Chemical EngineeringScience, 1976, Vol. 31, pp. 59--69. Pergamon Press.

Printed in Great Britain

DEVELOPMENT OF SOLVAY CLUSTERS

OF CHEMICAL REACTIONS
DROR MAY and DALE F. RUDD
ChemicalEngineeringDepartment,Universityof Wisconsin,Madison,W153706,U.S.A.

(Received30 May 1975;accepted 16July 1975)

Abstract--The Solvay soda ash process is the classic example of the replacement of an infeasible reaction by a
cluster of feasible chemical reactions involvingthe dosed-cycle use of intermediate chemicals. Many industrial
processes are based on this strategy.Previously,there had been no principlesto guidethe developmentof the proper
sequence. In this paper we present certain practical methods of synthesis useful in creating thermodynamically
feasible closed-cyclechemical reaction sequences.

1. INTRODUCTION the right rapidly at reasonable operating conditions with

Ernest Solvay in 1860 discovered the following cluster of
six chemical reactions each of which shifts rapidly to the
right at industrially reasonable operating conditions.
CaCO3 = CaO + CO2 1,000°C
CaO + H20 = Ca(OH)2 100°C
Ca(OH)2 + 2NH4C1 = CaCI2+ 2NH3 + 2H20
120°C
2NH3 + 2H20 + 2CO2 = 2NH4HC03 60°C
2NH4HCO3 + 2NaC1 = 2NaHCO3 + 2NH4CI 60°C
2NaHCO3 = Na2CO3 + H20 + CO2.2000C
The net result is the conversion of salt and limestone into
soda ash and calcium chloride, a chemical reaction that
does not occur directly under industrial conditions
2NaC1 + CaCO3 = Na2CO3 + CaC12.
The Solvay soda ash process based on these reactions is
the classic example of the closed-cycle use of clusters of
intermediate chemicals and chemical reactions to bypass
an important but unwilling chemical reaction.
Similar Solvay clusters drive a score or more commer-
ciai processes including those that manufacture sulfuric
acid, carbon tetrachloride, ethyl ether, isopropanol,
aniline, hydrogen peroxide, ethylene glycol, butadiene,
acetaldehyde, hydrogen cyanide, sodium thiosulfate,
Chlorine and vinyl acetate [2]. There is now interest in the
development of Solvay clusters for the thermal-chemical
splitting of water to obtain hydrogen[l] and for minerals
separation [4].
These processes are distinguished by their internal
generation and consumption of intermediate chemicals
that apparently have little relation to the net chemical
reaction. In the Solvay soda ash process above ammonia
and its compounds do not appear in the net reaction but
are intimately involved in the reaction sequence that
comprise the net reaction. The development of such
obscure sequences of reaction is a poorly understood and
a critical part of the art of industrial chemistry.
An abundant literature is available on the analysis of
proposed chemical reaction sequences, as Wentorf and
Hanneman illustrate [5]. The criteria that identify useful
sequences include that the reactions individually move to
59
sufficient yield, safety, and economy. Unfortunately,
there are no principles to guide the synthesis or
development of closed-cycle sequences of reactions [3].
Three conditions must be met by every single reaction.
First, the reaction must be stoichiometrically consistent
because of the principle of mass conservation. Second,
the theoretical equilibrium conditions must guarantee the
formation of the reaction products. Third, the reaction
must proceed towards equilibrium at a sufficiently high
rate.
The stoichiometric integrity of a Solvay cluster is
non-negotiable in that intermediate materials must be
produced and consumed in exact amounts. Some flexibil-
ity exists in the thermodynamic conditions of equilibrium
by changes in the temperature and pressure at which the
reactions are executed; but this is a limited flexibility.The
development of new catalysts can speed slow reactions
and increase selectivity. However, no catalyst can
overcome unfavorable equilibrium. It is only by the
introduction of the intermediate reactions of a Solvay
cluster that thermodynamic infeasibility can be bypassed.
Hence our concern with these two dominant features of
chemical reactions; stoichometric integrity and favorable
equilibrium.
In this paper we examine the role that a geometric
representation of the problem can play in the synthesis of
Soivay clusters. It is shown that the stoichiometry of the
net reaction ought to be represented as a polygon and that
any Solvay cluster must form polygons that nest inside
the net reaction polygon. Further, we show that ther-
modynamically feasible Solvay clusters form a ladder
pattern on a particular free energy-reaction condition
diagram, and that a useful link exists between that
diagram and the cluster stoichiometry. The synthesis of
thermodynamically feasible Solvay clusters is shown to
be a problem in pattern recognition.
2. NESTED POLYGONS
The following notation is used, letters in the beginning
of the alphabet (A, B, C...) denote reactants in the main
reaction, and those near the end of the alphabet
(Z, Y, X, W...) denote products of the main reaction. The
main reaction is presumed to be difficult to execute at
60 D. MAY and D. F. RUDD

