&mid .&gin&t@ S&a-, 1976, Vol. 31. pp. 701-703. Pergamon Press.

Printed in Great Britain

ACCESSIBLE DESIGNS IN SOLVAY

CLUSTER SYNTHESIS

DALE F. RUDD
The Chemical Engineering Department and The Mathematics Research Center,
University of Wisconsin, Madison, WI 53706,U.S.A.

(Received 15 October 1975;accepted 8 January 1976)

Abstract-Sdlvay clusters are sets of intermediate chemical reactions that execute a desired net reaction. We show
that May-Rudd polygons give access to all Solvay clusters that involve two and three intermediate reactions
regardless of the number of chemical species involved, and to all clusters that involve fewer than nine chemical
species regardless of the number of chemical reactions. More elaborate Solvay clusters are accessible providing they
exhibit a planar topological structure.

INTRODUCTION synthesis that creates stoichiometrically consistent and

In this paper we examine the limits placed on any theory
of Solvay cluster synthesis that involves the use of
May-Rudd polygons. May and Rudd[ l] proposed a theory
for synthesizing sets of chemical reactions to replace a
desired but infeasible net reaction, the Solvay soda ash
process being the classic example of this method.
Doubtless, more elaborate theories of Solvay cluster
synthesis will be developed and we are concerned with
the inherent limitations imposed by the use of this
particularly useful way of representing the system
stoichiometry. The accessible designs are identified by
use of topological arguments.
SOLVAY CLUSTRRSYNTIWIS
In the Solvay soda ash process the infeasible net
reaction
2NaCl+ CaCO3= NaXO3 + CaC12
is replaced by the six intermediate reactions, each of
which moves rapidly to the right at industrially reasonable
reaction conditions.
thermodynamically feasible sets of reactions, and that
directs the search for superior clusters. We do not discuss
this theory in detail, but merely outline the reasoning.
Synthesis begins with the selection of a class of half
reactions based on a chemical species such as Cl*or Oz. A
free energy-reaction condition diagram is formed, and
thermodynamically feasible sequences of reaction appear
as a ladder pattern on this diagram. Synthesis continues
by the introduction of new sets of half reactions carefully
selected to give access to potentially useful chemistry.
This leads to a wide variety of Solvay clusters that pass
the test of stoichiometric and thermodynamic feasibility
and which must be examined further to identify commer-
cially attractive clusters.
A polygon representation of the emerging Solvay
clusters is suggested to guide the selection of useful half
reaction sets. The net reaction to be bypassed and the
intermediate reactions to be exploited form a nested
polygon with each face of the polygon representing a
single reaction. This pictorial representation of the
stoichiometry is very effective in suggesting new direc-
tions to examine in Solvay cluster synthesis.

CaCO3= CaO + CO*, 1,OOO”C (1) DUALITY

CaO + Hz0 = Ca(OH)z, 100°C
Ca(OH)z + 2NHXl= CaClz + 2NH3+ 2H20,12O”C (3)
2NH3+ 2H20 + 2COz= 2NH.,HCO,, 60°C
2NHJ-IC0, + 2NaCl= 2NaHC0, + 2NHXl,6O”C
2NaHC0, = Na#ZO, + Hz0 + CO*,200°C. (6)
A significant number of commercial processes employ
this replacement technique to bypass difficult reactions.
The central problem in industrial chemistry is the
discovery of new clusters of reactions to manufacture a
wide variety of chemicals.
May and Rudd developed a theory of Solvay cluster
Figure 1 shows the May-Rudd polygon representing the
(2) stoichiometry of the classic Solvay soda ash process.
Each face in the polygon corresponds to a single reaction
numbered in the previous section. The perimeter sum of a
face is equal to the reaction stoichiometry with the
(4) reactants directed clockwise and the products coun-
terclockwise. The net reaction forms the 7th outside
(5) infinite face into which the polygon is embedded. These
diagrams are drawn in the plane and permit no crossing of
lines. By construction the May-Rudd polygon is a planar
graph.
Also shown in Fig. 1 by the dotted lines is a second
graph known as the geometric dual of the May-Rudd
polygon. The dual is formed by placing seven points one
on each face of the polygon and by joining the points
according to the following rules. If two faces E and Fi are
adjacent draw a line joining the points pi and pi that

