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Advanced Data Analysis and
Modelling in Chemical Engineering
Advanced Data Analysis and
Modelling in Chemical Engineering
Denis Constales
Gregory S. Yablonsky
Dagmar R. D’hooge
Joris W. Thybaut
Guy B. Marin
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Preface
This book is written by Denis Constales, Dagmar D’hooge, Joris Thybaut, and Guy Marin
from Ghent University (Belgium) and Gregory Yablonsky from St. Louis University (United
States), who has been affiliated with Ghent University as a visiting professor for more than
15 years. During that period, we have been working toward the development of a center
of chemico-mathematical collaboration, organizing, among other things, the workshops
and conferences related to “Mathematics in Chemical Kinetics and Chemical (Bio)
Engineering” (MACKiE). More generally, we have attempted to contribute to the integration
of “Science-Technology-Engineering-Mathematics” (STEM).
Our book is a first consolidation of our efforts in this respect. It is about advanced data analysis
and modeling in chemical engineering. We dare to use the term “advanced,” as we aim to help
the reader to increase the level of understanding of the physicochemical phenomena relevant
for the field of chemical engineering using effective mathematical models and tools. This does
not mean that these models have to be complex, but rather that the complexity of a
mathematical model and the corresponding tools have to be optimal. Also, we would like to
stress that, in our opinion, the role of mathematics is not limited to that of servant of all masters,
a tireless and beautiful Cinderella, but that it provides an inexhaustible source of powerful
concepts, both theoretical and experimental.
Our Team
Denis Constales is associate professor at the Department of Mathematical Analysis in the
faculty of Engineering and Architecture of Ghent University. He obtained his doctorate there
and specialized in applied mathematics, with specific research interest in special functions,
integral transforms, and the application of computer algebra techniques.
Gregory S. Yablonsky is professor at St. Louis University. He is a representative of the
Soviet-Russian catalytic school, being a postdoctoral student of Mikhail Slin’ko and
having collaborated with Georgii Boreskov. He also was a member of the Siberian
chemico-mathematical team together with Valerii Bykov, Alexander Gorban, and Vladimir
Elokhin. He gained international experience working in many universities of the world,
xiii
xiv Preface
including St. Louis, United States; Ghent, Belgium; Singapore; Belfast, N. Ireland, United
Kingdom.
Dagmar R. D’hooge is assistant professor in Polymer Reaction Engineering and Industrial
Processing of Polymers at Ghent University. He is a member of the Laboratory for Chemical
Technology and associate member of the Department of Textiles. He was a visiting researcher
in the Matyjaszewski Polymer Group at Carnegie Mellon University (Pittsburgh, United States)
and the Macromolecular Chemistry Group at Karlsruhe Institute of Technology (Germany).
His research focuses on the development and application of multiscale modeling platforms for
designing industrial-scale polymerization processes and polymer processing units for both
conventional and high-tech polymeric materials.
Joris W. Thybaut is full professor in Catalytic Reaction Engineering at the Laboratory for
Chemical Technology at Ghent University. After obtaining his PhD on single-event
microkinetic modeling of hydrocracking and hydrogenation, he went to the Institut des
Recherches sur la Catalyse (Lyon, France) for a postdoc on high throughput experimentation.
Today, he investigates rational catalyst and reactor design for the processing of conventional
and, more particularly, alternative feedstocks.
Guy B. Marin is senior full professor in Catalytic Reaction Engineering and is head of the
Laboratory for Chemical Technology at Ghent University. He was educated in the tradition
of the thermodynamic and kinetic school of the Low Countries as well as of the American
school, with Michel Boudart as a postdoctoral adviser, and benefited from the Dutch school
of catalysis. The investigation of chemical kinetics, aimed at the modeling and design of
chemical processes and products all the way from molecule up to full scale, constitutes the core
of his research.
The authors abbreviated the title of this book to ADAMICE, which can suggest several
phonetic associations, the most primordial of which refers to Adam. It is quite symbolic
that Adam’s name in Hebrew shares an etymology with clay and blood, both of which are
catalytic substrates in chemistry and biochemistry. Maybe we can think of Adam as the
first ever model, and a very advanced model, too.
We gratefully acknowledge the outstanding skills, tireless activity, patience, and understanding
of our editing aide, Mrs Annelies van Diepen.
CHAPTER 1
Introduction
1.1 Chemistry and Mathematics: Why They Need Each Other
Chemistry needs mathematics. Mathematics needs chemistry. Since the Dark Ages, in
chemistry, or alchemy as it was called then, the so-called cross rule was well known for
answering questions regarding the preparation of solutions of a certain desired concentration.
This rule is not needed to answer simple questions, like which ratio of 100% alcohol and
pure water must be mixed to prepare a 50% alcohol solution: 50:50. For more complicated
questions, however, such as how to prepare a 30% alcohol solution from two solutions with
concentrations of 90% and 10% alcohol, the cross rule comes in handy (see Scheme 1.1A).
The rule works as follows. Write the desired concentration in the middle and the input
concentrations on the left. Then calculate the difference between the number on the top left (90)
and the one in the middle (30), and then write that number in the bottom right (60). Then
write the difference between the number on the bottom left (10) and the one in the middle (30)
in the top right (20). From this it follows that the solutions need to be mixed in a ratio of
20:60 ¼ 1:3. Scheme 1.1B shows the cross rule in generalized form, with α > γ > β.
90 20 = 30 − 10 a g−b
→
→
→
30 γ
→
→
→
10 60 = 90 − 30 b a−g
(A) (B)
Scheme 1.1
Cross rule: (A) example and (B) generalized form.
Now, how can we prove this rule? Our procedure should meet the requirement:
aα + bβ ¼ γ (1.1)
where α and β are known concentrations of solutions I and II and γ is the concentration of
the desired solution III. The constants a and b are the parts of solutions I and II that are
needed for preparing solution III. Obviously, the balance equation
a + b ¼ 1 or b ¼ 1 a ðor a + b ¼ 100%Þ (1.2)
Advanced Data Analysis and Modelling in Chemical Engineering. http://dx.doi.org/10.1016/B978-0-444-59485-3.00001-1

1
2 Chapter 1
must hold. Substituting Eq. (1.2) into Eq. (1.1) yields

aα + ð1 aÞβ ¼ γ (1.3)
from which follows that
γβ
a¼ (1.4)
αβ
Consequently,
γ β αγ
b¼1a¼1 ¼ (1.5)
αβ αβ
and the ratio is given by

γβ αγ
a:b¼ : ¼ ðγ βÞ : ðα γ Þ (1.6)
αβ αβ
which is the cross rule.
Thus, mathematics is needed for solving typical problems of chemistry. Such problems are
solved in every chemical laboratory, every pharmacy, and even in most kitchens. To do so, in
this case we are using what is known as linear algebra.
Mathematics needs chemistry too, not only for demonstrating its power and usefulness but also
for formulating new mathematical problems.
1.2 Chemistry and Mathematics: Historical Aspects

A mutual attraction between mathematics and chemistry was growing gradually during the 18th,
19th, and 20th centuries. Antoine Lavoisier’s law of the conservation of mass and John Dalton’s
law of multiple proportions could not have been discovered without precise weight
measurements. Chemistry transformed into a quantitative science, and Lavoisier and Dalton
became pioneers of chemical stoichiometry. From another side, Arthur Cayley, the creator of the
theory of matrices, applied his theory to the study of chemical isomers in the 1860s and 1870s.
Since the mid-19th century, various new concepts of physical chemistry, in particular laws of
chemical kinetics, have been developed. A few examples are
• the mass-action law by Guldberg and Waage.

• the “normal classification of reactions” by van’t Hoff.
• the temperature dependence of the reaction rate by Arrhenius.
• electrochemical relationships by Nernst.
• quasi-steady-state principle by Chapman and Bodenstein.
• theory of chain reactions by Semenov and Hinshelwood.
• model for the growth of microorganisms by Monod.
Introduction 3
All these principles have been proposed based on the solid mathematical foundation of
algebraic and differential equations. Moreover, the greatest chemical achievement,
Mendeleev’s periodic table, was created using a detailed critical review of quantitative data,
first of all, the atomic masses of known elements. A legend says that after the presentation of his
table in 1869, Mendeleev was asked, “Why did you categorize the elements based on their
mass and not on their first letter?” In fact, the mass of an element is not a chemical property; it is
not its ability to react with other substances, nor its likeliness to explode, and it is not even
a smell. So the number of an element in Mendeleev’s periodic table remained very formal—just
a number, the element’s place in the table—until, in 1913, Moseley discovered a mathematical
relationship between the wavelength of X-rays emitted by an element and its atom number.
This discovery was a great step in the understanding that the number of the element in the
periodic table is equal to the number of electrons (and the number of protons) belonging to a
single atom of this element.
During the “Sturm-und-Drang” quantum period of the 1920s, Heisenberg’s matrix mechanics
and Schrödinger’s equation have been established as “very mathematized” cornerstones
of the rigorous theory of elementary chemical processes, which changed the field of chemistry
dramatically.
Finally, in the 20th century, researchers discovered many critical chemical phenomena.
In the first half of the century, these were mainly of a nonisothermal nature (Semenov,
Bodenstein, Hinshelwood), while in the second half they concerned isothermal phenomena, in
particular oscillating reactions (Belousov, Zhabotinsky, Prigogine, Ertl). In the 1950–60s
special attention was paid to studying very fast reactions by the relaxation technique (Eigen).
All reaction and reaction-diffusion nonsteady-state data have been interpreted based on the
dynamic theories proposed by prominent mathematicians of this century, including Poincaré
and Lyapunov, Andronov, Hopf, and Lorenz.
1.3 Chemistry and Mathematics: New Trends

A new period of the interaction between chemistry and mathematics was shaped out by the
computer revolution of the 1950–60s. Making a general statement about the difference between
the classical and contemporary scientific situations, one can carefully say that
• The classical situation was characterized by a search for general scientific laws.
Albert Einstein described the discovery of these new laws as “a flight from the miracle”:
“The development of this world of thoughts is in a certain sense a continuous flight
from the miracle.”
• The focus of the contemporary scientific situation has changed. From the epoch of the great
scientific revolutions we have moved to the epoch of the intellectual devices, mostly
computers, from the Divine Plan to a collection of models.
4 Chapter 1
This type of division had to be made carefully: never say “never” and a period of great scientific
discoveries may still lie ahead. Nevertheless, chemistry and chemical engineering have
been much influenced by the computer revolution, which is still ongoing. Apparently, this has
been a strong additional factor for the shaping of the new discipline “mathematical chemistry.”
Although this term was used previously by Lomenosov in the 18th century, the systematic
development of this area only started in the 1950s. At this time, Neal Amundson and Rutherford
Aris published the first papers and books describing the corresponding mathematical
models in much detail and creating the foundation of the discipline (Aris, 1965, 1969, 1975;
Aris and Amundson, 1958a,b,c).
Presently, a whole battery of efficient computational methods has been developed for modeling
chemical systems at different levels (nano-, micro-, meso-, and macrolevel). We are now able
to cover a variety of chemical aspects using an enormous number of available methods, such as
• computational chemistry, in particular methods based on density functional theory.
• computational chemical kinetics, in particular CHEMKIN software and various “stiff”
methods of solving sets of ordinary and partial differential equations.
• computational fluid dynamics.
• sophisticated statistical methods.
From the other side, during this period many rigorous theoretical results in mathematical
chemistry have been obtained, especially in the area of chemical dynamics. Wei and Prater (1962)
developed a concept of “lumping,” presenting a general result for first-order mass action-law
systems. Many results have been obtained at the boundary between chemical thermodynamics
and chemical kinetics. In 1972, Horn and Jackson (1972) posed the problem of searching the
relationships between the structure of the detailed mechanism and its kinetic behavior. This
theory was developed further in the 1970s and 1980s by Yablonsky et al. (Gorban et al.,
1986; Yablonskii et al., 1983, 1991) and independently by Feinberg (1987, 1989), Clarke (1974),
and Ivanova (1979). Horn (1964) was the first to pose the problem of attainable regions for
chemical processes. In the 1970s, Gorban constructed a theory of “thermodynamically
unattainable” regions, that is, regions that are impossible to reach from certain initial conditions
(Glansdorff and Prigogine, 1971; Gorban, 1984). For more details on this chenucogeometric
theory based on thermodynamic Lyapunov functions (see Gorban, 1984; Yablonsky et al., 1991).
Theoretical breakthroughs in the understanding of chemical critical phenomena (multiplicity,
oscillations, waves) were achieved by different groups of chemists. The Belgian school of
irreversible thermodynamics (Prigogine and Nicolis) provided insight into the origin of these
phenomena based on the concepts of the “thermodynamic stability criterion” and “dissipative
structure” (Glansdorff and Prigogine, 1971; Nicolis and Prigogine, 1977; Prigogine, 1967).
The group led by Aris (Minneapolis, Minnesota, USA) presented a uniquely scrupulous study
of the dynamic properties of the nonisothermal continuous stirred-tank reactor (CSTR)
based on bifurcation theory (Farr and Aris, 1986). The first part of this paper’s title, “Yet who
Introduction 5
would have thought the old man to have had so much blood in him?” is a quotation from
Shakespeare’s Macbeth. Finally, Ertl and coworkers (Berlin, Germany) constructed a
theoretical model of kinetic oscillations in the oxidation of carbon monoxide over platinum
(Ertl et al., 1982; Ertl, 2007), which may be called the “Mona Lisa of heterogeneous catalysis”
as it has been an attractive object of catalysis studies for a long time. The model developed by
Ertl et al. (1982) describes many peculiarities of this reaction, including surface waves.
Two recent trends in mathematical chemistry are model reduction and chemical calculus.
In model reduction, two approaches are popular: manifold analysis (Maas and Pope, 1992) and
so-called asymptotology of chemical reaction networks (Gorban et al., 2010), which is a
generalization of the concept of a rate-limiting step. The chemical calculus approach, which
was created in collaboration between Washington University in St. Louis, Missouri (USA) and
Ghent University (Belgium), is focused on precise catalyst characterization using
pulse-response data generated in a temporal analysis of products (TAP) reactor (Constales
et al., 2001; Gleaves et al., 1988, 1997; Yablonsky et al., 2007). With the TAP method, during
an experiment the change of the catalyst composition as a result of a gas pulse is
insignificant. At present, chemical calculus can be considered as a mathematical basis for
precise nonsteady-state characterization of the chemical activity of solid materials. For
a critical review of theoretical results, see Marin and Yablonsky (2011).
Despite evident progress in the development of both computational and theoretical areas, there
still are only a few achievements that can be considered as fruits of synergy between the
essential physicochemical understanding, a rigorous mathematical analysis and efficient
computing. When we talk about “advanced data analysis,” the adjective “advanced” means
an attempt to achieve this unachievable ideal. From this point of view, our book is such an
attempt. In every chapter, we try to present different constituents of the modeling of
chemical systems, such as a physicochemical model framework, some aspects of data analysis
including primary data analysis, and rigorous results obtained by mathematical analysis.
The term “advanced” may also relate to a new, high level of physicochemical
understanding and it does not necessarily entail a more complex model. In many situations, “to
understand” means “to simplify” and we are not afraid to present simple but essential
knowledge. Finally, to be “advanced” means to be able to pose new practical and theoretical
questions and answer them. Formulating new questions is extremely important for the
progress of our science, which is still, as chemists say, “in statu nascendi.”
1.4 Structure of This Book and Its Building Blocks

