Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
2. NESTED POLYGONS
60
industriallyreasonable conditions.
A + B + C ....... X + Y + Z .
(I)
A+L=N
N + B = Z + L.
(4a)
N + O = Z.
(4b)
(5)
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
A
A
im
62
yields of which are less than a few per cent, and this
involves the engineering of extensive separation and
recycle systems. However, it is generally agreed that for a
reaction to be commercially feasible its Gibbs free energy
difference must be less than about 10 kcal/gmole. In a
Solvay cluster, a very large negative Gibbs free energy
difference is not desired, since it indicates excessive
stability of intermediate chemicals, which will cause
problems elsewhere in the cluster. The necessary
conditions are
~Gj~<~
(6)
(1 la)
(llb)
!
I
TL
REACTION CONDITIONS
T.
I "w4//,
r. T3
r.
REACTION CONDITIONS
(a)
(b)
Common difference
Z-B=A
N-L=A
N-L=Z-B=A
netA + B = Z
(7)
reaction (1) A + L = N
(8a)
net
(1)
(2)
reaction (2) B + N = L + Z.
(8b)
Reaction
Common difference
netA +B+C=Z
Z-B-C=A
(1) A + L = N
N-L
(2) N + K = L
+P+Q
(3) B + C + P + Q
=K+Z
(12a)
(12b)
(12c)
=A
(13a)
(13b)
P+Q-K=N-L=A(13c)
(13d)
(10b)
where Gj is the free-energy of formation of compound j.
The differences between N-type and L-type intermediates identifies species A as the common difference. It
can be seen that the thermodynamic necessary conditions
appear as the ladder structure on the free energy-reaction
condition diagram shown in Fig. 5(b). Movement to the
right and left on a given line involves changing the state of
reactants and products, and the conditions under which a
H2
63
Cli~
~.
RHCl
,.=
300eK
1500"K
TEMPERATURE
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 intermediate 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).
(14)
(15)
64
(16a)
(16b)
(16c)
(16d)
Q
g
>(.9
r,,
tO
Z
bJ
|
W
W
I,I.
m
o
E
i
3OO
5OO
Z
I
W
W
t ['K]
IO00
15OO
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 representation 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
300
500
t['K]
I000
1500
65
,a
z
hi
U.
500
['K]
IO00
1500
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
(17a)
(17b)
66
),,
n,,
I&l
tL
Q2
i
300K
1500K
TEMPERATURE
Fig. 12. The introduction of [-1/202] as a common difference and an artificial common edge.
solution procedure, because oxygen is involved in
numerous reactions. A number of these reactions, plotted
on the G-T diagram in Fig. 13, are
C - CO =
1/2C - 1/2CO2 =
2FeO - Fe203 =
Pb - PbO =
2Fe304 - 3Fe203 =
2Mn304- 3Mn203 =
Cu20 - 2CuO =
MnO - MnO2 =
2PbO - P304 =
!/202
1]202
1/202
1/202
1/202
1/202
1/202
1/202
1/202
(18)
C
0
2HCI
-I0 -
3O0
500
I000
",k " - . , a
1500
rt-K]
Fig. 13. The use of an artificial common edge, Fig. 12, to construct
a free energy-reaction condition diagram with [-1/202] as the
common difference.
67
['KI
O,
>tel
Z
bJ
i
bJ
LI
h
300
,500
I000
1500
3OO
t [K]
500
IOOO
15OO
Fig. 14b.
Fig. 14c.
(21)
- 2HCI
+ C12
= 02
N - L = C12
N
1
H 2 0 - 2HC1 + ( - L) = 302.
(19a)
(19b)
(20)
2HCl
C + H20 = CO + H2.
2HCI
/
CIz
/J~'CIz
Fig. 15. The superpositionof Fig. 6 and Fig. 12to obtain a multiplecommondifferenceshown in Fig. 16.
(22)
68
e-q
CONCLUSIONS
tO
Z
tO
W
Ilg
U.
300
500
I000
1500
T ['K]
H2
HE
2 HCl
2HCI
Cl2
H2
2HCl
2HCI
Cl2
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 involved
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 Chemistry, 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.