composition profile in the column cannot cross), and the end-points
(pure component and azeotropes) are the same.
Hence RCM gives qualitative information on

the feasibility of obtaining a given product from a mixture by simple distillation

the necessary concentration of solvent or entrainer (a solvent or entrainer is a

third component added to an azeotropic-forming binary mixture in order to
achieve a separation). The right amount of solvent/entrainer must be added to
move the feed mixture to the correct distillation region on the map - one in
which the desired product can be reached by a residue curve.

How complex distillation systems can be designed to separate azeotropic

mixtures.

5 Conditions of feasibility for distillation

If a distillation is to be feasible (give the desired product compositions), the following
criteria must be satisfied:
1. Feed, distillate and bottoms must be on the same straight line (mass balance line)
by lever rule.
2. Bottom and distillate composition must lie (to a very close approximation) on
the same residue curve.
Note: The feed composition does not have to lie on the same residue curve as the
bottom and distillate. In fact, when a separatrix is curved, the feed does not even have to
lie in the same distillation region as the bottom and distillate! (see figure below.)
However, the liquid on the feed plate must be on the residue curve.

When all separatrices are straight, the feed composition must be in the same distillation
region as the bottoms and distillate compositions.
Thus, given the RCM (or at least the DRD) and the feed composition, we can
determine the range of possible product compositions. Since residue curves do not
cross separatrices, the distillate and bottoms compositions must be in the same
distillation region. However, even within the distillation region containing the feed,
only a certain sub-range can contain the product composition (Perry 7th edn, Fig. 1361). The sub-range must contain all the portions of residue curves that can be
intersected at least twice by a straight line through the feed composition, as required
by criterion 1 and 2.
Figure (a) below shows the portions of ONE particular residue curve that can be
intersected twice by mass balance (straight) lines through a given feed point F. If we
draw this for ALL residue curves (b), we obtain a bow-tie shaped area centered on the
feed, formed by all the dots representing possible product compositions.

(a)

(b)

Example A: Design a distillation system to break a lowboiling binary azeotrope AB using entrainer E (Perry 7th edn
p.13-70). The DRD is shown on the right.

Solution:
First, sketch a few residue curves in the region of concern.

Since the entrainer will be recycled, it is likely not be pure E

but will be the AE azeotrope. We mix this with the feed to get
a mixture M (shown by the mixing point on the right.

The mixture M is separated in an azeotropic distillation

column, getting pure B as bottom products and AE binary
solution out the top. From the lever rule, M and the products
must lie on a straight line, as shown. We check that this
distillation is feasible by verifying that a residue curve can be
drawn through the top and bottom products.

Then we separate the AE binary mixture in a simple

distillation column. The distillate will be pure A, while the
bottoms will be the AE azeotrope, which we re-use in the first
column.
A flowsheet of the system is sketched below.

Example B: Design a distillation system to break an intermediate-boiling binary

azeotrope AB using entrainer E (Perry 7th edn p.13-71). (This is a mirror image of
example A!)

Example C: Separation of ethanol-water solution by using cyclohexane entrainer

(Perry 7th edn p.13-75). See also accompanying presentation on Blackboard.

The following show the RCM and the phase diagram (the latter is for the temperature
in the decanter). Note the low boiling ternary azeotrope on the rcm and the presence of
two liquid phases on the phase diagram.

The process is shown below:

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Graphical analysis of process:

1. Feed (EW) is separated into W (B3) and EW azeotrope (D3) in column C3.
2. EW azeotrope (D3) is distilled together with entrainer-rich ternary mixture O4 in
column C1, bringing us into region 3 (bottom right) and producing ethanol and
near-ternary azeotrope D1.
3. Upon condensing D1 splits into two liquid phases, entrainer-rich O4 and entrainerpoor A4. This phase split enables us to escape out of distillation region 3.
4. A4 is distilled in column C2 (operating in region 1) to produce ternary azeotrope
D2 and E-W mixture B2, which is similar to the original feed
5. B2, which is a binary mixture similar to the original feed, is fed back to column
C1.