Now we are going to briefly discuss the contents of this book, explaining its logic and
reasoning. Chapters 2–8 are organized as a sequence of building blocks: “chemical
composition”—“complex chemical reaction”—“chemical reactor.” Chapter 9 complements
6 Chapter 1
these chapters, providing information about model discrimination and parameter estimation
methods. Chapter 10 deals with specific problems of modeling polymerization processes and
Chapter 11 describes advanced theoretical analysis focusing on computer algebra. Next, a more
detailed, chapter-by-chapter description of the book follows.
In Chapter 2, a new original approach is presented based on a new unified C-matrix, which
generates three main matrices of chemical systems representing both chemical composition and
complex chemical transformation. These three matrices are the molecular matrix, the
stoichiometric matrix, and the matrix of Horiuti numbers, and the original algorithm is derived
in this chapter.
In Chapter 3, the theoretical “minimum minimarum” is explained. This toolbox serves the
primary analysis of data of chemical transformations and the construction of typical kinetic
models, both steady-state and nonsteady-state. In the course of the primary analysis, the
reaction rate is extracted from the observed net rate of production of a chemical component.
Although the procedure is rather simple, its understanding is not trivial.
Using methods from graph theory, it is explained which part of the kinetic description is
influenced by the complexity of the detailed reaction mechanism and which part is not. This is
an important step in the so-called “gray-box” approach, which is widely applied in chemical
engineering modeling.
As the title of Chapter 4 suggests, this chapter lays out physicochemical principles of
simplifications of complex models, that is, assumptions on quasi-equilibrium and quasi-steady-
state, assumptions on the abundance of some chemical components, and the assumption of a rate-
limiting step. These principles are systematically used in the primary analysis of complex models.
Chapter 5 is devoted to the basic reactor models used in chemical engineering: the batch
reactor, the CSTR, the plug-flow reactor, and the TAP reactor with its modification, the
thin-zone TAP reactor. Special attention is paid to the reaction-diffusion reactor, the detailed
analysis of which opens up wide perspectives for the understanding of different types of
reactors, such as catalytic, membrane and biological reactors.
Chapter 6 reflects on new areas and problems at the boundary of chemical thermodynamics and
chemical kinetics, that is, estimating features of kinetic behavior based on thermodynamic
characteristics. New methods of chemico-geometric analysis are described. Recently found,
original, equilibrium relationships between nonequilibrium data, which can be observed in
special experiments with symmetrical initial conditions, are theoretically analyzed in detail for
different types of chemical reactors. The known problem of kinetic control versus
thermodynamic control is explained in a new way.
Chapter 7 is about stability and bifurcations. Typical catalytic mechanisms and corresponding
models for the interpretation of complex dynamic behavior, in particular multiplicity of
steady states and oscillations, are presented.
Introduction 7
Chapter 8 provides original results for optimal configurations of multizone reaction-diffusion

reactors, and compares these with results for a cascade of reactors known from the literature.
Chapter 9 offers a classical toolbox of model discrimination and parameter identification
methods. Such methods are constantly modified and they are a “golden treasure” to every
modeler.
Chapter 10 provides a formal apparatus, in particular integrodifferential equations, for
describing the physicochemical properties of polymers and their complex transformations.
Finally, the focus of Chapter 11 is on advanced methods of theoretical analysis, especially
computer algebra. Most of the results presented in this chapter, that is, critical simplification,
the analytical criteria for distinguishing nonlinear from linear behavior, are original.
Summarizing, the building of mathematical chemistry has not been completed. This book
covers only a number of selected rooms of this structure. It is not easy to live in a building that
has been only partly completed, but there is no alternative, and generally in science this is a
typical story. In addition, in many countries of the Near East where rainfall is scarce, it is
customary for families to move into new houses long before all rooms have been prepared. So,
we are moving…
References
Aris, R., 1965. Introduction to the Analysis of Chemical Reactors. Prentice-Hall, Englewood Cliffs, NJ.
Aris, R., 1969. Elementary Chemical Reactor Analysis. Prentice-Hall, Englewood Cliffs, NJ.
Aris, R., 1975. The Mathematical Theory of Diffusion and Reaction in Permeable Catalysts. Clarendon Press,
Oxford.
Aris, R., Amundson, N.R., 1958a. An analysis of chemical reactor stability and control-I: the possibility of local
control, with perfect or imperfect control mechanisms. Chem. Eng. Sci. 7, 121–131.
Aris, R., Amundson, N.R., 1958b. An analysis of chemical reactor stability and control-II: the evolution of
proportional control. Chem. Eng. Sci. 7, 132–147.
Aris, R., Amundson, N.R., 1958c. An analysis of chemical reactor stability and control-III: the principles of
programming reactor calculations. Some extensions. Chem. Eng. Sci. 7, 148–155.
Clarke, B.L., 1974. Stability analysis of a model reaction network using graph theory. J. Chem. Phys. 60, 1493–1501.
Constales, D., Yablonsky, G.S., Marin, G.B., Gleaves, J.T., 2001. Multi-zone TAP-reactors theory and application: I.
The global transfer matrix equation. Chem. Eng. Sci. 56, 133–149.
Ertl, G., (2007). Reactions at surfaces: from atoms to complexity, Nobel Lecture, December 8.
Ertl, G., Norton, P.R., Rüstig, J., 1982. Kinetic oscillations in the platinum-catalyzed oxidation of CO. Phys. Rev.
Lett. 49, 177–180.
Farr, W.W., Aris, R., 1986. Yet who would have thought the old man to have had so much blood in him?
Reflections on the multiplicity of steady states of the stirred tank reactor. Chem. Eng. Sci. 41, 1385–1402.
Feinberg, M., 1987. Chemical reaction network structure and the stability of complex isothermal reactors—I. The
deficiency zero and deficiency one theorems. Chem. Eng. Sci. 42, 2229–2268.
Feinberg, M., 1989. Necessary and sufficient conditions for detailed balancing in mass action systems of arbitrary
complexity. Chem. Eng. Sci. 44, 1819–1827.
Glansdorff, P., Prigogine, I., 1971. Thermodynamic Theory of Structure, Stability, and Fluctuations. Wiley, London.
Gleaves, J.T., Ebner, J.R., Kuechler, T.C., 1988. Temporal analysis of products (TAP)—a unique catalyst
evaluation system with submillisecond time resolution. Catal. Rev. Sci. Eng. 30, 49–116.
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Gleaves, J.T., Yablonskii, G.S., Phanawadee, P., Schuurman, Y., 1997. TAP-2: an interrogative kinetics approach.
Appl. Catal. A 160, 55–88.
Gorban, A.N., 1984. Equilibrium Encircling: Equations of Chemical Kinetics and Their Thermodynamic Analysis.
Nauka, Novosibirsk.
Gorban, A.N., Bykov, V.I., Yablonskii, G.S., 1986. Thermodynamic function analogue for reactions proceeding
without interaction of various substances. Chem. Eng. Sci. 41, 2739–2745.
Gorban, A.N., Radulescu, O., Zinovyev, A.Y., 2010. Asymptotology of chemical reaction networks. Chem. Eng.
Sci. 65, 2310–2324.
Horn, F.J.M., 1964. Attainable and Non-Attainable Regions in Chemical Reaction Technique. In: Proceedings of the
third European Symposium on Chemical Reaction Engineering. Pergamon Press, London, pp. 1–10.
Horn, F., Jackson, R., 1972. General mass action kinetics. Arch. Rat. Mech. Anal. 47, 81–116.
Ivanova, A.N., 1979. Conditions of uniqueness of steady state related to the structure of the reaction mechanism.
Kinet. Katal. 20, 1019–1023 (in Russian).
Maas, U., Pope, S.B., 1992. Simplifying chemical kinetics: intrinsic low-dimensional manifolds in composition
space. Combust. Flame 88, 239–264.
Marin, G.B., Yablonsky, G.S., 2011. Kinetics of Chemical Reactions—Decoding Complexity. Wiley-VCH,
Weinheim.
Nicolis, G., Prigogine, I., 1977. Self-Organization in Non-Equilibrium Systems: From Dissipative Structures to
Order Through Fluctuations. Wiley, New York, NY.
Prigogine, I., 1967. Introduction to Thermodynamics of Irreversible Processes, third ed. Wiley-Interscience,
New York, NY.
Wei, J., Prater, C.D., 1962. The structure and analysis of complex reaction systems. In: Eley, D.D. (Ed.), Advances in
Catalysis. Academic Press, New York, NY, pp. 203–392.
Yablonskii, G.S., Bykov, V.I., Gorban, A.N., 1983. Kinetic Models of Catalytic Reactions. Nauka, Novosibirsk.
Yablonskii, G.S., Bykov, V.I., Gorban, A.N., Elokhin, V.I., 1991. Kinetic Models of Catalytic Reactions.
Comprehensive Chemical Kinetics, vol. 32. Elsevier, Amsterdam.
Yablonsky, G.S., Constales, D., Shekhtman, S.O., Gleaves, J.T., 2007. The Y-procedure: how to extract the
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Sci. 62, 6754–6767.
CHAPTER 2
Chemical Composition and

Structure: Linear Algebra
2.1 Introduction
The following questions often arise in the practice of chemical engineering:
• Given a set of components of known atomic composition, establish which of them are
key to determine, together with the element balances, the amounts of all others.
Furthermore, find a way of generating all possible reactions involving these components.
This will be addressed by the augmented molecular matrix, introduced in Section 2.2.
• Given a set of reactions, determine which of these are key to describing all other reactions
as combinations of this set and how to do this. Also determine which additional balances
appear and which thermodynamic characteristics (enthalpy change, equilibrium
coefficient) are dependent. This will be addressed by the augmented stoichiometric matrix,
introduced in Section 2.3.
• For a set of reactions involving intermediates, which typically cannot be measured,
determine the overall reactions, that is, the ones not involving such intermediates, and find
the numbers by which these can be written as combinations of the given reactions (the
so-called Horiuti numbers). This will be addressed by augmenting a specially crafted
stoichiometric matrix, as explained in Section 2.4.
What is a matrix? It is a square or rectangular array of numbers or expressions, placed

between parentheses, for example:

1 3 7
(2.1)
2 4 3
In this case there are two rows and three columns, and we call this a 2 3 matrix, mentioning
first the number of rows and then the number of columns. There can be no empty spaces left in
the matrix. Matrices are widely used in engineering to represent a variety of mathematical
objects and relationships. We will gradually introduce them, in close connection with the
requirements from chemistry and engineering that justify their use.
Let us start with chemical reactions. A statement such as
2H2 + O2 ! 2H2 O (2.2)
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10 Chapter 2
describes a chemical process, a reaction, that consumes two molecules of hydrogen gas,
H2, and one molecule of oxygen gas, O2, to produce two molecules of water, H2O. Such
a reaction does not actually occur as the collision of the three gas molecules involved, but
rather as a complicated, not yet fully elucidated set of reaction steps. Nevertheless,
Eq. (2.2) describes the overall reaction and can readily be tested experimentally: two
moles of hydrogen and one mole of oxygen are transformed into two moles of water.
The statement in Eq. (2.2) implies that all H2 and O2 should be completely transformed
into H2O so that no H2 or O2 should be left. Thus, Eq. (2.2) is a falsifiable statement,
and therefore scientific.
If we ignore the direction of the arrow in Eq. (2.2), it can be viewed as an equality of sorts:
2H2 + O2 ≜2H2 O (2.3)
where “≜”denotes the equality of all atom counts on both sides. This is not an absolute equality:
O2 and 2H2 together are not the same as 2H2O, but they are amenable to transformation
into each other. Eq. (2.3) can be rewritten as
2H2 O2 + 2H2 O≜zero (2.4)
By convention, the terms that originate from the left-hand side, the reactants, are assigned a
negative sign, and the products are assigned a positive sign. Maybe we could associate this
equation to a (1 3) matrix? The matrix
½ 2 1 2 (2.5)
would be the most natural choice, but since the meaning of the columns (H2, O2, and H2O)
would be lost, we introduce a typographical convention for indicating the meaning of the
columns:
H2 O2 H2 O
(2.6)
½ 2 1 2
Note that the chemical symbols in Eq. (2.6) are hints, not part of the matrix!
Another reaction might occur between the same reactants, namely the synthesis of
hydrogen peroxide:
H2 + O2 ! H2 O2 (2.7)
This reaction can be represented by the matrix:
H 2 O2 H2 O2
(2.8)
½ 1 1 1
Chemical Composition and Structure: Linear Algebra 11
and it is logical to represent the system of both reactions, Eqs. (2.2), (2.7), by the 2 4 matrix:
H 2 O2 H2 O H2 O2

2 1 2 0 (2.9)
1 1 0 1
Note that for this matrix the rows are not labeled. We could add more hints by adding the names
of the reaction products to the left of the matrix, as in
H2 O2 H2 O H2 O2

H2 O 2 1 2 0 (2.10)
H2 O2 1 1 0 1
but initially we will consider the rows of this stoichiometric matrix as merely stoichiometric
information: how many molecules of reactants (negative entries) produce how many
molecules of products (positive entries)? Components that do not occur in a particular reaction
have a zero entry in that row. Reactions are the building blocks of a chemical description,
but before we can handle them more formally, we must also express how each component
combines its constituent elements. This is done in the molecular matrix.
2.2 The Molecular Matrix and Augmented Molecular Matrix

2.2.1 The Molecular Matrix
For every component present in the reaction mixture under consideration, its elemental
composition must be specified in order to verify that all elements are properly preserved.
The most convenient and complete way of specifying the elemental composition is by a matrix
in which the columns correspond to the elements, with possibly one column reserved for
electric charge, and the rows signify the different molecules, ions, radicals, and so forth, that are
being considered. This is called the molecular matrix M. For instance, for a mixture consisting
of H2, CH4, C2H6, and C2H4, the molecular matrix is given by
C H
2 3
H20 2
6
CH4 6 1 477 (2.11)
M¼ 6 7
C2 H6 4 2 65
C2 H4 2 4
Based on this molecular matrix, the molar masses of the components can be determined
from the atomic masses of the elements. For instance, the molar mass of C2H6 is two times
the atomic mass of C plus six times that of H. To express such relationships in a very
compact manner, mathematicians have devised a special way of multiplying matrices: the
12 Chapter 2
atomic masses of the elements can be grouped in a column vector mA (in this case consisting of
two rows),

H 1:008
mA ¼ (2.12)
C 12
and the molar masses of the components can go in a 4 1 column vector mM:
2 3
H2 2:016
CH4 6 7
6 16:032 7
mM ¼ 6 7 (2.13)
C2 H6 4 30:048 5
C2 H4 28:032
Then in compact form, mM ¼ MmA. In general, a product of two matrices B and C is
defined only if the number of columns of B equals the number of rows of C, and the
product P ¼ BC will have the number of rows of B and the number of columns of C.
A general entry Pij of P is then given by definition as a sum of products of entries of
row i of B and entries of column j of C:
Pij ¼ Bi1 C1j + Bi2 C2j + ⋯ + Bip Cpj (2.14)
where p is the number of columns of B (and rows of C).
Furthermore, when a set of mathematical objects ν1, ν2, …, νn can be multiplied by real
numbers ai and the sum of the products satisfies the equation a1 ν1 + a2 ν2 + ⋯ + an νn ¼ 0,
where not all real numbers a1, a2, …, an are zero, they are said to be linearly dependent,
otherwise they are called linearly independent. For instance, the equations x + y ¼ 5 and
x y ¼ 9 are linearly independent, but if we add the equation x ¼ 7, they become dependent,
since x + y ¼ 5 plus x y ¼ 9 minus twice x ¼ 7 yields 0 ¼ 0. A set of linearly independent
objects that is maximal, that is, to which no object can be added without losing linear
independence, is called a basis. In the previous example, x + y ¼ 5 by itself is not a basis
since x y ¼ 9 can be added to it without losing linear independence, but the set of
these two equations does form a basis since no third equation can be added to this set
independently.
2.2.2 Application of the Molecular Matrix to Element Balances
In practice, it is often crucial to calculate the balance for each of the elements present in
the components of a mixture. Now the questions arise how many of these balances
are independent and which amounts can be deduced from other ones given the element
balance values. To solve this problem in a systematic way, a certain ordering of the
components must be chosen; typically, the best known or most easily measured components
should be listed first. Then the molecular matrix can be augmented by adding a unit matrix,
that is, a matrix with ones on the main diagonal and zeros elsewhere, to its right. For the
molecular matrix represented by Eq. (2.11), we obtain
Ct Ht H2 CH4 C2 H6 C2 H4
2 3
H2 0 2 1 0 0 0
CH4 6 61 4 0 1 0 077 (2.15)
6 7
C2 H6 4 2 6 0 0 1 05
C2 H4 2 4 0 0 0 1
This matrix is best interpreted as a form of double bookkeeping as used in accounting:
in the first two columns, the counts of the elements C and H, now called Ct and Ht,
for total C and H, are tallied (debit); in the next four columns, the components are figured
(credit).
An augmented molecular matrix can be transformed to a Reduced Row Echelon Form or
RREF. This method is essential to all matrix transformations in this chapter. The idea behind
the RREF is that we work from the first column all the way to the rightmost one. For each
column we determine whether it is possible to eliminate it by finding a nonzero entry, or
pivot, in a row that has not been considered before. If not, we skip to the next column. If a pivot
is found, we use it to eliminate all other entries in that row. We also move the pivot row
up as far as possible. We cannot tell in advance where all the pivots will be found; we
must find them one by one since the elimination procedure can change zero entries into
nonzero ones and vice versa. In general, we also do not know in advance how many pivots
will be found. However, in the special case of a matrix augmented with a unit matrix,
we do know that their number will be equal to the number of rows.
As an example, consider the augmented matrix for a mixture consisting of H2, CH4, C2H6,
and C2H4 given by Eq. (2.15). In order to find the RREF, we start with the first column and
find a nonzero entry in the second row. We move this second row up to the first position:
2 3
1 4 0 1 0 0
60 07
6 2 1 0 0 7 (2.16)
6 7
42 6 0 0 1 05
2 4 0 0 0 1
The pivot is in bold. Note that the hints labeling the rows are absent, since their identity
will not be preserved during the reduction of the matrix.
Next, we use the first row to eliminate all other entries of the first column. The second
row requires no action since the value there is already zero. We subtract twice the first row
from the third row, changing the matrix to
14 Chapter 2
2 3
1 4 0 1 0 0
60 0 07
6 2 1 0 7 (2.17)
6 7
40 2 0 2 1 05
2 4 0 0 0 1
Similarly, we subtract twice the first row from the fourth row, resulting in
2 3
1 4 0 1 0 0
60 0 0 07
6 2 1 7 (2.18)
6 7
40 2 0 2 1 0 5
0 4 0 2 0 1
Now we tackle the second column. The first row has already been assigned a pivot, so we
do not consider it for elimination purposes. In the second row, we find a nonzero value,
2, by which we divide the entries in this row:
2 3
1 4 0 1 0 0
6 7
60 1 1=2 0 0 07 (2.19)
6 7
60 2 0 2 1 0 7
4 5
0 4 0 2 0 1
Now we use this second row for the elimination of the entries in the other rows of the
second column, including the first row. So we subtract four times the second row from the
first, add twice the second row to the third, and add four times the second row to the fourth.
The result of these operations is
2 3
1 0 2 1 0 0
6 7
6 0 1 1=2 0 0 07 (2.20)
6 7
60 0 1 2 1 0 7
4 5
0 0 2 2 0 1
When looking at the third column to find a pivot, we do not consider the first and second
rows because they have already been assigned pivots. We do, however, find a suitable
entry, 1, in the third row and use this as a pivot. We add twice the third row to the
first, subtract half of it from the second, and subtract twice the third row from the fourth.
This results in
2 3
1 0 0 3 2 0
60 1 0 1 1=2 0 7
6 7 (2.21)
6 7
4 0 0 1 2 1 05
0 0 0 2 2 1
Finally, in the fourth column we do not consider the first three rows, because they already
have pivots, but find a nonzero value in the fourth row, 2, and choose it as a pivot. First
we divide the entries in the fourth row by this value,
2 3
1 0 0 3 2 0
60 1 1=2 07
6 1 0 7 (2.22)
6 7
40 0 1 2 1 05
0 0 0 1 1 1=2
and then add three times the fourth row to the first, subtract it once from the second, and
add it twice to the third:
2 3
1 0 0 0 1 3=2
6 0 1 0 0 1=2 1=2 7
6 7 (2.23)
6 7
4 0 0 1 0 1 15
0 0 0 1 1 1=2
We have now obtained the RREF. Fig. 2.1 shows a map of this matrix indicating the subareas.
Fig. 2.1
Map of subareas in the RREF of Eq. (2.23).
16 Chapter 2
Because the molecular matrix was augmented with a unit matrix, the pivot columns together
form a unit submatrix indicating the key elements and key components. Key elements of a
certain chemical mixture are those the amounts of which cannot be determined from the
amounts of other elements; key components are those the amounts of which, together with
the amounts of the key elements, uniquely determine the amounts of the other, nonkey
components.
Every row has a pivot; the first two rows have pivots in element columns and are related
to pseudoreactions in which precisely one atom of the element is “created” as the result
of a transformation of components. Contrary to ordinary chemical reactions, there is no
balance of the pivotal element in these pseudoreactions, but instead an excess of a single
atom in the products. For instance, the first row in Eq. (2.23) represents the pseudoreaction
C2H6 > 3/2 C2H4 with an excess of one C atom in the product: reactants and products
contain two and three C atoms, respectively. Similarly, the pseudoreaction in the second row,
1/2 C2H4 > 1/2 C2H6, has an excess of one H atom (two H atoms in reactants, three in
products).
The pivots of the third and fourth rows are not elements but the components H2 and CH4.
They represent the reactions C2 H6 >H2 + C2 H4 , in which a single unit of H2 is formed,
and C2 H6 >CH4 + 1=2 C2 H4 , in which a single unit of CH4 is formed. These rows
corresponding to reactions form a stoichiometric basis for all reactions involving the
components considered.
The first four columns are pivot columns, in which only entries 1 occur as pivots and all
other entries are zero. The fifth and sixth columns have no pivot, and correspond to components
that are not key. Their amounts can be deduced from the element balances and the key
components. The coefficients can be read off at once in the columns, which were obtained
from the pseudoreactions and reactions. In the fifth column, the amount of C2H6 equals
nC2 H6 ¼ nCt + 1=2nHt nH2 nCH4 (2.24)
and in the sixth, the amount of C2H4 equals
nC2 H4 ¼ 3=2nCt 1=2nHt + nH2 + 1=2nCH4 (2.25)
In this example, if we assume that nC2 H4 can be written as a linear combination:
nC2 H4 ¼ αnCt + βnHt + γnH2 + δnCH4 (2.26)
and consider the effect of the first pseudoreaction, C2H6 > 3/2 C2H4, in which C is “created”
and H2 and CH4 do not participate, nCt increases by 1, nC2 H4 by 3/2, and nHt , nH2 , and nCH4 are
not affected.
Consequently, α must equal 3/2. In the same way, β, γ, and δ are determined uniquely by the
second, third, and fourth pseudoreactions and reactions.
Summarizing, to analyze the element balances