industriallyreasonable conditions.

A + B + C ....... X + Y + Z . (I)

Intermediate chemical species that enter into a Solvay

cluster are denoted by letters near the middle of the
alphabet and are divided into two classes; an L-class of
intermediate (L, K, J...) and an N-class of intermediates
(N, O, P...). The L-class are intermediates that we elect
to use to drive certain reactions in the Solvay cluster and
the N-class are the intermediates that are generated by
those reactions. For example, the reaction
A+B=Z
(2) cluster (3a), (3b). This divides the triangle of the net
has the following Solvay cluster:
reaction (1) A+L=N (3a) Solvay cluster. The properties of these polygons are
reaction (2) N + B = Z + L. (3b) extremely interesting and useful.
In reaction (3a) species L is an independent intermediate
and N is the product of the reaction of A and L. Notice
how the role is reversed in reaction (3b). The segregation
of intermediates into L-class and N-class intermediates is
dependent on the order of the individual reactions in the
Solvay cluster, and is therefore an arbitrary but useful
convention.
A property of a Solvay cluster is that the intermediates
that are produced by reactions in the cluster must also be
consumed by other reactions in the cluster the net result
being the main reaction. Further, the intermediates must
be generated and consumed in different ways within the
cluster, leading to the need for separating the products of
reaction. For example, the following sequence of reac-
tions is not a Solvey cluster:
A +B=N+O (4a)
N + O = Z. (4b)
Since, the intermediates N and O are produced and
consumed in the same way, and the reaction sequence can
be written as the topologically simple form:
A +B = N + O =Z. (5)
These simpler sequences can be examined quite easily
since they do not involve the introduction of foreign
intermediates~ only the rearrangement of the reactants
and products of the mean reaction.
Any balanced chemical reaction can be represented by
a polygon constructed with directed edges denoting the
reactants and products. The reactants are assigned a
clockwise direction and a negative si~, and the products
a counter clockwise direction and a positive sign. The
perimeter sum of any polygon representing a balanced
chemical reaction must equal zero. The order in which
the reactants and products appear in the perimeter of the
polygon is arbitrary and has no significance. Figure 1
illustrates this geometric notation.
A Solvay cluster divides the main reaction polygon into
Fig. I. Polygonrepresentation of reaction (2).
as many regions as there are reactions in the cluster. For
instance, in Fig. 2 the net reaction (2) is replaced by the
reaction into two regions, and the perimeter sum of each
region gives the corresponding reaction. Figure 3 illus-
trates the geometric representation of typical industrial
A ®
Fig. 2. The nested polygonsof the Solvaycluster (3a) and (3b).
Each regioncorrespondsto an independentreaction.
The set of nested polygons for any Solvay cluster must
form an acyclic directed graph, since the perimeter sum of
each and every loop must represent a balanced chemical
reaction. A chemical reaction must have reactants and
products, and the corresponding polygon cannot have
edges all in the same direction.
Whenever the border line between sub-region is formed
with edges all of the same direction, no L-class
intermediates are involved in that local reaction scheme
and the nested polygon does not form a Solvay cluster. All
interior border lines must consist of sequences with edges
in both directions. Figure 4 illustrates several important
classes of Solvay structures.
This simple nested polygon representation of the
stoichiometry of Solvay clusters is very important in
synthesis. New reactions can be added to a partially
developed polygon and the stoichiometric consequences
assessed immediately and pictorially. The geometry of the
partially completed polygon can give valuable leads to
where and how new reactions ought to be brought in. We
develop this idea further in the next section.
3. CLUSTER ANALYSISBY THE COMMON DllqI'ERENCE
It is necessary that the chemical equilibrium reside with
the products to some extent in each of the individual
reactions that comprise the Solvay cluster. Commercial
processes have been built about reactions the equilibrium
 Development of Solvay clusters of chemical reactions 61

