Gumersindo Feijoo, Juan Manuel Lema, Maria Teresa Moreira

Mass Balances for Chemical Engineers

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Gumersindo Feijoo, Juan Manuel Lema,
Maria Teresa Moreira

Mass Balances
for Chemical
Engineers
Authors
Prof. Dr. Gumersindo Feijoo Prof. Dr. Maria Teresa Moreira
Universidade de Santiago de Compostela Universidade de Santiago de Compostela
Department of Chemical Engineering Department of Chemical Engineering
15782 Santiago de Compostela 15782 Santiago de Compostela
Spain Spain

Prof. Dr. Juan Manuel Lema

Universidade de Santiago de Compostela
Department of Chemical Engineering
15782 Santiago de Compostela
Spain

ISBN 978-3-11-062428-1
e-ISBN (PDF) 978-3-11-062430-4
e-ISBN (EPUB) 978-3-11-062431-1

Library of Congress Control Number: 2020932486

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Cover image: simoningate / iStock / Getty Images Plus
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Printing and binding: CPI books GmbH, Leck

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Contents
1 Conservation principles 1
1.1 The law of conservation of mass 1
1.2 General balance equation 1

2 Balances in systems without chemical reaction 5

2.1 Formulation of the general equation of macroscopic mass
balance 5
2.1.1 Overall balance 5
2.1.2 Component balance 6
2.2 Macroscopic mass balances for systems without chemical
reaction at steady state 7
2.2.1 Overall balance 7
2.2.2 Component balance 8
2.3 Heuristic rules for the solution of problems on mass balance 8
2.4 Recirculation, purge or bypass 16
2.4.1 Recirculation/recycle and purge streams 16
2.4.2 Bypass stream 24
2.5 Air–water balance 26
2.5.1 Absolute and relative humidity 27
2.5.2 Psychometric diagrams 27
2.6 Study of the nonstationary state 31
2.7 Proposed problems 34
2.7.1 Balances to units and systems 34
2.7.2 Balances with recirculation, bypass and/or purge 37
2.7.3 Balances in the air–water balance 45
2.7.4 Mass balances in nonstationary state 49

3 Balances in systems with chemical reaction 51

3.1 Stoichiometry 51
3.1.1 Algebraic formulation 52
3.1.2 Conversion 55
3.1.2.1 Intensive conversion 57
3.1.2.2 Conversion 57
3.1.2.3 Relationship between molar conversion and degree of
conversion 59
3.1.3 Limiting reactant and excess 59
3.1.4 Multiple reactions: yield and selectivity 66
3.2 Chemical equilibrium in systems with chemical reactions 71
3.2.1 Chemical equilibrium with gas-phase reactions 71
3.2.2 Acid–base reactions 83
VI Contents

3.2.3 Solubility product 89

3.3 Kinetic aspects: reaction rate 91
3.3.1 Integrated equations of reaction rate 91
3.3.2 Factors influencing reaction rate 93
3.3.2.1 Temperature 93
3.3.2.2 Catalysts 93
3.3.3 Application to Metabolic Engineering 95
3.4 Proposed problems 99
3.4.1 Stoichiometry 99
3.4.2 Systems in equilibrium 107
3.4.3 Kinetic controlled systems 112

4 Balances in multiple systems 115

4.1 Analysis of degrees of freedom 115
4.1.1 Specification of a system 115
4.1.2 Calculation of the number of degrees of freedom 115
4.2 Solution strategies 118
4.3 Synthesis of methanol 126
4.3.1 Degrees of freedom 128
4.3.2 Simulation based on mass balances: sequential modular
method 129
4.4 Circular economy: obtaining sodium alginate from marine
algae 139
4.4.1 Simulation based on mass balances 143
4.5 Proposed case studies 150
4.5.1 Production of iodine (I2) 150
4.5.2 Biomass gasification 151
4.5.3 Alkylation: iso-octane synthesis 152
4.5.4 Catalytic desalkylation of toluene for benzene production 153
4.5.5 Synthesis of sulfuric acid 154
4.5.6 Second-generation bioethanol production 156
4.5.7 Synthesis of β-galactosidase 157
4.5.8 Biogas conditioning for a cogeneration system 159