(1) list the elements and components present in the order of decreasing ease of
measurement.
(2) form the molecular matrix by entering the number of atoms of an element for each
component in its own row.
(3) augment this matrix by adding a unit matrix to its right.
(4) perform the operations resulting in the RREF.
Then, in the result:
(1) every row is still stoichiometrically valid.
(2) every pivot column corresponds to a value that must be known, either that of an
element balance or of a key component.
(3) every nonpivot column corresponds to an unknown value that can be deduced from the
pivots using the matrix coefficients in that column.
(4) the rows for which all elemental entries are zero form the basis of stoichiometrically
possible reactions.
Because the matrix is augmented with a unit matrix, the total number of pivot columns
always equals the number of rows, which is also the number of components. It also equals
the number of key elements plus the number of key components. The number of key
elements can be less than the total number of elements, when some element columns
have no pivot.
Example 2.1 Fixed Ratio of Elements

Consider a mixture consisting of the isomers c-C4H8, t-C4H8, and the dimer C8H16. In order to
determine which are the key elements, and the key and nonkey components, we first construct
the molecular matrix as
2C H 3
c-C4 H8 4 8
6 7 (2.27)
t-C4 H8 4 4 8 5
C8 H16 8 16
We augment it to the matrix:
C Ht c-C4 H8 t-C4 H8 C8 H16

2 t 3
4 8 1 0 0
6 7 (2.28)
44 8 0 1 05
8 16 0 0 1
18 Chapter 2
with RREF
C Ht c-C4 H8 t-C4 H8 C8 H16
2 t 3
1 2 0 0 1=8
6 7 (2.29)
40 0 1 0 1=2 5
0 0 0 1 1=2
An unusual event occurs here: the second column, even though elemental, has no pivot. It
therefore contains a nonkey element, and we can read from it that Ht is twice Ct in all
components of the mixture. Next, c-C4H8 and t-C4H8 are the two key components, and the
amount of C8H16 is always given by
nC8 H16 ¼ 1=8nCt 1=2nc-C4 H8 1=2nt-C4 H8 (2.30)

The general result that can be derived from this example is the fundamental equation:
Number of key components ¼ number of components number of key elements (2.31)

The number of key components is thus a property of the reaction mixture, but the key components
actually chosen depend on the ordering: the components listed first will be chosen to be key
components. This is why it is useful to order the components by decreasing ease of measurement, so
that the components whose values can be measured more easily will be selected as key components.
The RREF method is completely mechanical, so it requires no insight and when performed
correctly will always give the same result: even though different nonzero entries might be
chosen as pivots in its course, the final result will always be the same. Conceptually, the
RREF means that given an ordering of variables, we try and eliminate all possible (pivot)
variables when they can be expressed in terms of other variables that come later in the
ordering.
Verifying that the element balances hold is an essential way of making sure that no
components were overlooked. Then the determination of the key components is not
arbitrary, since it only depends on knowing the composition of the mixture of all
participating components.
Example 2.2 Different Order of Components

Rework the example with the molecular matrix given by Eq. (2.11), but now with the reverse order
of components.
Solution:
The new molecular matrix is
C H
2 3
C 2 H4 2 4
C 2 H6 6
62 677 (2.32)
6 7
CH4 4 1 45
H2 0 2
After augmentation with a unit matrix, this matrix becomes

Ct Ht C2 H4 C2 H6 CH4 H2
2 3
2 4 1 0 0 0
6 7
62 6 0 1 0 07 (2.33)
6 7
6 7
61 4 0 0 1 07
4 5
0 2 0 0 0 1
Its RREF is readily computed to be
Ct Ht C2 H4 C2 H6 CH4 H2
2 3
1 0 0 0 1 2
6 7
60 1 0 0 0 1=2 7 (2.34)
6 7
6 7
60 0 1 0 2 27
4 5
0 0 0 1 2 1
so that now the key components are C2H4 and C2H6 (because they come earlier in the
ordering). The basic reactions are C2 H4 + 2H2 >2 CH4 and C2 H6 + H2 >2CH4 . The amounts
of the nonkey components work out to
nCH4 ¼ nCt 2nC2 H4 2nC2 H6 (2.35)
and
nH2 ¼ 2nCt + 1=2nHt + 2nC2 H4 + nC2 H6 (2.36)
Example 2.3 Mixture Containing a One-Atom Molecule

Calculate the balances for a mixture containing the molecules C (atomic carbon), CO, CO2,
and O2.
Solution:
The fact that atomic carbon also occurs among the components does not require any special
treatment; only the usual care must be taken to distinguish the Ct elemental column from the
C atomic carbon column. The molecular matrix is
C O
2 3
C 1 0
6 7
CO 661 177 (2.37)
6 7
CO2 6
41 275
O2 0 2
20 Chapter 2
and after augmentation,

Ct Ot C CO CO2 O2
2 3
1 0 1 0 0 0
6 7
61 1 0 1 0 07 (2.38)
6 7
61 2 0 0 1 07
4 5
0 2 0 0 0 1
Its RREF is then
Ct Ot C CO CO2 O2
2 3
1 0 0 0 1 1
6 7
60 1 0 0 0 1=2 7 (2.39)
6 7
60 0 1 0 1 17
4 5
0 0 0 1 1 1=2
The key components are C and CO (as dictated by the order of components) and the amount of
the nonkey components can be calculated from
nCO2 ¼ nCt nC nCO (2.40)
and
nO2 ¼ nCt + 1=2nOt + nC + 1=2nCO (2.41)
Example 2.4 Combination of Two Groups of Elements

Consider the components acetylene (C2H2), hydrochloric acid (HCl), and vinyl chloride
(C2H3Cl). Determine the key components and balances.
Solution:
The augmented molecular matrix is
Ct Ht Clt C2 H2 HCl C2 H3 Cl
2 3
2 2 0 1 0 0
6 7 (2.42)
40 1 1 0 1 05
2 3 1 0 0 1
with RREF
Ct Ht Clt C2 H2 HCl C2 H3 Cl
2 3
1 0 1 0 3=2 1=2
6 7 (2.43)
40 1 1 0 1 05
0 0 0 1 1 1
so that C and H are the independent elements and Cl is dependent according to
nClt ¼ nCt + nHt (2.44)
In this case, C2H2 is the only key component because C2H3Cl is a combination of the two groups
of elements C2H2 and HCl.
The amounts of the nonkey components are
nHCl ¼ 3=2nCt + nHt + n C2 H2 (2.45)

and
n C2 H3 Cl ¼ 1=2nCt n C2 H2 (2.46)
2.2.3 Remarks
The method indicated in this section works equally well for ions and radicals, ionic
or not. In the case of negative ions, the excess electrons must be specified as well, since
electrons are distinct from all elements; similarly, in the case of positive ions, the
deficit in electrons must be indicated. This will ensure that charge is always properly
preserved. When different isotopes of an element occur, they must be counted separately
along with the different components they occur in. Sometimes unconventional “elements” such
as active catalyst sites are used. Sometimes subcomponents can be used as pseudoelements
(water in hydrates, building blocks of polymers, amino acids).
2.3 The Stoichiometric Matrix

In general, a stoichiometric matrix represents a set of reactions involving given components.
The columns of this matrix correspond to the different components, the rows correspond to the
different reactions, and the entries are stoichiometric coefficients, which by convention are
negative for the reactants and positive for the products.
In Section 2.2, we have shown how the molecular matrix, when augmented with a unit
matrix and converted to the corresponding RREF, yields a basis for all stoichiometrically
acceptable reactions. In reality, however, many of these reactions may be chemically
impossible. Therefore, a special stoichiometric matrix can be considered, in which only
selected reactions occur.
2.3.1 Application of the Stoichiometric Matrix to Reactions
Consider the set of reactions

2H2 + O2 >2H2 O (2.47)
H2 + O2 >H2 O2 (2.48)
22 Chapter 2
which is represented by the stoichiometric matrix S

H2 O2 H2 O H2 O2

2 1 2 0 (2.49)
1 1 0 1
while the molecular matrix M of the components that participate in these reactions is
HO
2 3
H2 2 0
6 7
O2 6 0 2 7 (2.50)
6 7
H2 O 6
42 15
7
H2 O2 2 2
If we wish to verify, for instance, that hydrogen atoms are conserved by the first reaction,
Eq. (2.47), we must count them in every term on either side, and then subtract these values:
there are four hydrogen atoms on both sides and subtraction yields zero. An equivalent but
mathematically more elegant method is to use the entries of the stoichiometric matrix and the
molecular matrix as follows: we read 2 for the coefficient of H2 in the first row of the
stoichiometric matrix and multiply by 2, the number of H atoms in H2 as indicated by the
molecular matrix, and so on. The result is then (2)(2) + (1)(0) + (2)(2) + (0)(2) ¼ 0, which by
definition is precisely the entry (1,1) of the product of the stoichiometric and molecular
matrices SM. Similarly, the entry (ij) of that product expresses the difference in atom counts of
element j in reaction i. Consequently, we can express the balance of all reactions for all
elements compactly as the zero matrix with all entries zero:
SM ¼ 0 (2.51)
It is useful to compute the RREF of a stoichiometric matrix because the pivots will reveal
the key components, and the nonpivot columns will reveal the balances obeyed by the
nonkey components. In this example, the RREF equals
H 2 O2 H2 O H2 O2
" #
1 0 2 1 (2.52)
0 1 2 2
so that the key components are H2 and O2, and the relationships are read off in the
nonpivot columns, 3 and 4, as
ΔnH2 O ¼ 2ΔnH2 + 2ΔnO2 (2.53)
and
ΔnH2 O2 ¼ ΔnH2 2ΔnO2 (2.54)
where Δ indicates that we are expressing the changes in amounts that are caused by these
reactions.
Example 2.5 Effect of the Reactions Chosen

Returning to the molecules c-C4H8, t-C4H8, and the dimer C8H16 of Example 2.2, we can propose
the reactions
c-C4 H8 + t-C4 H8 >C8 H16 (2.55)
and
c-C4 H8 >t-C4 H8 (2.56)
which are represented by the stoichiometric matrix
c-C
4 H8 t-C4 H8 C8 H
16
1 1 1 (2.57)
1 1 0
with RREF
c-C H t-C4 H8 C8 H16
4 8
1 0 1=2 (2.58)
0 1 1=2
so that c-C4H8 and t-C4H8 are key components, and the balance in the nonpivot column reads
Δn C8 H16 ¼ 1=2Δn c-C4 H8 1=2Δn t-C4 H8 (2.59)
If, however, we retain only the first reaction, overlooking the second, isomerization reaction, the
stoichiometric matrix is
c-C4 H8 t-C4 H8 C8 H16

(2.60)
½ 1 1 1
with RREF
c-C4 H8 t-C4 H8 C8 H16
(2.61)
½1 1 1
Then there is only one key component, c-C4H8, and the nonpivot columns indicate the balances
Δn t-C4 H8 ¼ Δn c-C4 H8 (2.62)

and
Δn C8 H16 ¼ Δn c-C4 H8 (2.63)
Comparing this use of the stoichiometric matrix to that of the molecular matrix (Section 2.2), we
observe the following:
• When considering the molecular matrix, the element balances (Ct, Ht, etc.) provide us
with absolute values. In the current setting of reactions, we can state facts only about changes
in the number of molecules of the components, not about their total amounts.
24 Chapter 2
• Because the stoichiometric matrix may contain fewer reactions than the ones generated by
the molecular matrix, there may be more balances and fewer key components in the
stoichiometric matrix than in the molecular matrix.
• The determination of key components from the stoichiometric matrix depends on more
choices than in the case of the molecular matrix, since it involves selecting specific reactions.
Therefore, the result of this procedure may be different.
• Again, since the components listed later tend to be expressed in terms of the ones listed
earlier, the order of listing should be according to decreasing ease of measurement.
In this application, the stoichiometric matrix was not augmented, and we cannot tell by
which linear combination of the original reactions the final result was obtained. Sometimes it is
useful to keep track of the original reactions, for example when thermodynamic data such as
enthalpy changes are required or for the calculation of equilibrium coefficients.
2.3.2 The Augmented Stoichiometric Matrix
Adding the hypothetical reaction