2 No CI

.o ",~i

,.t, O "~

Fig. 3. Several illustrative Solvay clusters: Solvay soda ash process, thermochemical splitting of water, production
of acetaldehyde.

C
im

®
Q

Fig. 4. Several important classes of Solvay clusters.

62 D. MAY and D. F. RuDn

yields of which are less than a few per cent, and this It is extremely useful to represent the above graphically
involves the engineering of extensive separation and using the rearranged inequalities.
recycle systems. However, it is generally agreed that for a
reaction to be commercially feasible its Gibbs free energy Gz - GB > GA + e all conditions (1 la)
difference must be less than about 10 kcal/gmole. In a
Solvay cluster, a very large negative Gibbs free energy GN - GL<~GA + e conditions (1) (llb)
difference is not desired, since it indicates excessive
stability of intermediate chemicals, which will cause GN - GL + ,>~ Gz - Ga conditions (2). (llc)
problems elsewhere in the cluster. The necessary
conditions are These criteria are shown in Fig. 5(a) in which
temperature is taken as the variable that defines the
~Gj~<~ (6) reaction conditions. Reactions (Sa) and (8b) must be run at
sufficiently different conditions to insure the close
for any reaction j in the Solvay cluster, where e is the approach or crossing by the N - L line of the A and Z - B
maximum value of Gibbs free energy of reaction, on the lines. If such conditions cannot be found, the proposed
order of 10 kcal/gmole. Solvay cluster is not feasible.
This thermodynamic criterion is necessary but not
sufficient to qualify a Solvay cluster as industrially
attractive. Reaction rate problems, lack of selectivity,
difficult materials handling and separations, and other
problems confound the search for commercially useful
reaction sequences. However, the thermodynamic criter-
ion necessarily must be met by all reactions and is, for
!
this reason, a useful basis for the development of general
principles of reaction sequence synthesis. We restrict
ourselves to this dominant and necessary but not I i I I "w4//,
sufficient condition for assessing the feasibility of Solvay TL T. r. T3 r.
REACTION CONDITIONS REACTION CONDITIONS
clusters, with the understanding that further screening
will eliminate some of these clusters. (a) (b)
We now show how it is useful to classify chemical Fig. 5. The ladder pattern to identify. Solvay clusters that
reactions according to their common differences and how satisfythe maximumfree energycriterion.
the concept of the common difference leads to a graphical
representation of the thermodynamic necessary condi- Notice further that the ladder-like plot in Fig. 5(a) does
tions. We then show that the common difference between not involve the free energy of any reaction, but it involves
reactions is also a common edge in the polygon differences of the free energy of formation of the certain
representation of reaction stoichiometry, thereby linking species that enter into the reactions. These particular
the stoichiometric and thermodynamic criteria. This then differences in free energy are identified as the common
leads in the next section to methods for the synthesis of difference between the N and L type intermediates. By
Solvay clusters that are thermodynamically feasible. rearranging the equations we define the common differ-
Let us now examine the two step Solvay cluster shown ence.
in Fig. 2.
Reaction Common difference
netA + B = Z (7) net A+B=Z Z-B=A (12a)
(1) A+L=N N-L=A (12b)
reaction (1) A + L = N (8a) (2) B+N=L+Z N-L=Z-B=A (12c)

reaction (2) B + N = L + Z. (8b) Similarly we examine the three-step cluster of Fig. 5(b)