Nomenclature 161

Glossary 163

Bibliography 165
 Contents VII

Appendices

Appendix A Systems of units: Excel CONVERT function 171

Appendix B Graphic symbols for process flow diagrams 177

Appendix C Solving nonlinear equations 183

Appendix D Solving a system of linear equations 194

Index 201
1 Conservation principles

1.1 The law of conservation of mass

Conservation laws define the fundamentals of science and engineering. The most
common statements of these laws express that “mass (or energy) cannot be created
or destroyed,” “the mass (or energy) of the universe is constant,” “the mass (or en-
ergy) of an isolated system is constant” and so forth. That is, there are certain char-
acteristics of matter that remain constant when a physical or chemical change takes
place in a system. The constancy of these properties, that is, their conservation, is
the main object of the study of the so-called principles of conservation.
Although the ancient Greeks first proposed the idea that the total amount of
matter in the universe is constant, the French chemist Lavoisier1 enunciated the
law of conservation of mass based on countless experiments where he measured
the mass of all the components of a wide range of chemical reactions. This law states
that, despite chemical reactions or physical transformations, mass is conserved –
that is, it cannot be created or destroyed – within an isolated system. In other words,
in a chemical reaction, the mass of the products will always be equal to the mass of
the reagents.
Therefore, chemical reactions can be visualized as a rearrangement of atoms
and bonds, while the number of atoms involved in a reaction remains unchanged.
This assumption allows us to represent a chemical reaction as a balanced equation,
in which the number of moles of any element involved is the same on both sides of
the equation.
A more general statement of this law consists in pointing out that matter is nei-
ther created nor destroyed, it is only transformed. This fact is valid for practically
all physical and chemical changes, with the exception of nuclear reactions, where
part of the matter is transformed into energy.

1.2 General balance equation

The calculation and design of industrial unitary equipment requires the resolution
of equations that describe the systems under study and relate the variables involved
to each other (flow rate, T, P, composition, energy, etc.).
Using the conservation principle of matter, a series of equations (=balances)
can be formulated between the various units, systems and flows of the processes.
Accordingly, it is possible to:

1 Antoine-Laurent de Lavoisier (1743–1794): French scientist considered the father of modern

chemistry.

https://doi.org/10.1515/9783110624304-001
2 1 Conservation principles

1. Calculate mass flows by reducing in situ measurements.

2. Close the mass flows (=close the mass balances) to describe the system compre-
hensively or compare the actual (measured) values with the target values.

These balances give an idea of “how much” the change in a given system meant.
Now, we cannot solve these equations without some knowledge and interpretation
of the transport mechanism. That is, in addition to “how much,” we need to know
“at which rate” the change occurs. This value is given by kinetic laws:
– Physical kinetics: friction (motion), conduction–convection and radiation (en-
ergy), and diffusion (matter).
– Chemical kinetics: for systems where a chemical reaction occurs.

A third important element to take into account is the information about natural and/
or nonnatural restrictions. These restrictions can take the form of the following:
– physical equilibrium,
– chemical equilibrium,
– boundary conditions,
– other (economic, safety, legislation, etc.).

The knowledge of all this information is the first step for the definition of a mathe-
matical model from which it is possible to analyze, simulate, design a system and/
or process.
The basic principle used in modeling of chemical engineering process is based
on the concept of balances (momentum, mass and energy). The application of bal-
ances must refer to a system defined by a control volume, perfectly delimited in
space by a control surface. Generally speaking, any balance can be expressed in a
general form as follows (Figure 1.1):

Input + Generation = Output + Accumulation

Figure 1.1: Mass balance scheme.

 1.2 General balance equation 3

– Input/Output: This corresponds to the flow of property (mass and/or energy)

that crosses the limits of the system in a given time.
– Accumulation: This corresponds to the amount of property within the system
after a time t, so it can be both positive and negative.
– Generation: This corresponds to the amount of property that appears or disap-
pears within the system without initially being present or having been trans-
ferred across the system boundaries.