2H2 O + O2 >2H2 O2 (2.64)
to the previous system, Eqs. (2.47), (2.48), results in the stoichiometric matrix
H2 O2 H2 O H2 O2
2 3
2 1 2 0
6 7 (2.65)
S ¼ 4 1 1 0 15
0 1 2 2
Augmenting this matrix with a unit matrix

H2 O2 H2 O H2 O2 R1 R2 R3
2 3
2 1 2 0 1 0 0
4 1 (2.66)
1 0 1 0 1 05
0 1 2 2 0 0 1
eventually results in the following RREF:
H2 O2 H2 O H2 O2 R1 R2 R3
0 2 3
R1 1 0 2 1 0 1 1
(2.67)
R02 4 0 1 2 2 0 0 1 5
R03 0 0 0 0 1 2 1
Fig. 2.2 shows a map of this matrix indicating the subareas. Every row represents a reaction,
possibly a zero reaction, in which there are no reactants or products. Here this is the case
for R30 , for which the coefficients are read off the third row in the columns representing
the reactions: (1)R1 + (2)R2 + (1)R3, where R1, R2, and R3 represent the reactions in,
respectively, Eqs. (2.47), (2.48), (2.64). This produces the zero reaction R30 . The first row in the
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expanding somewhat and having its walls
densely covered, in three bands
corresponding to the antimeres, with
innumerable minute spines (h) or
needles, sometimes supplemented by
large teeth (t) that point forwards
somewhat obliquely to the axis of the
proboscis.[403]
In the curious East Indian genus
Pipetta (Loman) the sucking and sifting
mechanism is low down in the proboscis,
and the organ is prolonged into a very
fine tube, the lips growing together till
they leave an aperture of only ·007 mm.
for the absorption of liquids.
In some cases, where the proboscis
Fig. 277.—Longitudinal section through one itself is short, as in Pallene, this
“antimere” of the proboscis in Phoxichilus
charybdaeus. G, g′, Principal and secondary mechanism is carried backwards into the
ganglia; h, sieve-hairs; L, lip; mt, oral tooth; N, fore-part of the body; and, in the latter
N′, inner and outer nerve-cords; t, proboscis- genus, the narrow oesophagus which
teeth. (After Dohrn.) succeeds the masticatory apparatus is
likewise provided with extrinsic muscles.
Fig. 278.—Transverse sections through the proboscis of Ph. charybdaeus. A,
Anterior, through the principal ganglionic mass (G); B, posterior, at the level of
the sieve-hairs (h). Coec, Intestinal caeca; Dil. M, dilator muscles; N, inner
nerve-ganglion, with circular commissure; N′, outer nerve; or, chitinous lining of
oral cavity; R M, Ret.M, retractor muscles. (After Dohrn.)
The oesophagus is followed by a long

gastric cavity, which sends forth caecal
diverticula into the chelophores (when
these are present), and four immensely
long ones into the ambulatory legs. The
caeca are attached to the walls of the limb
cavities, especially at their extremities in
the tarsi, by suspensory threads of
connective tissue, and the whole gut,
central and diverticular, is further
supported by a horizontal septal
membrane, running through body and
legs, which separates the dorsal blood-
vessel and sinus from the gut, the nervous
system and the ventral sinus, giving
support also to the reproductive glands. A Fig. 279.—Transverse section through the basal
short and simple rectum follows the joint of the third leg in Phoxichilus
charybdaeus, ♀. Cut, Cuticle; Hyp, hypodermis;
gastric cavity. Int, intestinal caecum; N, nerve-cord; Ov, ovary;
In Phoxichilus, which lacks the three Sept, septum. (After Dohrn.)
anterior appendages in the female and the
two anterior in the male, two pairs of
caeca run from the gut into the cavity of the proboscis (Fig. 278, B, coec.).[404]
Circulatory System.—The heart has been especially studied by Dohrn in
Phoxichilus. It consists of a median vessel running from the level of the eyes to the
abdomen, furnished with two pairs of lateral valvular openings, and sometimes,
though not always, with an unpaired one at the posterior end. The walls are
muscular, but with this peculiarity that the muscular walls do not extend around the
heart dorsally, in which region its lumen is only covered by the hypodermis and
cuticle of the back. The blood-spaces of the body are separated into dorsal and
ventral halves by the septal membrane already referred to, which is perforated in the
region of the lateral processes by slits placing the two cavities in communication;
this septal membrane runs through the limbs to their tips, and far into the
proboscis, where it is attached to the edge of the superior antimere. The blood is a
colourless plasma with several kinds of corpuscles, of which the most remarkable are
amoeboid, actively mobile, often coalescing into plasmodia. The course of the
circulation is on the whole outwards in the inferior or ventral sinus, inwards towards
the heart in the superior, save in the proboscis, where the systole of the heart drives
the blood forwards in the dorsal channel. The beat is rapid, two or three times in a
second, according to Loman, in Phoxichilidium. Especially in the species with small
body and exaggerated legs, the movement of the circulatory fluid is actuated more
by the movements of the limbs and the contractions of the intestinal caeca than by
the direct impulse of the heart.
Nervous System.—The nerve-chain consists of a fused pair of supra-
oesophageal ganglia, which innervate (at least in the adult) the chelophores, and of
ventral ganglia, whence proceed the nerves to the other limbs. The ganglia of the
second and third appendages are fused with one another, sometimes also with the
ganglia of the first ambulatory legs; the ganglia of the three posterior pairs of legs
are always independent (though the development of their longitudinal commissures
varies with the body-form), and they are succeeded by one or two pairs of ganglia,
much reduced in size, situated in the abdomen, of which the posterior one
innervates the muscles of the abdomen and of the anal orifice. Each lateral nerve
divides into two main branches, which supply the parts above and below the septal
membrane. The nerve-supply of the proboscis is very complicated. Its upper
antimere is supplied from the pre-oral, its two lateral antimeres from the first post-
oral, ganglion, and each of these three nerves divides into two branches, of which the
inner bears six to eight or more small ganglia, which annular commissures passing
round the pharynx connect one to another. Of these ganglia and commissures the
anterior are the largest, and with these the outer lateral nerve-branches of the
proboscis merge. The immediate origin of the nerves to the chelophores is from the
median nerve that springs from the under side of the supra-oesophageal ganglion to
run forward into the proboscis, but it is noteworthy that the chelophores receive
twigs also from the lateral nerves of the proboscis which arise from the post-oral
ganglia.
Eyes.—Eyes are the only organs of special sense known in the Pycnogons. The
deep-water Pycnogons, in general those inhabiting depths below four or five
hundred fathoms, have in most cases imperfect organs, destitute of lens and of
pigment, so imperfect in many cases as to be described as wanting. It is rare for the
eyes to be lacking in shallow-water species, as they are, for instance, in
Ascorhynchus minutus, Hoek, dredged by the Challenger in 38 fathoms, but, on the
other hand, it is no small minority of deep-water species that possess them of
normal character and size, even to depths of about 2000 fathoms.
In all cases where eyes are present, they are simple or “monomeniscous” eyes, four
in number, and are situated in two pairs on an “oculiferous tubercle,” sometimes
blunt and low, sometimes high and pointed, placed on the so-called cephalothorax,
or first, compound, segment of the body. The anterior pair are frequently a little
larger, sometimes, as in Phoxichilidium mollissimum, Hoek, very much larger, than
the posterior. The minute structure of the eye has been investigated by Dohrn,
Grenacher, Hoek, and Morgan. The following account is drawn in the first instance
from Morgan’s descriptions.[405]
The eye of a Pycnogon (Phoxichilidium) is composed of three layers, an outer layer
of specialised ectoderm cells (hypodermis) that secrete the cuticular lens, a middle
layer of visual or retinal elements, and an inner layer of pigment-cells. The elements
of the middle layer consist of much elongated cells, whose branching outer ends are
connected with nerve-fibrils and interwoven in a protoplasmic syncytium, whose
middle parts are occupied by the nuclei and whose inwardly directed ends form the
retinal rods or bacilli. The pigment-cells of the inner layer are of various forms,
those towards the middle of the eye being small and flattened, those at the sides
being, for the most part, long and attenuated, so seeming, as Morgan remarks, to
approximate in character to the retinal elements. The pigment-layer is easily
dispersed and reveals beneath it a median vertical raphe, caused by the convergence
of the cells of the middle layer from either side, and along the line of this raphe the
optic nerve joins the eye, though its subsequent course to its connection with the
retinal elements is obscure. It is at least clear that the retina is an “inverted” retina,
with the nerve-connected bases of its cells lying outwards and their bacillar
extremities directed inwards.
In a longitudinal vertical section of the eye of a larva (Tanystylum), at a stage
when three pairs of walking legs are present, Morgan shows us the pigment-layer
apparently continuous with the hypodermis just below the eye, and in close
connection with the middle layer at the upper part of the eye. From this we are
permitted to infer a development by invagination, in which the long invaginated sac
is bent and pushed upwards till it comes into secondary contact with the hypoderm,
so giving us the three layers of the developed eye. This manner of formation is
precisely akin to that described by Parker, Patten, Locy, and others for the median
eyes of Scorpions and of Spiders, and the organ is structurally comparable to the
Nauplius- or median eye of Crustacea. But neither in these cases nor in that of the
Pycnogon is the whole process clear, in consequence chiefly of the obscurity that
attends the course of the optic nerve in both embryo and adult. For various
discussions and accounts, frequently contradictory, of these phenomena, the reader
is referred to the authors quoted, or to Korschelt and Heider’s judicious summary.
[406]
There seems to be a small structure, of some sort or other, between the ocelli on
either side. Dohrn thought it might be auditory, Loman that it might be secretory,
but its use is unknown.
Integument.—The chitinised integument is perforated by many little cavities,
some of them conical and tapering to a minute external pore, the others more
regularly tubular. Sometimes, but according to Hoek rarely, the tubular pore-canals
communicate with, or arise from, the conical cavities. The pore-canals transmit a
nerve for the supply of sensory hairs, often forked, which arise from the orifice of the
canal in little groups of two or more, sometimes in rosettes of eight or nine. These
setae are small or rudimentary in Ascorhynchus and totally wanting in Colossendeis;
they appear to be extremely large and stellate in Paranymphon. The conical cavities
contain proliferated epithelial cells, blood corpuscles, and cells of more doubtful
nature that are perhaps glandular. According to Dohrn, glands exist in connection
with both kinds of integumentary perforations, and he suspects that they secrete a
poisonous fluid in response to stimuli affecting the sensory hairs; Hoek, on the other
hand, is inclined to ascribe a respiratory function to the cavities; but indeed, as yet,
we must confess that their use is undetermined.
Reproductive Organs.—In each sex the generative organs consist of a pair of
ovaries or testes lying above the gut on either side of the heart; in the adult they are
fused together posteriorly at the base of the abdomen, and send long diverticula into
the ambulatory legs. In the female Phoxichilidium, at least, as Loman has lately
shown, the fusion is complete, and the ovary forms a thin broad plate, spreading
through the body and giving off its lateral diverticula. The diverticula of the testes
reach to the third joint of the legs, those of the ovaries to the fourth, or sometimes
farther. The ova ripen within the lateral diverticula, chiefly, and sometimes (Pallene)
exclusively, in the femora or fourth joints of the legs,[407] which, in many forms, are
greatly swollen to accommodate them; the spermatozoa, on the other hand, are said
to develop both within the legs and within the thoracic portions of the testis. The
genital diverticula may end blindly within the leg, or communicate through a duct
with the exterior by a valvular aperture placed on the second coxal joint. Such
apertures occur, as a rule, on all the legs in the females, in Rhynchothorax and
Pycnogonum on the last only. In the males an aperture is present on all the legs in
Decolopoda and Phoxichilidium; on the last three in Nymphon and Phoxichilus; in
most genera on the last two; in Pycnogonum and Rhynchothorax on the last only.
Very commonly the female individuals are somewhat larger than the males, and in
some species (Ammothea, Trygaeus) the latter are distinguished by a greater
development of spines or tubercles on the body and basal joints of the legs (Dohrn).
The act of fecundation has been observed by Cole[408] in Anoplodactylus. The
animal reproduces towards the end of August. Consorting on their Eudendrium
(Hydroid) colony, the male climbs upon the female and crawls over her head to lie
beneath her, head to tail; and then, fertilisation taking place the while, the hooked
ovigerous legs of the male fasten into the extruding egg-masses and tear them away.
The whole process is over in five minutes. The fresh egg-masses are more or less
irregular in shape, and white in colour like little tufts of cotton.
Each ball of eggs that the male carries represents the entire brood of one female,
and in Phoxichilidium Loman has seen a male carrying as many as fourteen balls.
Fertilisation is external, taking place while the eggs are being laid. The spermatozoa
have small rounded heads and long tails, and are thus unlike the spermatozoa of
most Crustacea.
Development.—Until the hatching of the embryo, the eggs of the Pycnogons are
carried about, agglutinated by cement-substance into coherent packets, on the
ovigerous legs of the males. They are larger or smaller according to the amount of
yolk-substance present, very small in Phoxichilidium and Tanystylum (Morgan),
where they measure only ·05 mm. in diameter; larger in Pallene (·25 mm.); larger
still (·5–·7 mm.) in Nymphon. In Pallene each egg-mass commonly contains only
two eggs; in the other genera they are much more numerous, rising to a hundred or
more in Ammothea (Dohrn). The egg-masses may be one or more on each ovigerous
leg, sometimes (Phoxichilidium angulatum, Dohrn) a single egg-mass is held by
both legs; they are extremely numerous in Phoxichilus, and in Pycnogonum they
coalesce to form a broad pad beneath the body. The fact that it is the male and not
the female that carries the eggs was only announced in 1877 by Cavanna;[409] before,
and by some even after his time, the two sexes were constantly confused.[410]
Segmentation is complete, symmetrical
in the forms with smaller eggs, unequal in
those burdened with a preponderance of
yolk (Morgan). In Pallene, as in the
Spider’s egg, what is described as at first a
total segmentation passes into a
superficial or centrolecithal one by the
migration outwards of the nuclei and the
breaking down of the inner ends of the
wedge-shaped segmentation-cells. The
blastoderm so formed becomes
concentrated at the germinal pole of the
egg. A thickened portion of the
blastoderm (which Morgan compares to
the “cumulus primitivus” of the Spider’s
egg) forms an apparently blastoporal
invagination (though Morgan calls it the
stomodaeum), and from its sides are
budded off the mesodermal bands.
Meisenheimer has recently given a
minute account of the early development
of Ammothea, a form with small yolkless
Fig. 280.—Young larva (nat. size ·1 mm.) of
eggs. Here certain cells of the uniform
Ammothea fibulifera, Dohrn. C.G, Brain; gl, gld,
gland and duct of chelophore; pr, proboscis; I, and almost solid blastosphere grow
II, III, IV, appendages. (After Dohrn.) inwards till their nuclei arrange
themselves in an inner layer of what (so
far as they are concerned) is a typical
gastrula, but without any central cavity. The inner layer subsequently, but slowly,
differentiates into the mid-gut, and into dorsal and lateral offshoots, the sources of
the heart and of the muscles and connective tissues respectively. The further
development of the egg takes place, as is usual in Arthropods, by the appearance, in
a longitudinal strip or germ-band which enwraps the yolk, of paired thickenings
which represent the cerebral and post-oral ganglia, and of others from which arise
the limbs. Of these latter, the chelophores are the first to appear, on either side of
the mouth; in Pallene the fourth pair appears next in order, followed by the fifth and
sixth, and by the third and seventh just before the hatching out of the embryo; the
second is lacking in this particular genus. Thus in Pallene (Dohrn, Morgan), and in
some others, e.g. Nymphon brevicollum (Hoek), the free larva is from the first
provided with its full complement of limbs. Certain other species of Nymphon hatch
out in possession of four or five pairs of limbs, but in the great majority of cases
studied the larval Pycnogon is at first provided with three pairs only, the three
anterior pairs of the typical adult.[411] Numerical coincidence, and that alone, has
often led this “Protonymphon” larva to be compared with the Crustacean Nauplius.
In the annexed figure of a young larval Ammothea (Achelia), we see the
unsegmented body, the already chelate chelophores (furnished with the provisional
cement-glands already described), the other two pairs of appendages each with a
curious spine at its base, the gut beginning to send out diverticula (of which the first
pair approach the chelophores) but still destitute of the anus (which is only to be
formed after the development of the abdomen), the proboscis, and one pair of eyes
situated close over the pre-oral ganglia. The subsequent changes are in this genus
extremely protracted, and terminate with the loss of the chelae, a process which
occurs so late in life that the chelate individuals were long looked upon as belonging
to a separate genus, the original Ammothea of Hodge, until Hoek proved their
identity with the clawless Achelia.
The developmental history of Phoxichilidium and Anoplodactylus is peculiar. The
young larvae have the claws of the second and third appendages hypertrophied to
form enormous stiff tendril-like organs, with which they affix themselves to the
bodies of Hydroid Zoophytes (Coryne, Eudendrium, Tubularia, Hydractinia, etc.),
feeding as the adults do: afterwards losing these elongated tendrils in a moult, they
pass into the gastral cavity of the Hydroid; in our native species the larva issues from
the Hydroid and begins its independent life at a stage when three pairs of
ambulatory legs are present and the fourth is in bud.[412] The Phoxichilidium larvae
were first noticed by Gegenbaur in Eudendrium,[413] again by Allman in Coryne
eximia.[414] George Hodge made detailed and important observations,[415] and
showed, in opposition to Gegenbaur, that it was the larva which entered the Hydroid
and not the egg that was laid therein.[416]
Fig. 281.—Larva of Phoxichilidium sp., showing tendril-like appendages of the