If the net reaction is not thermodynamically feasible Reaction Common difference

netA +B+C=Z Z-B-C=A (13a)
AGnet= Gz - (GA + GB) > E all reaction conditions (1) A + L = N N-L =A (13b)
(9) (2) N + K = L +P+Q P+Q-K=N-L=A(13c)
(3) B + C + P + Q =K+Z (13d)
and if the Solvay cluster is to be feasible
The differences between N-type and L-type inter-
AG1 = G~ - (GA + GL) ~<e reaction conditions (1) mediates identifies species A as the common difference. It
(10a) can be seen that the thermodynamic necessary conditions
A G2 = ( GL + Gz) - ( Ge + GN) <<-e reaction conditions (2) appear as the ladder structure on the free energy-reaction
(10b) condition diagram shown in Fig. 5(b). Movement to the
right and left on a given line involves changing the state of
where Gj is the free-energy of formation of compound j. reactants and products, and the conditions under which a
 Developmentof Solvayclustersof chemicalreactions
H2
RHCl
Fig.6. The free energy-reactionconditiondiagramfor the decompositionof HC1.The commondifferenceis [C12].
given reaction should be executed; the jump from line to
line corresponds to executing a reaction, The jumps
between lines can only occur if the lines are within the e
distance. The general trend is that of climbing from
reactants to products along the ladder defined by the
common difference equations.
In summary, the necessary thermodynamic conditions
identifying the feasible Solvay clusters can be represented
by suitable inequalities that can be plotted on a free
energy-reaction condition diagram. Some of these lines
must approach each other within a suitable e to form a
ladder structure. If a proposed Solvay cluster does not
exhibit the proper geometric pattern on this diagram, the
cluster is not thermodynamically feasible.
We next demonstrate the simultaneous use of the
nested polygon representation and the free energy-
reaction condition diagram to synthesize reaction sequ-
ences that are both thermodynamically and stoichiometri-
tally feasible.
4. COMMONDIFFERENCEAS A COMMONEDGE
The development of Solvay clusters involves the
simultaneous concern for the maintenance of the
stoichiometdc integrity of the reaction sequence and
concern for the thermodynamic feasibility of every
individual reaction. Each proposed cluster must form a
nested polygon within the polygon representing the net
reaction, and the cluster must form a free energy-reaction
condition diagram that exhibits the proper pattern of free
energy differences intersections. Without some well
defined method the search for feasible Solvay clusters is
hopelessly complicated by the large number of inter-
mediate chemicals and reactions forming geometric
combinatorial problems currently beyond comprehension.
We make a critical observation. In Fig. 5(a) we have
chosen to represent the thermodynamic inequalities in
terms of free energy differences GA, G N - G L and
Gz - Ge. Notice in Fig. 2 that A is the common edge to
reaction (Sa) and the net reaction (7), that being
represented algebraicly by eqns (12a) and (12b).
tin the illustrativeexampleswe deal with simplifiedchemistry
recognizing the reality of complex competing reactions and
nonstoichiometric compounds,but ignoring these to ease com-
prehension.
*It is convenient to think of the left-hand side of (15) as
half-reactionsto be assembled into a Solvay cluster.
63
~. Cli~
,.=
300eK 1500"K
TEMPERATURE
Stoichiometric integrity and thermodynamic feasibility
are linked by the common edge A in the nested polygon
notation and the common difference A in the free
energy-reaction condition diagram.
This observation leads to the general principle that the
thermodynamic feasibility of a reaction sequence can be
tested on a single free energy-reaction condition diagram
so long as the reaction cluster forms nested polygons with
a common edge. A single free energy-reaction condition
diagram can be used to test the feasibility of a large class
of proposed Solvay clusters, that class being defined by
the common edge selected.
We now demonstrate how feasible Solvay clusters can
be synthesized by the sequential selection of reactions
with a particular common edge and by the recognition of
the ladder pattern in the free energy-reaction condition
diagram thus defined.t
Figure 6 illustrates the infeasible chemical reaction
2HCI = H2 + CI2. (14)
The infeasibility is shown in the free energy-reaction
condition diagram by the distance between the Gc~2and
the Gmc~-Ga: lines. We recognize that the free
energy-reaction condition diagram has been constructed
using C12 as the common difference.
The following chemical reactions also have Clz as the
common difference and can be plotted on the same free
energy-reaction condition diagram
COC12- CO = Ch
2CICh - 2CrCh = C12
2FeCI3 - 2FeCh = Ch
C r C h - CrCh = Ch
2MnCL- 2MnCh = Ch
CuCh- Cu = Ch (15)
HgCh- Hg = CI~
1/2MnCh - 1/2Mn = 02
2CrCh- 2CrCI~ = 02
2CuCI- 2Cu = Ch
P b C h - Pb = Ch.
Which of these half-reactions are candidates for feasible
Solvay dusters*?
All of the chemical reactions above have an edge in
common with the net reaction and therefore can be nested
within the net reaction polygon; they all are members of
64 D. MAY and D. F. RUDD