The extent of description of the balances can be defined at various scales:

– Macroscopic balance (also called integral): It is applied to a volume element
and allows to know what happens between two instants of time. It is character-
ized by the knowledge of only one value of each variable, which will be the
mean value of the whole system.
– Microscopic balance (also called differential): A differential element of volume is
applied and allows to know what happens in an instant of time; therefore, there
is a variation of the property (mass/energy) with space (x, y, z) and time (t).

At the same time, the existence of chemical reaction (generation term) or nonsta-
tionary state (accumulation term) implies notorious differences in the type of equa-
tion of the balances and, therefore, in their resolution. Appendices C, D and E show
the basic mathematical aspects and their application in Excel for solving systems of
linear and nonlinear equations.
The synoptic description of a process is usually represented through flow dia-
grams, which help to understand how the flow of materials or energy is carried out in
a process or in an equipment. Different representation options are considered: block
diagram, process flow diagram and piping and instrumentation diagram (P&ID).
The block diagram is represented by means of boxes or rectangles in which the
input and output flows are identified (usually with an identifying number in a
rhombus over each process line). Process flow diagrams include symbols represent-
ing major equipment items and process lines (including bypass and recycle streams).
The physical properties, quantities, temperatures and pressures of the materials can
be indicated for each process line in the stream table that typically compiles an in-
ventory of the different flows. More exhaustive information is included in the P&ID
such as instrumentation and control details, vents and drains and relief and safety
valves.
2 Balances in systems without chemical reaction

2.1 Formulation of the general equation of macroscopic mass

balance
2.1.1 Overall balance

The rigorous formulation of the mass balance for a control volume (V) delimited by
a control surface (A) (Figure 2.1) in which the density (ρ) of the system varies con-
tinuously with position and over time is presented in the following expression:
( ) ( ) ( )
mass accumulation mass input mass output
= −
rate rate rate

Applying it to the entire control volume,

ð ð
! !  d
ρ · v · n · dA + · ρ · dV = 0 (2:1a)
A dt V

dM
Δm + =0 (2:1b)
dt

where m is the mass flow rate expressed in mass units (kg/s) and M, mass of the
system in mass units (kg).
In eqs. (2.1a) and (2.1b), the term generation is null, because mass is a con-
served magnitude. Therefore, in that arbitrary volume, mass is continuously enter-
ing and exiting, the difference between the two is accumulating.
In many cases it is interesting to know the total flows of input/output material
without it being essential to know the value of the velocity at each point of the
input/output surfaces. In these cases, the average velocity <v> can be used. In addi-
tion, if the density is uniform across each step surface, a simple form of the above
equations is obtained:

dM
Δðρ · hvi · AÞ + =0 (2:2)
dt

If the balance is established in moles instead of units of mass, it must be taken into
account that the generation may not be null. For example, if there is a chemical
reaction, the number of moles of product may be different than the number of reac-
tants. By calling “g” the amount of mass, in moles, produced or consumed per unit
of time and volume, the moles generated per unit of time will be
ð
g · dV = 0 (2:3)
V

https://doi.org/10.1515/9783110624304-002
6 2 Balances in systems without chemical reaction

vy
vz y
z+Δz
z Side Input Output

vx vx x ρvx|x ΔyΔz ρvx|x+Δx ΔyΔz

x x+Δx
y ρvy|y ΔxΔz ρvy|y+Δy ΔxΔz

z ρvz|z ΔxΔy ρvz|z+Δz ΔxΔy

vz – ρvx is the density of mass flow in the direction

vy z
y+Δy x: (kg/m2s)
– ΔyΔz delimits the surface perpendicular to the
x direction of flow for which the flow density is
y defined

Figure 2.1: Density of material flow in the control volume for each of the control surfaces that
delimit it.

If the molar density or system concentration (moles/volume) is denoted as “C,” the

overall balance of mass in molar units would be as follows:
ð ð ð
! ! d
C · v · n · dA + · C · dV = g · dV (2:4a)
A dt V V
ð
dN
Δn + = g · dV (2:4b)
dt
V

where n is the mass flow expressed in molar units (kmol/s) and N, mass of the sys-
tem in molar units (kmol).