larval palps and ovigerous legs. (After Dohrn.)
Moseley has the following interesting note in his Challenger Report:[417] “The most
interesting parasite observed was a form found in the gastric cavities of the
gastrozoids of Pliobothrus symmetricus (West Indies, 450 f.), contained in small
capsules. These capsules were badly preserved, but there seemed little doubt that
they contained the remains of larvae of a Pycnogonid, so that the deep-sea
Pycnogonids, which are so abundant, very possibly pass through their early stages in
deep-sea Stylasteridae.... The gastrozoids containing the larvae were partly aborted.”
A Pycnogon larva, doubtfully ascribed to Nymphon, has been found living in
abundance ectoparasitically on Tethys in the Bay of Naples.[418]
Habits.—Of the intimate habits of the Pycnogons we can say little. Pycnogonum
we often find clinging, as has been said, close appressed to some large Anemone
(Tealia, Bolocera, etc.), whose living juices it very probably imbibes. The more
slender species we find climbing over sea-weeds and Zoophytes, where sometimes
similarity of colour as well as delicacy of form helps to conceal them; thus
Phoxichilidium femoratum (Orithyia coccinea, Johnston) is red like the Corallines
among which we often find it, P. virescens green like the filamentous Ulvae, the
Nymphons yellowish like the Hydrallmania and other Zoophytes which they affect.
On the New England coast, according to Cole, the dark purple Anoplodactylus
lentus, Wilson (Phoxichilidium maxillare, Stimpson), is especially abundant on
colonies of Eudendrium, whose colour matches its own, the yellowish Tanystylum
orbiculare frequents a certain yellowish Hydroid, and of these two species neither is
ever found on the Hydroid affected by the other; while, on the other hand, Pallene
brevirostris, whose whitish, almost transparent body is difficult to see, is more
generally distributed.[419] The deep-sea Pycnogons (Colossendeis, Nymphon) are
generally (if not universally) of a deep orange-scarlet colour, a common dress of
many deep-sea Crustacea.
The movements of the Pycnogons are singularly slow and deliberate; they are
manifestly not adapted to capture or to kill a living prey. Linnaeus accepted from J.
C. König the singular statement that they enter and feed upon bivalve shells,
“Mytilorum testes penetrat et exhaurit”; but the statement has never been
reaffirmed.[420]
Loman describes Phoxichilidium as feeding greedily on Tubularia larynx, and
especially on the gonophores. It grasps them with its claws, sucks them in bit by bit
till the proboscis is filled as far as the sieve, whereupon that part of the proboscis
squeezes and kneads the mass, letting only juices and fine particles pass through
into the alimentary canal. The lateral caeca and the rectum are separated by
sphincter muscles from the stomach; the former are in turn filled with food and
again emptied; the contents of the alimentary canal are in constant rolling
movement, and the faeces are eliminated by the action of a pair of levatores ani, in
round pellets.
The Pycnogons, or some of them, can swim by “treading water,” and Pallene is
said by Cole to swim especially well; they more often progress half by swimming,
half by kicking on the bottom. They move promptly towards the light, unless they
have Hydroids to cling to, and Cole points out that when they crawl with all their
legs on the bottom they move forwards towards the light,[421] but backwards when
they swim in part or whole. The legs move mostly in a vertical plane, horizontal
movements taking place chiefly between the first and second joints. Tanystylum is
uncommonly sluggish and inert; it sinks to the bottom, draws its legs over its back
and remains quiet, while Pallene, by vigorous kicks, remains suspended.
The long legs of the Pycnogons are easily injured or lost, and easily repaired or
regenerated. This observation, often repeated, is as old as Fabricius: “Mutilatur
etiam in libertate sua, redintegrandum tamen; vidi enim in quo pedes brevissimi
juxta longiores enascentes, velut in asteriis cancris aliisque redintegratis.” In such
cases of redintegration of a leg, the reproductive organ, the genital orifice, and the
cement-gland are not restored until the next moult.[422]
Systematic Position.—To bring this little group into closer accord with one or
other of the greater groups of Arthropods is a problem seemingly simple but really
full of difficulty.
The larval Pycnogon, with its three pairs of appendages, resembles the Crustacean
Nauplius in no single feature save this unimportant numerical coincidence; nor is
there any significance in the apparent outward resemblance to isolated forms (e.g.
Cyamus) that induced some of the older writers, from Fabricius downwards and
including Kröyer and the elder Milne-Edwards, to connect the Pycnogons with the
Crustacea. To refer them, or to approximate them to the Arachnids, has been a
stronger and a more lasting tendency.[423] Linnaeus (1767) included the two species
of which he was cognisant in the genus Phalangium, together with P. opilio.
Lamarck, who first formulated the group Arachnida (1802), let it embrace the
Pycnogons; and Latreille (1804, 1810), who immediately followed him, defined more
clearly the Pycnogonida as a subdivision of the greater group, side by side with the
subdivision that corresponds to our modern Arachnida (“Arachnides acères”), and
together with a medley of lower Crustacea, Myriapoda, Thysanura, and Parasitic
Insects; he was so cautious as to add “j’observerai seulement, que je ne connais pas
encore bien la place naturelle des Pycnogonides et des Parasites,” and Cuvier, setting
them in a similar position, adds a similar qualification.[424]
Leach (1814), whose great service it was to dissociate the Edriophthalmata and the
Myriapoda from the Latreillian medley, left the group Arachnida as we still have it
(save for the inclusion of the Dipterous Insect Nycteribia), and divided the group
(with the same exception) into four Orders of which the Podosomata, i.e. the
Pycnogonida, are one. Savigny (1816), less philosophical in this case than was his
wont, assumed the Crustacean type to pass to the Arachnidan by a loss of several
anterior pairs of appendages, and appears to set the Pycnogons in an intermediate
grade, marking the pathway of the change. He considered the seven pairs of limbs of
the Pycnogons to represent thoracic limbs of a Malacostracan, and, like so many of
his contemporaries, was much biased by the apparent resemblance of Cyamus to
Pycnogonum. The reader may find in Dohrn’s Monograph a guide to many other
opinions and judgments, some of them of no small morphological interest and
historical value[425]; but it behoves us to pass them by, and to inspect, in brief, the
case as it stands at present. The obvious features in which a Pycnogon resembles a
Spider or other typical Arachnid, are the possession of four pairs of walking legs, and
the pre-oral position and chelate form of the first pair of appendages; we may
perhaps also add, as a more general feature of resemblance, the imperfect
subservience of limbs to the mouth as compared with any of the Crustacea. The
resemblance would still be striking, in spite of the presence of an additional pair of
legs in a few Pycnogons, were it not for the presence of the third pair of appendages
or ovigerous legs of the Pycnogon, whose intercalation spoils the apparent harmony.
We are neither at liberty to suppose, with Claus, that these members, so important
in the larva, have been interpolated, as it were, anew in the Pycnogon; nor that they
have arisen by subdivision of the second pair, as Schimkewitsch is inclined to
suppose; nor that they have dropped out of the series in the Arachnid, whose body
presents no trace of them in embryo or adult. In a word, their presence precludes us
from assuming a direct homology between the apparently similar limbs of the two
groups,[426] and at best leaves it only open to us to compare the last legs of the
Pycnogon with the first abdominal, or genital, appendages of the Scorpion and the
Spider. On the other hand, if we admit the seventh (as we must admit the occasional
eighth) pair of appendages of Pycnogons to be unrepresented in the prosoma of the
Arachnids, then, in the cephalothorax of the former, with its four pairs of
appendages, we may find the homologue of the more or less free and separate part of
the cephalothorax in Koenenia, Galeodes, and the Tartaridae. There is a
resemblance between the two groups in the presence of intestinal diverticula that
run towards or into the limbs, as in Spiders and some Mites, and there are certain
histological and embryological resemblances that have been in part referred to
above; but these, such as they are, are not adequate guides to morphological
classification. We must bear in mind that such resemblances as the Pycnogons seem
to show are not with the lower Arachnids but with the higher; they are either
degenerates from very advanced and specialised Arachnida, or they are lower than
the lowest. Confronted with such an issue, we cannot but conclude to let the
Pycnogons stand apart, an independent group of Arthropods[427]; and I am inclined
to think that they conserve primitive features in the usual presence of generative
apertures on several pairs of limbs, and probably also in the non-development of any
special respiratory organs. But inasmuch as the weight of evidence goes to show that
subservience of limbs to mouth is a primitive Arthropodan character, the fact that
the basal elements of the anterior appendages have here (as in Koenenia) no such
relation to the mouth must be taken as evidence, not of antiquity, but of
specialisation. In like manner the suctorial proboscis cannot be deemed a primitive
character, and the much reduced abdomen also is obviously secondary and not
primitive.
Classification.—No single genus more than another shows signs of affinity with
other groups, and no single organ gives us, within the group, a clear picture of
advancing stages of complexity. On the contrary, the differences between one genus
and another depend very much on degrees of degeneration of the anterior
appendages, and we have no reason to suppose that these stages of degeneration
form a single continuous series, but have rather reason to believe that degeneration
has set in independently in various ways and at various points in the series. But
while we are unable at present to form a natural classification[428] of the Pycnogons,
yet at the same time a purely arbitrary or artificial classification, conveniently based
on the presence or absence of certain limbs, would run counter to such natural
relationships as we can already discern.
The classification here adopted is a compromise between a natural system, so far
as we can detect it, and an artificial one.
Two forms, separated from one another by many differences, show a minimum of
degeneration, namely Decolopoda on the one hand, and the Nymphonidae on the
other. The former genus has five pairs of legs, and this peculiarity is shared by
Pentanymphon. In both groups the three anterior limbs are all present and well
formed, save only that the ovigerous legs, which have ten joints in Decolopoda, are
reduced to five joints in the Nymphons, and their denticulate spines, of which
several rows are present in the former, are reduced to one row in the latter; on the
other hand, a greater or a less degeneration of these limbs marks each and all of the
other families.
Decolopoda is very probably the most primitive form known, though it has
characters which seem to be the reverse of primitive in the dwarfish size of its
chelophores and the crowded coalescent segmentation of the trunk. Colossendeis, in
spite of its vanished chelophores, is probably closely allied: the shape and
segmentation of the body and the several rows of smooth denticles on the ovigerous
legs are points in common. The Eurycydidae are closely allied to Colossendeidae;
they agree with Decolopoda in the two-jointed scape of the chelophore, and with
Ammotheidae in the deflexed mobile proboscis. The true position of Rhynchothorax
is very doubtful.
The Nymphonidae and Pallenidae are closely allied, and the Phoxichilidiidae have
points of resemblance, especially with the latter. Nymphon compares with
Decolopoda in the completeness of its parts, and is more typical in its long well-
segmented body, and in its highly-developed chelae; but it already shows reduction
in the scape of the chelophore, in the palps, and in the armature of the ovigerous
legs.
The Phoxichilidae and Pycnogonidae (Agnathonia, Leach; Achelata, Sars), though
differing greatly in aspect, are not improbably allied to one another; and whether
this be so or not, the complete absence of chelophores and of palps affords an
arbitrary character by which they are conveniently separated from all the rest.
The following table epitomises the chief characters of the several families:—
Pycnogonida. Proboscis. Chelophores. Palps. Ovigerous Teeth Legs. Trunk- Genital
legs. on do. segments. Openings.
♂ ♀
(Cryptochelata,
Sars)—
Decolopodidae Fixed, Complete, 10 joints 10 joints ♂, Four 5 Condensed, 1, 2, 1, 2,
decurved small, scape 2– ♀ rows, coalescent 3, 4, 3, 4,
jointed simple 5, 5
Colossendeidae Somewhat 0 10 10 ♂, ♀ Many 4 Coalescent 1, 2, 1, 2,
mobile, rows, 3, 4 3, 4
sometimes simple
decurved
Eurycididae Mobile, Scape 2– 10 10 ♂, ♀ More 4 Well 3, 4 1, 2,
stalked, jointed, chelae than one segmented 3, 4
deflexed rudimentary row,
serrate
Hannonia „ Rudimentary 0 10 ♂, ♀ Scattered 4 „ „ „
spines
Ammotheidae Mobile, „ 4–9 10 (or less) Few, 4 Condensed, „ „
deflexed ♂, ♀ scattered, segmented
serrate or
smooth
? Large, 0 8 (5) 10 ♂, ♀ Toothed 4 „ 4 4
Rhynchothoracidae fixed, tubercles
aberrant
(Euchelata, Sars)—
Nymphonidae Large, fixed Large, scape 1– 5 (7) 8–10 ♂, ♀ One row, 4–5 Well 2, 3, 1, 2,
jointed serrate segmented 4 3, 4
(5) (5)
Pallenidae „ „ 0 or 10 ♂, ♀ „ 4 „ (1, „
rudimentary 2),
3, 4
Phoxichilidiidae „ „ 0 5–6 ♂ One row, 4 „ 1, 2, „
simple 3, 4
(Achelata, Sars)—
Phoxichilidae Large, fixed 0 0 7♂ Scattered, 4 Well 2, 3, 1, 2,
simple segmented 4 3, 4
Pycnogonidae „ 0 0 9♂ Small, 4 Segmented, 4 4
irregular condensed
CLASS PYCNOGONIDA.[429]
Marine Arthropoda, with typically seven (and very exceptionally eight) pairs of
appendages, of which none have their basal joints subservient to mastication, the
first three are subject to suppression, the first (when present) are chelate, the second
palpiform, the third ovigerous, and the rest form ambulatory limbs, usually very
slender and long; with a suctorial proboscis, a limbless, unsegmented abdomen, and
no manifest respiratory organs.
Fig. 282.—Decolopoda australis, Eights. A, × 1: from a specimen obtained at the
South Shetlands by the Scotia Expedition. B, First appendage, or chelophore. (A,
original; B, after Hodgson.)
Fam. 1. Decolopodidae.—Appendage I. dwarfed, but complete and chelate,