stoichiometrically feasible Solvay clusters. In Fig. 7 we

observe that few of these reactions satisfy the ther-
modynamic conditions defined in Fig. 5. One obvious
Solvay cluster stands out, that being

Net reaction: 2HCI = H2 + C12 (16a)

(1) 2HCI + 2CrCh = H2 + 2CrCh (16b)
(2) 2MnCI3 + 2CRC13= 2CRC12+ 2MnCL (16c)
(3) 2MnC14 = 2MnC13+ C12. (16d)
Q

>-
(.9
r,,
tO
Z
bJ
|
W
W
I,I.

m
o
E
i

3OO 5OO IO00 15OO

Z t ['K]
I
W Fig. 8. The heavy lines identify one ladder pattern, that
W
correspondingto reactions (16).
b.

300 500 I000 15OO

t[-K]
Fig. 7. The search for Solvayclusters involvingreactions (15).

To ease comprehension Fig. 8 emphasizes the pattern that

identifies the cluster above. In Figs. 9 and 10 a second and
third Solvay cluster are identified. The polygon represen- ,~
tation of these three clusters are shown in Fig. 11
emphasizing their common edge of C12.
The following procedure emerges from this example.
1. Define common difference, and assemble a set of
reactions based on this difference.
2. Plot this reaction set on a free energy-reaction
condition diagram.
3. Apply the ladder rules to this diagram and identify
the proper feasible Solvay clusters.

5. A R T I F I C I A L COMMON DIFFERENCE

SO far our attention has been focused on chemical

species that appear in the net reaction or are directly tied 300 500 I000 1500

to those species by the concept of a common difference.

In the example, the chlorides of chromium, manganese,
iron, and the like appear via their reactions that have
chlorine as a common difference.
We are not restricted by this route to alternate
chemistry. Other apparently unrelated compounds can be
introduced using the concept of an artificial common
t['K]
Fig. 9. A second ladder pattern for reactions (15).
edge. Chemical heuristics focus our attention on reactions
that have as their common difference, halogens, Sulfur,
oxygen and other compounds that partake in numerous
reactions. These common differences are translated into
 Developmentof Solvayclusters of chemicalreactions 65

common edges that are artificial to the original problem.

As we shall see the concept of an artificial common edge
is not even restricted to single molecules but can take the
form of any linear combination of molecules. The artificial
common edge need not appear in the final Solvay cluster,
it is mainly a theoretical tool for the construction of an
expanded set of clusters. We illustrate by example.
Now, suppose that chromium and mercury compounds
were ruled out in the previous example. Let us further
assume that no useful cluster was found when either He or
,a 2HC1 has been considered as a common difference. Is it
possible to synthesize feasible new Solvay clusters under
these restrictive circumstances?
The problem is that we do not have a proper common
difference to get started. This problem can be circum-
vented by introducing a new intermediate into the
z
polygon, and defining an artificial common edge. In Fig. 12
hi an artificial common edge [-1/202] was created by
U. introducing H20 into the polygon. In effect the overall
reaction (16a) was replaced by a Solvay cluster of two
reactions, not necessarily feasible.