2.1.2 Component balance

The mass balance is applicable not only to all the material that enters, exits, ac-
cumulates or is generated in the system, but also to any component. Thus, al-
though it must be borne in mind that in the case of a chemical reaction, the term
generation will not be zero, not even working in units of mass. The generation
can be negative (when the component is a reactant) or positive (if the component
is a product).
The formulation of the balance of the component “i” is obtained from eqs. (2.1a)
and (2.1b) by replacing ρ by ci (mass concentration), m by mi and M by Mi. Strictly
speaking ! v should also be replaced by !
vi , because if there are concentration gradients
the individual components will not move with the same velocity ! v . However, in sys-
tems considered from a macroscopic point of view, this difference is not significant:
 2.2 Macroscopic mass balances for systems without chemical reaction at steady state 7

ð ð ð
! ! d
ci · v · n · dA + · ci · dV = Gi · dV (2:5a)
A dt V V

ð
dMi
Δmi + = Gi · dV (2:5b)
dt V

Equation (2.5b) can be expressed as a function of the mass fraction, wi (kg compo-
nent/kg total mass), or molar, xi (mol component/total moles):
ð
dðwi · MÞ
Δðwi · mÞ + = Gi · dV (2:6a)
dt V

ð
dðxi · N Þ
Δðxi · nÞ + = gi · dV (2:6b)
dt V

2.2 Macroscopic mass balances for systems without chemical

reaction at steady state

If, in a stationary process, each output and input flow can be measured and ana-
lyzed, the usefulness of the macroscopic balance is limited, except for checking the
consistency of the experimental data. However, if there are one or more points
where it is not practical or possible to take the necessary data, they can be calcu-
lated applying the mass balances. In addition, another usefulness of the mass bal-
ances is their application to carry out the previous calculations in the design of
units and the simulation of processes.
For systems in stationary state without chemical reaction, both the accumulation
and generation term are zero in the total balance and in the component balances.

2.2.1 Overall balance

Equation (2.2) would be simplified to

Δðρ · hvi · AÞ = 0 (2:7)

Equation (2.7) can also be expressed as a function of mass flow or volume flow:

Δðρ · hvi · AÞ = Δm = Δðq · ρÞ = 0 (2:8)

Therefore, if subindexes 1 and 2 refer to input and output, respectively,

Σðρ · hvi · AÞ1 = Σðρ · hvi · AÞ2 (2:9a)

Σm1 = Σm2 (2:9b)
8 2 Balances in systems without chemical reaction

Σðq · ρÞ1 = Σðq · ρÞ2 (2:9c)

2.2.2 Component balance

Equations (2.6a) and (2.6b) would be simplified to

Δðwi · mÞ = 0 ) Σðwi · mÞ1 = Σðwi · mÞ2 (2:10a)

Δðxi · nÞ = 0 ) Σðxi · nÞ1 = Σðxi · nÞ2 (2:10b)

If the density remains constant, the balance of a component can also be defined
from volumetric flow and mass concentration:

Σðq · ci Þ1 = Σðq · ci Þ2 (2:11)

2.3 Heuristic rules for the solution of problems on mass balance

The following steps can be defined to solve mass balance problems (Figure 2.2):
1. Representation of the system scheme or process flow diagram with identification
and enumeration of the different streams and selection of the suitable basis of cal-
culation: The basis of calculation is defined as the numerical value of an extensive
quantity, which is arbitrarily chosen to facilitate calculations and on which other
resulting extensive quantities are referred to. In general, different priority criteria
are considered for the choice of the calculation basis: (i) a quantity of one of the
components of the system, which does not react chemically and which enters and
leaves the system as part of a single stream; (ii) a quantity of one of the flows en-
tering or leaving the system, usually the one for which more information is avail-
able and (iii) a time interval.
2. Mass balance calculations can be made on the basis of any conventional set of
flow quantities or flow velocities. Therefore, when balancing a process, one
must select an overall quantity or one of the components (e.g., mass, number of
moles, etc.), in such a way that all unknowns are determined in a way that they
are consistent with this basis. Guidelines for choice:
i. If the value of a flow or a flow velocity is provided as data from the prob-
lem statement, it is usually convenient to use that quantity as a basis for
calculation.
ii. If the flow or flow velocities of any of the streams are not known, one value
should be assumed. In this case, a quantity of flow is chosen for which the
composition is known. If the composition data are in mass or molar frac-
tion, the most appropriate calculation basis will be the total mass or num-
ber of total moles, respectively.
 2.3 Heuristic rules for the solution of problems on mass balance 9