scape with two joints; II. 9–10–jointed; III. well developed in both sexes, 10–
jointed, the terminal joints with about four rows of teeth; five pairs of legs, destitute
of accessory claws; genital apertures on all the legs (Bouvier).
Decolopoda australis, Eights[430] (1834), a remarkable form from the South
Shetlands, recently re-discovered by the Scotia expedition. The animal is large,
seven inches or more in total span, in colour scarlet; it was found in abundance in
shallow water and cast upon the shore. The body is greatly condensed, the proboscis
is “clavate, arcuated downwards,” and beset with small spines. A second Antarctic
species, D. antarctica, has been described by Bouvier. The presence of a fifth pair of
legs distinguishes Decolopoda from all known Pycnogons, except Pentanymphon.
Stebbing would ally Decolopoda with, or even include it in, the Nymphonidae; but
the presence of a second joint in the chelophoral scape, the number of joints in, and
the armature on, the ovigerous legs, and the deflexed proboscis, are all characters
either agreeing with or tending towards those of the Eurycididae; while the
Colossendeidae would be very like Decolopoda were it not for the complete
suppression of the chelophores. It seems convenient to constitute a new family for
this remarkable form.
Fam. 2. Colossendeidae (Pasithoidae, Sars).—Appendage I. absent in adult;
appendage II. very long, 10–jointed; appendage III. 10–jointed, clawed, with many
rows of teeth; auxiliary claws absent; segments of trunk fused; proboscis very large,
somewhat mobile; genital apertures, in at least some cases, on all the legs.
Pasithoe, Goodsir (1842), which Sars assumes as the type of the family, is here
relegated to Ammothea.[431] Colossendeis, Jarszynsky (1870) (Anomorhynchus,
Miers (1881), Rhopalorhynchus, Wood-Mason (1873)), remains as the only genus
commonly accepted: large, more or less slender short-necked forms; world-wide,
principally Arctic, Antarctic, and deep-sea; about twenty-five species.[432] The largest
species, C. gigas, Hoek, from great depths in the Southern Ocean, has a span of
about two feet. The North Atlantic C. proboscidea and Antarctic C. australis are very
closely related to one another. Carpenter would retain the genus Rhopalorhynchus
for R. kröyeri, W.-M. (Andamans), R. clavipes, Carp. (Torres Straits), and R.
tenuissimus, Haswell (Australia), all more or less shallow-water species, excessively
attenuated, with the second and third body-segments elongated, the caudal segment
excessively reduced, the club-shaped proboscis on a slender stalk, and other
common characters. Pipetta weberi, Loman (1904), is a large and remarkable form
from the Banda Sea, apparently referable, in spite of certain abnormal features, to
this family; the proboscis is extraordinarily long and slender; the palps have eight
joints, the ovigerous legs eleven.
Fam. 3. Eurycididae (Ascorhynchidae, Meinert).—Appendage I. more or less
reduced; appendage II. 10–jointed (absent in Hannonia); appendage III. 10–
jointed, clawed, with more than one tow of serrated teeth; proboscis movably
articulated and more or less bent under the body; auxiliary claws absent.
Eurycide, Schiödte (1857) (Zetes,
Kröyer, 1845): Appendage I. with two-
jointed scape, without chelae in adult;
one species (E. hispida, (Kr.)), from the
North Atlantic and Arctic, and two others
from the East Indies, recently described
by Loman. Barana arenicola, Dohrn
(1881), is nearly allied. Ascorhynchus, G.
O. Sars (1876) (Gnamptorhynchus,
Böhm, 1879; Scaeorhynchus, Wilson,
1881), very similar to Eurycide, with Fig. 283.—Eurycide hispida, Kr.; side view.
which, according to Schimkewitsch, it
should be merged, includes large,
smooth, elongated forms, with long neck and expanded frontal region, and a long
proboscis lacking the long scape that supports the proboscis in Eurycide; about
twelve species, world-wide, mostly deep-water. Barana castelli, Dohrn, from Naples
is akin to the foregoing genera, but seems to deserve generic separation from B.
arenicola. Ammothea longicollis, Haswell, from Australia, is, as Schimkewitsch has
already remarked, almost certainly a Eurycide, as is also, probably, Parazetes
auchenicus, Slater, from Japan.
Hannonia typica, Hoek (1880), from Cape Town, is a remarkable form, lately
redescribed by Loman. The chelophores are much reduced, the palps are absent; the
ovigerous legs are 10–jointed, and clawed; the terminal joints of the latter bear long
straight spines, scattered over their whole surface; the proboscis is borne on a
narrow stalk, and sharply deflexed. The eggs form a single flattened mass, as in
Pycnogonum. While the lack of palps would set this genus among the Pallenidae, the
remarkable proboscis seems to be better evidence of affinity with Ascorhynchus and
Eurycide.[433]
Nymphopsis, Haswell (1881), is a genus of doubtful affinities, placed here by
Schimkewitsch. The first appendage is well-developed and chelate; the palps are 9–
jointed, the ovigerous legs are 7–jointed, none of the joints being provided with the
compound spines seen in Nymphon and Pallene. It is perhaps an immature form.
Schimkewitsch has described another species, N. korotnevi, and Loman a third, N.
muscosus, both from the East Indies.
Fam. 4. Ammotheidae.—Akin to Eurycididae in having the proboscis more or
less movably jointed to the cephalic segment, and appendage I. reduced, non-chelate
in the adult; the body is compact and more or less imperfectly segmented;
appendage II. 4–9–jointed; appendage III. clawless, and the number of joints
sometimes diminished, with a sparse row of serrated spines; auxiliary claws usually
present.
Ammothea, Leach (1815) (including Achelia, Hodge (1864) = the old non-chelate
individuals): appendage I. very small, 2–jointed; appendage II. 8–9–jointed; caudal
segment fused with last body-segment; about eighteen species, four from the South
Seas, two or three from the East Indies, the rest mostly Mediterranean and North
Atlantic, in need of revision. Ammothea longipes, Hodge, is the young of Achelia
hispida, Hodge; and Ammothea magnirostris, Dohrn, is apparently the same
species. A. fibulifera, Dohrn, seems identical with Achelia echinata, Hodge (of
which A. brevipes, Hodge, is the young), and so probably is A. achelioides, Wilson;
Endeis didactyla, Philippi (1843), is very probably the same species. A.
uniunguiculata, Dohrn (? Pariboea spinipalpis, Philippi (1843)), has no auxiliary
claws. Leionymphon, Möbius (1902), contains nine Antarctic forms, allied to
Ammothea (including A. grandis, Pfeffer, and Colossendeis gibbosa, Möb., which
two are probably identical), with characteristic transverse ridges on the body, a large
proboscis, a 9–jointed palp, and somewhat peculiar ovigerous legs. Cilunculus,
Fragilia, and Scipiolus are new genera more or less allied to Leionymphon,
described by Loman (1908) from the Siboga Expedition.[434] Tanystylum, Miers
(1879) (including Clotenia, Dohrn (1881), and Discoarachne, Hoek (1880)), has
appendage I. reduced to a single joint or a small tubercle, and appendage II. 4–6–
jointed; world-wide; about eight species. Austrodecus glacialis and Austroraptus
polaris are two allied Antarctic species, described by Hodgson (1907), the former a
curious little form with a pointed, weevil-like proboscis, no chelophores, and 6–
jointed palp. Trygaeus communis, Dohrn (1881), from Naples, has a 7–jointed, and
Oorhynchus aucklandiae, Hoek (1881), a 9–jointed palp; the former has only seven
joints in the ovigerous leg. Lecythorhynchus armatus, Böhm (1879), with
rudimentary 2–jointed chelophores, and L. (Corniger) hilgendorfi, Böhm, with
small tubercles in their place, both from Japan, have also 9–jointed palps: the
former, at least, is apparently an Ammothea. Several insufficiently described genera,
Phanodemus, Costa (1836), Platychelus, Costa (1861), Oiceobathes, Hesse (1867),
and Böhmia, Hoek (1880), seem to be referable to this group; all have chelate
mandibles, and may possibly be based on immature forms.
Goodsir’s Pasithoe vesiculosa[435] is, in my opinion, undoubtedly Ammothea
hispida, Hodge, and so also, I believe, is his Pephredo hirsuta; P. umbonata,
Gould[436] (Long Island Sound), is, with as little doubt, Tanystylum orbiculare,
Wilson.
Fam. 5. Rhynchothoracidae.—The animal identified by Dohrn as
Rhynchothorax mediterraneus, Costa (1861), is a minute and very remarkable form,
without chelophores, with large 8–jointed palps, reduced by fusion to five joints,
and 10–jointed, clawed ovigerous legs, which last are provided on the last five joints
with peculiar toothed tubercles. The general aspect of the body is somewhat like that
of an Ammothea, which genus it resembles in the ventral insertion of the ovigerous
legs and the somewhat imperfect segmentation of the body. It differs from
Ammotheidae in the possession of a claw on appendage III. It is highly peculiar in
the structure of the mouth, in having a long forward extension of the oculiferous
tubercle jutting out over the proboscis, in the extreme shortness of the intestinal
caeca and ovaries which scarcely extend into the legs, and in the absence of cement-
glands from the fourth joint of the legs; these last are present only in the third joint
of the penultimate legs. A single pair of generative orifices are found on the last legs.
A second species, R. australis, Hodgson, comes from the Antarctic.
Fig. 284.—Rhynchothorax mediterraneus, Costa. A, Body and bases of legs; B,