2HC1 - H20 - C12 = -1/202 (17a)

- 11202 = H 2 - H20. (17b)
300 500 IO00 1500
T ['K] These two reactions are indicated on the G-T diagram in
Fig. 12 and as expected the resulting cluster is infeasible.
Fig. 10. A third ladder pattern for reactions (15). Now we have an excellent common difference to start the

H2

2HCI

Hz

2HCl

H2

Fig. 11. The Solvay clusters corresponding to the patterns appearing in Figs. 8, 9 and 10.

CESVol.31,No.1--E
66 D. MAY amt D. F. RUDO

),,
n,,
I&l
z

tL

J Q2
i

300°K 1500°K
TEMPERATURE

Fig. 12. The introduction of [-1/202] as a common difference and an artificial common edge.

solution procedure, because oxygen is involved in Applying the ladder-rules to Fig. 13 reveals a number of
numerous reactions. A number of these reactions, plotted feasible Solvay clusters that do not use chromium or
on the G-T diagram in Fig. 13, are mercury compounds. Two out of many possible clusters
are given in Fig. 14 with their polygon presentation.
C - CO = - !/202
1/2C - 1/2CO2 = - 1]202 6. MULTIPLE COMMONDIFFERENCES
2FeO - Fe203 = - 1/202 To demonstrate a new principle let us assume that the
Pb - PbO = - 1/202 reactions corresponding to the jumps from the line
2Fe304 - 3Fe203 = - 1/202 (18) 2 H C 1 - H 2 0 - C 1 2 to either -1/202, C u 2 0 - 2 C u O or
2Mn304- 3Mn203 = - 1/202 MnO - MnO2 are not desirable. Consequently, there exist
Cu20 - 2CuO = - 1/202 no feasible path on the G-T diagram (Fig. 13), that leads
MnO - MnO2 = - 1/202 from the reactants to the products.
2PbO - P304 = - 1/202

C
0
2HCI

-I0 - I I I I I I I e I I ",k " - . , a

3O0 500 I000 1500

rt-K]
Fig. 13. The use of an artificial common edge, Fig. 12, to construct Fig. 14a. Two feasible clusters synthesized using [,I/202] as the
a free energy-reaction condition diagram with [-1/202] as the artificial common edge. The ladder patterns are shown in Figs. 14b
common difference. and 14c.
 Development of Solvay clusters of chemical reactions 67

I I I I I [ I I I ] i

O,

>-

tel
Z
bJ
i
bJ
L¢I
h

300 ,500 I000 1500 3OO 500 IOOO 15OO

t [°K] r ['KI
Fig. 14b. Fig. 14c.

An enormous number of new Solvay clusters may be corresponding free-energies, which amounts to the
obtained by a combination of two reaction-sets, each with super-position of lines from Fig. 7 on the line 2HC1-
its distinctive common difference. In this case the H20 - C12 in Fig. 13. The resulting dotted lines in Fig. 16
polygons of Figs. 6 and 12 are superimposed, and the show a few of these super-imposed free-energy lines.
resulting polygon is given in Fig. 15(a), another combina- On this new G - T diagram the starting point is no longer
tion is illustrated in Fig. 15(b). Now we have to find some the line 2HC1- H20 - C12, but one of the dotted lines. By
way to represent two different sets of reactions on the using the ladder rules with Fig. 16 we generate many new
same G - T diagram. feasible Solvay clusters; an obvious one is given by the
Inspection of Fig. 13 shows that there is one line, i.e. lines,
one reaction, that explicitly involves C12; this is the line
2HC1 - H20 - C12. Without jeopardizing stoichiometry we 2HC1 - H20 - 2(MnCh - MnC13)
can replace C12by any reaction taken from the set whose 2MnO - Mn203 (21)
common difference is C12.This is easily seen by adding the C-CO.
two equations, (19a) and (19b) to obtain (20).
The corresponding reactions are,
H20 - 2HCI + C12 = ½02 (19a)
N - L = C12 (19b) 2HC1 + Mn203 + 2MnC13 = 2MnO + H20 + 2MnC14
N 1
H 2 0 - 2HC1 + ( - L) = 302. (20) 2MnCL = 2MnCI3 + C12
2MnO + CO = Mn203 + C (22)
The G - T diagram is obtained by summation of the C + H20 = CO + H2.