701
702
2NaCI
c)
--L
8
0”
z
i mental graphs play an important role in the incompletely
Fig. 1. The May-Rudd polygon for the Solvay soda ash process
with the geometric dual dotted.
intersects the edge common to the two faces. The line is
directed from the face in which the edge is a product to
the face in which the edge is a reactant. The net reaction
point corresponds to the 7th exterior face in Fig. 1.
We now make an important observation. The dual of
the May-Rudd polygon is the material flow sheet. This is
shown in greater detail in Fig. 2 for the Solvay soda ash
process. The whole purpose of using the May-Rudd
polygon is to guide the synthesis of useful process flow
sheets and we now have identified the link that exists
between the tool used to synthesize the flow sheet and the
flow sheet itself.
Whitney in 1933proved that the dual of a planar graph
is also planar and that an undirected planar graph is at the
most 2-isomorphic. A planar graph in which direction
conveys information and which is 2-isomorphic in its
undirected form is unique. Also a planar graph cannot be
the dual of a nonplanar graph. Conclusion: The May-
Rudd polygon is the unique dual of a planar process flow
NET REACTION
SOLVAY
CLUSTER
Na,CO
CaCO,
f
Fig. 2. The process flow sheet is the geometric dual of the
May-Ruddpolygon.
DALE F. RUDD
sheet and a planar process flow sheet is a unique dual of a
May-Rudd polygon.
NONF’LANARGRAPHS
We have shown that only a planar process flow sheet
can exhibit a May-Rudd polygon. This implies that strict
adherence to any synthesis policy that restricts attention
to May-Rudd polygons cannot give access to nonplanar
Solvay clusters. Is this a serious restriction? Quite a bit
can be said about this restriction using the theory of
nonplanar graphs.
Figure 3 shows two fundamental nonplanar graphs,‘
Kuratowski’s first and second graphs. Kuratowski’s first
graph is the nonplanar graph with the smallest number of
vertices, and Kuratowski’s second graph is the nonplanar
graph with the smallest number of edges. These funda-
developed theory of nonplanar graphs and are used here
to determine the accessible designs in Solvay cluster
synthesis.
K5 K3.3
Fig. 3. Kuratowski’s first and second nonplanar graphs. The tirst
graph Ks gives a bound on the number of chemical reactions and
the second graph K,, gives a bound on the numberof species.
Kurutowski’s first graph. If we view the first graph as a
process flow sheet of the form shown in Fig. 2, we see that
this represents a process with one net reaction and four
reactions of the Solvay cluster, each corresponding to a
vertex in the graph. Any graph with fewer vertices than
Kuratowski’s first graph must be planar. We conclude that
any Solvay cluster involving two or three intermediate
reactions must be planar and is accessible through the
May-Rudd polygon.
Kuratowski’s second graph. If we view the second
graph as a nonplanar May-Rudd polygon the edges
correspond to the chemical species involved in the net
reaction and the Solvay cluster. We see that this
involves nine chemical species, each corresponding to an
edge. Any graph with fewer edges than Kuratowski’s
second graph must be planar. We conclude that any
Solvay cluster that involves less than nine chemical
species must be planar and is accessible through the
May-Rudd polygon.
CONCLUSIONS
The line of thought developed rested on three critical
observations: First that the May-Rudd polygon and the
process flow diagram are geometric planar duals, second
that Kuratowski’s first graph bounds the nnmber of
reactions that can enter into a nonplanar Solvay cluster,
and third that Kuratowski’s second graph bounds the
 Accessible designsin Solvayclustersynthesis
number of chemical species that can enter into a
nonplanar Solvay duster. It was shown that the May-
Rudd polygon in process synthesis gives access to all
Solvay clusters that utilize two and three intermediate
chemical reactions regardless of the number of chemicals
involved and all Solvay clusters that involve less than nine
chemicals regardless of the number of intermediate
chemical reactions used.
Solvay clusters as elaborate as the Solvay soda ash
process that involves six chemical reactions and a dozen
chemicals are accessible by a properly conceived theory
of synthesis that utilizes the May-Rudd polygon and there
703
is no limit to the size cluster that can be synthesized.
However, there may exist inaccessible nonplanar clusters
beyond the stated bounds.
Planar embedding is being studied to extend the
May-Rudd polygon to nonplanar cluster synthesis.
REFERENCES
[l] May D. and Rudd D. F., Chem. Engng Sci. 197631 59.
[2] Deo N., Graph Theory with Applications to Engineering and
Computer Sciences. Prentice-Hail, Englewood CUTS, New
Jersey 1974.