terminal joints of palp. (After Dohrn.)
Fam. 6. Nymphonidae.—Appendage I. well-developed, chelate; II. well-
developed, usually 5–jointed; III. well-developed in both sexes, usually 10–jointed,
the terminal joints with one row of denticulated spines.
Nymphon, Fabr. (1794), about forty-five recognised species, of which some are
but narrowly defined. Closely allied are Chaetonymphon, G. O. Sars (1888),
including thick-set, hairy species, about eight in number, from the North Atlantic,
Arctic, and Antarctic; and Boreonymphon, G. O. Sars (1888), with one species (B.
robustum, Bell, Fig. 276), also northern, in which the auxiliary claws are almost
absent. Nymphon brevicaudatum, Miers (= N. horridum, Böhm), an extraordinary
hispid form from Kerguelen,[437] is also peculiar. Pentanymphon, Hodgson (1904),
from the Antarctic (circumpolar), differs in no respect save in the presence of a fifth
pair of legs; one species.
The only other genus is Paranymphon, Caullery (1896) (one species, Gulf of
Gascony, West of Ireland, Greenland), in which the palp is (6–)7–jointed, the
ovigerous leg 8–jointed, and the auxiliary claws are absent.
Fam. 7. Pallenidae.—As in Nymphon, but appendage II. absent or rudimentary.
Pallene, Johnston (1837): about ten species (Mediterranean, North Atlantic,
Arctic, Australia). P. languida, Hoek, Australia, lacks auxiliary claws, and is
otherwise distinct; but P. novaezealandiae, G. M. Thomson, is typical.
Pseudopallene, Wilson (1878):[438] appendage III. clawed; auxiliary claws absent;
four (or more) species (North Atlantic, Arctic, Antarctic). P. (Phoxichilus) pygmaea,
Costa (1836), and P. spinosa, Quatref., seem to belong to this genus or to Pallene.
Cordylochele, G. O. Sars (1888): closely allied, but with front of cephalic segment
much expanded and chelae remarkably swollen, includes three very smooth,
elongated, northern species, to which Bouvier has added one from the Antarctic;
Pallene laevis, Hoek, from Bass’s Straits, is somewhat similar. Neopallene, Dohrn
(1881): as in Pallene, but with a rudimentary second appendage in the female, and
no generative aperture on the last leg in the male (one species, Mediterranean).
Parapallene, Carpenter (1892): as in Pallene, but without auxiliary claws, and with
the two last segments of the trunk (which in Pallene are coalesced) independent
(about ten species, East Indies and Australia); Pallene grubii, Hoek (Phoxichilidium
sp., Grube, 1869), is probably congeneric. Pallenopsis, Wilson (1881): appendage I.
2–jointed; appendage II. rudimentary, 1–jointed; appendage III. clawless; auxiliary
claws present; slender forms, including some formerly referred to Phoxichilidium;
about fifteen species, world-wide. Pallene dimorpha, Hoek, from Kerguelen, with 4–
jointed palps, deserves a new generic appellation. P. longiceps, Böhm, from Japan,
with rudimentary 2–jointed palps in the male, is also peculiar.
Fig. 285.—Pallene brevirostris, Johnston, ♀ ,
Plymouth.
Fig. 286.—Phoxichilidium femoratum, Rathke, Britain. A, The animal with its
legs removed; B, leg and chela.
Fam. 8. Phoxichilidiidae.—Appendage I. well-developed; II. absent; III.

present only in the male, having a few simple spines in a single row. The last
character is conveniently diagnostic, but nevertheless the Phoxichilidiidae come very
near to the Pallenidae, with which, according to Schimkewitsch and others, they
should be merged; the two families resemble one another in the single row of spines
on the ovigerous legs and in the extension of the cephalic segment over the base of
the proboscis.
Phoxichilidium, M.-E. (1840): appendage III. 5–jointed; five or six species
(Mediterranean, North Atlantic, Arctic, Australia, Japan). Anoplodactylus, Wilson
(1878): appendage III. 6–jointed; auxiliary claws absent or very rudimentary; about
twelve species, cosmopolitan, of which many were first referred to Phoxichilidium.
A. neglectus, Hoek, comes from 1600 fathoms off the Crozets. Oomerus
stigmatophorus, Hesse (1874), from Brest, seems to belong to one or other genus,
but is unrecognisable. Anaphia, Say (1821), is in all probability identical with
Anoplodactylus, and if so the name should have priority. Halosoma, Cole (1904), is
an allied genus from California.
Fig. 287.—Anoplodactylus petiolatus, Kr., Britain. A, Dorsal view; B, side view.
Fam. 9. Phoxichilidae.[439]—Appendage I. and II. absent; appendage III.

present only in the males, 7–jointed, with minute scattered spines; auxiliary claws
well-developed; body and legs slender. The only genus is Phoxichilus (auctt., non
Latreille, Chilophoxus, Stebbing, 1902); the type is P. spinosus, Mont. (non
Quatrefages), from the N. Atlantic, and P. vulgaris, Dohrn, P. charybdaeus, Dohrn,
and P. laevis, Grube, are all very similar. Endeis gracilis, Philippi (1843), is probably
identical with P. spinosus, or one of its close allies. There are also known P.
meridionalis, Böhm, P. mollis, Carp., and P. procerus, Loman, from the East Indies;
P. australis, Hodgson, from the Antarctic; P. böhmii, Schimk., of unknown locality;
and forms ascribed to P. charybdaeus by Haswell and by Schimkewitsch from
Australia and Brazil.
Fam. 10. Pycnogonidae.—Appendages I. and II. absent; appendage III. present
only in the male, 9–jointed, with small, simple spines; auxiliary claws absent or
rudimentary; body and legs short, thick-set.
The only genus is Pycnogonum, Brünnich (1764) (Polygonopus, Pallas, 1766); the
type is P. littorale, Ström, of the N. Atlantic (0–430 fathoms), to which species have
also been ascribed forms from various remote localities, e.g. Japan, Chile, and
Kerguelen. P. crassirostre, G. O. Sars, a northern and more or less deep-sea form, is
distinct, and so also are P. nodulosum and P. pusillum, Dohrn, from Naples. P.
stearnsi, Ives, from California, is like P. littorale, except for the rostrum, which
resembles that of P. crassirostre. P. magellanicum, Hoek, P. magnirostre, Möbius,
both from the Southern Ocean; P. microps, Loman, from Natal, and four others
described by Loman from the East Indies, are the other authenticated species. Of P.
philippinense, Semper, I know only the bare record; and P. australe, Grube, is
described only from a larval form with three pairs of legs. P. orientale, Dana (first
described as Astridium, n.g.), is also described from an immature specimen, and
more resembles a Phoxichilus.

Advanced Data Analysis Modelling in Chemical Engineering 1St Edition Denis Constales Full Chapter

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Advanced Data Analysis & Modelling in

Chemical Engineering 1st Edition Denis

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

For information on all Elsevier publications

Publisher: John Fedor

Typeset by SPi Global, India

Advanced Data Analysis and Modelling in Chemical Engineering. http://dx.doi.org/10.1016/B978-0-444-59485-3.00001-1

must hold. Substituting Eq. (1.2) into Eq. (1.1) yields

1.2 Chemistry and Mathematics: Historical Aspects

• the mass-action law by Guldberg and Waage.

1.3 Chemistry and Mathematics: New Trends

1.4 Structure of This Book and Its Building Blocks

Chapter 8 provides original results for optimal configurations of multizone reaction-diffusion

Chemical Composition and

What is a matrix? It is a square or rectangular array of numbers or expressions, placed

Advanced Data Analysis and Modelling in Chemical Engineering. http://dx.doi.org/10.1016/B978-0-444-59485-3.00002-3

2H2 + O2 ≜2H2 O (2.3)

2H2 O2 + 2H2 O≜zero (2.4)

This reaction can be represented by the matrix:

2.2 The Molecular Matrix and Augmented Molecular Matrix

2.2.2 Application of the Molecular Matrix to Element Balances

Summarizing, to analyze the element balances

Example 2.1 Fixed Ratio of Elements

C Ht c-C4 H8 t-C4 H8 C8 H16

nC8 H16 ¼ 1=8nCt 1=2nc-C4 H8 1=2nt-C4 H8 (2.30)

Number of key components ¼ number of components number of key elements (2.31)

Example 2.2 Different Order of Components

After augmentation with a unit matrix, this matrix becomes

Its RREF is readily computed to be

Example 2.3 Mixture Containing a One-Atom Molecule

and after augmentation,

Example 2.4 Combination of Two Groups of Elements

nHCl ¼ 3=2nCt + nHt + n C2 H2 (2.45)

2.3 The Stoichiometric Matrix

2.3.1 Application of the Stoichiometric Matrix to Reactions

Consider the set of reactions

which is represented by the stoichiometric matrix S

Example 2.5 Effect of the Reactions Chosen

c-C4 H8 t-C4 H8 C8 H16

Δn t-C4 H8 ¼ Δn c-C4 H8 (2.62)

2.3.2 The Augmented Stoichiometric Matrix

Adding the hypothetical reaction

Augmenting this matrix with a unit matrix

The oesophagus is followed by a long

Fig. 281.—Larva of Phoxichilidium sp., showing tendril-like appendages of the

Fam. 1. Decolopodidae.—Appendage I. dwarfed, but complete and chelate,

Fig. 284.—Rhynchothorax mediterraneus, Costa. A, Body and bases of legs; B,

Fam. 8. Phoxichilidiidae.—Appendage I. well-developed; II. absent; III.

Fam. 9. Phoxichilidae.[439]—Appendage I. and II. absent; appendage III.

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