2HCl 2HCI

i /
/J~'CIz CIz

Fig. 15. The superpositionof Fig. 6 and Fig. 12to obtain a multiplecommondifferenceshown in Fig. 16.
68 D. MAY and D. F. RUDO

I I I I I I I I I I I The complementary procedure, to be used if the

previous simple one fails, is the following:
1. Introduce new species (one or more) into the
polgyon such that a new common difference can be
defined. The intermediate species should be selected to
generate a useful new common difference.
2. Follow the simple procedure.
e-q 3. If necessary, use more than a single common
difference, by proper superposition of the free energy
diagrams.
Examples of feasible Solvay clusters generated by this
w procedure are shown in Fig. 17.

tO CONCLUSIONS
Z
tO
We have demonstrated the usefulness of two particular
W
Ilg geometric representations in the synthesis of closed-cycle
U.
reaction sequences. The one is a polygon representation
of the complex stoichiometry of interdependent reactions,
and the other is a free energy plot based on certain
common differences of these reactions. A ladder-like
pattern in the free energy plot identifies sequences that
involve individual reactions for which equilibrium resides
sufficiently with the products. A large number of
thermodynamically feasible Solvay clusters can he
300 500 I000 1500
T ['K] synthesized rapidly for industrially important problems.
At the present state of development these methods
Fig. 16. The superposition of free energy lines using multiple apply to the synthesis of reaction sequences that satisfy
commonedges. the Gibbs free energy constraint. Within this large class of

H2 HE

2 HCl 2HCI

Cl2

H2

2HCl 2HCI

~ Cl2

Fig. 17. SeveralSolvayclusters synthesizedusingthe multiplecommonedgeconcept.

 Development of Solvay clusters of chemicalreactions
Solvay clusters more restrictive sub-classes can be
defined that involve efficient use of energy, rapid reaction
rates, easy separation, and selectivity of reactions.
Currently each synthesized feasible Solvay cluster must
be analyzed in more detail to determine these other
important criteria. Our method develops the basic
reaction sequences for this further screening.
In this paper, which appears to be the first published
work on methods for the synthesis of closed-cycle
reaction sequences, we have been concerned with the
development of a useful approach towards the initial
synthesis of Solvay clusters. From our suggested proce-
dures it is quite clear that a large number of ther-
modynamically feasible dusters can be generated. In a
subsequent paper we examine the underlying mathemati-
cal structure and develop methods that handle this
combinatorial problem, and produce more efficient Solvay
clusters. This approach is the basis for a computer-aided
search for feasible Solvay clusters.
Acknowledgements--This work was partiallysupportedby a grant
from the National ScienceFoundation.One of the authors (DFR)
was on the staff of the MathematicsResearch Center during part
of this study.
69
NOTATION
A, B, C,...K, L . . . . N, O. . . . X, Y, Z various
species, see text
E maximum value of Gibbs free energy of
reaction
AGj Gibbs free energy of reaction i
Gj Gibbs free energy of formation of species ]
Subscripts
A, B, C,... X, Y , Z , . . . indicating the species in-
volved
net the net reaction of a Solvay cluster
REFERENCES
[1] Chao R. E., Ind. Engng Chem., Proc. Res. Dev. 1974 13 94.
[2] Faith W. L., Keyes D. B. and Clark R. E., Industrial
Chemicals, 3rd edn. Wiley, New York 1965.
[3] MeissnerH. P., Processesand Systems in Industrial Chemis-
try, Chap, 10. Prentice Hall, EnglewoodCliffs, N.J. 1971.
[4] Novak R. and Schuster W., U.S. Pat. 3466196 (9 September
1969).
[5] Wentoff R. H. and Hanneman R. E., Science 1974 185 311.