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APPENDIX 1: Concentration profile for packed distillation column at

total reflux
In this appendix we prove that the variation of liquid concentration along a packed
distillation column operating at total reflux is the same as the variation of liquid
concentration in a batch still, and hence can be described by a residue curve.
Consider the column shown below:
Material balances between any cross-section and the top of the column:
Vyi = Lxi
V=L
hence
yi = xi
The rate of mass transfer from vapour to liquid over a differential section
of column is
Ldxi = kY dA (yi - Kixi)
but since yi = xi:
Ldxi = kY dA (xi - Kixi)
yi+dyi
xi+dxi

dxi

kY dA
1 Ki xi
L

Similarly for component j:

dx j

V, yi
L, xi

kY dA
1 K j x j
L

Dividing the last two equations, we get an equation for the relative chance

dxi
K 1 xi
i
dx j K j 1 x j

which is the same as Equation 1 for the residue curve for batch distillation
derived earlier.

LEADING QUESTIONS
1. Define an azeotrope, a high boiling azeotrope, a low boiling azeotrope.
2. When you boil a mixture, the temperature (a) always rises or stays constant (b)
always falls or stays constant (c) depends on whether the mixture form a high
boiling azeotrope or a low boiling azeotrope.
3. True or false: if you boil a mixture which forms an azeotrope, you always gets the
azeotrope in the last drops of residue.
4. What does RCM stand for?
5. Describe how to obtain a residue curve experimentally.
6. Is an RCM the same as a ternary phase diagram? If not, in which ways are they
different?
7. What is a saddle component? An end node?
8. How many saddles can there be in a distillation region? How many end nodes?
9. In a distillation region, which node or saddle do residue curves start from? end at?
10. Explain how the residue composition evolves in a ternary mixture with no
azeotrope,.
11. What is a separatrix of an RCM?

12

12. What is the difference between an RCM and a DRD? Which one actually shows
residue curves?
13. Test yourself by trying to draw the DRD from a number, and by writing down the
number for a given DRD in Perry.
14. Under what conditions will a residue curve be identical to the composition profile
along a distillation column?
15. Give the two RCM-based criteria for the feasibility of a distillation scheme. Show
how they lead to bowtie-shaped areas representing possible product composition.
What is the centre of the bow-tie?
16. Is it true that for distillation to be feasible, the feed and products' compositions
must lie on the same residue curve? How about in the same distillation region?

13

EXERCISES
Q1.

Explain the meaning of the mixture index (14735) and draw the corresponding DRD.
Do the same for mixture (41735). What do you notice?

Q2.

On the accompanying RCM, which residue curves can be intersected at least twice by a
straight line through the feed composition F, with F lying between the intersection
points? (The intersection points represent possible bottoms and distillate compositions
from a distillation column at or near total reflux.) Hence draw the bow-tie shaped region
of reachable product compositions.

Q3.

For a ternary mixture ABC, a few residue curves

have been obtained experimentally as shown. Do
the following azeotropes exist, and if so, are they
low boiling, high boiling or saddle azeotropes?
How can you tell?
(a)
(b)
(c)
(d)

AB azeotrope
BC azeotrope
AC azeotrope
ternary azeotrope

14

Q4.
Using the definition of distillation regions, draw DRD 213567 and explain why you
can't join the LI azeotrope to to the ternary azeotrope to form a separatrix.
Q5.

The RCM for water (W) - ethanol (E) - cyclohexane (C) is shown, with azeotropes
being denoted by a combination of letters.
(a) How many azeotropes are there?
(b) List the low-boiling binary azeotropes and the high-boiling binary azeotropes.
(c) Is the ternary azeotrope low-boiling, high-boiling or saddle?

Q6.

Pure ethanol is to be obtained from a 50-50 mixture of water and ethanol. Using the
RCM above, comment on the feasibility of the following schemes: (a) Introduce pure
cyclohexane as an entrainer in an azeotropic distillation column (b) Introduce a 50-50
mixture of cyclohexane and ethanol as entrainer in an azeotropic distillation column; (c)
Distill to get a near-WE azeotrope, then mix with CE azeotrope and distil in a second
column.

15