Figure 2.2: Steps on the path to the solution of mass balances.

iii. If the result or objective of the calculation are relative values, for example,
the mass ratio between two streams, the final value is independent of the
calculation basis.
3. Definition of system boundaries and formulation of the mass balances: For the
solution of this type of problems the technique of the “black box” can be used,
that is to say, a line is drawn around the process and it is considered exclu-
sively what enters or leaves it. This procedure defines the “system boundary
conditions” over which the balance sheets are defined. It should be noted that
10 2 Balances in systems without chemical reaction

not all balances are independent, so when formulating the balances of the “i”
components of the system and then an overall balance, the latter will be the
sum of the simple balances. Therefore, the number of independent equations in
each environment (number of degrees of freedom) will be equal to “i,” the total
number of components.
4. Solving the system of “i” linear or nonlinear equations that correctly represent
the “i” unknown values of the problem.

Example 2.1: Normally the air we breathe contains 20.8% (by volume) of O2, when in a confined
space, this percentage is below 19.5% of its total atmosphere, and the atmosphere is consid-
ered to be oxygen deficient. In these conditions, no worker can enter without auxiliary breath-
ing apparatus, since below this threshold there is an increase in breathing, accelerated beats
and poor coordination. Calculate whether there is a potential risk from a suboxygenated atmo-
sphere in a laboratory when two gas cylinders of 20 L of N2 (at 180 atm) are leaking. The dimen-
sions of the laboratory are 8 m long, 5 m wide and 3 m high. Consider atmospheric pressure
and 22 °C.

Solution:
Step 1: Diagram and data representation (Figure 2.3)

A B C D E F G H I
13 Solution:
14 1) Diagram and data representation
15
16 Legend
17 Data
18 Calculations
19 Solutions
20
21
22
23
24
25 Laboratory dimensions Gas cylinder
26 Length 8.0 m Gas N2
27 Width 5.0 m Number 2.0
28 Height 3.0 m Volume 20.0 L/unit
29 Pressure 1.0 atm Pressure 180.0 atm
30 Temperature 22.0 °C
31
32 Risk threshold 19.5 % O2
33

Figure 2.3: Process scheme and data representation.

Step 2: Basis of calculations

The objective of this problem is to determine whether the leakage of nitrogen gas cylinders can
cause a suboxygenated atmosphere in the laboratory; therefore, the volume of nitrogen confined
in the gas cylinder: 40 L will be considered as the basis for calculation.
 2.3 Heuristic rules for the solution of problems on mass balance 11

Step 3: Definition of system boundaries and formulation of the mass balances

In this problem the system boundary is the laboratory and the balances are formulated from
eq. (2.10b), where subindexes 1 and 2 refer to the initial and final instant (after the leak):

ðxi · nÞ1 =
ðxi · nÞ2

Balance for O2: ðnO2 Þ2 = ðnO2 Þ1 = ðnO2 Þlab
Balance for N2: ðnN2 Þ2 = ðnN2 Þ1 = ðnN2 Þlab + ðnN2 Þgas cylinder

So, the new oxygen concentration will be calculated by

ðnO2 Þ2
ðxO2 Þ2 =
ðnO2 Þ2 + ðnN2 Þ2

Step 4: Resolution of the mass balances

The number of moles of oxygen and nitrogen is calculated by applying the law of ideal gases
(Figure 2.4).

A B C D E F G H I
59 4) Solution to mass balance
60
61 Mol of oxygen:
62
63 - Application of the ideal gas law
64
65 P ⋅Vo2
P ⋅Vo2 = n⋅R⋅T n= =
66 1031.3 mol O2
67
R⋅T
68 P= 1.0 atm
69 VO2= 24,960.0 L Vo = Vair[xo ]air = VLab[xo ]air
2 2 2
70 M= 32.0 g/mol
71 R= 0.082 atm L/mol K
72 T= 295.2 K
73
74 Mol of nitrogen:
75
76 P= 1.0 atm
VN2 = Vair [xN2]air
77 VN2= 94,800.0 L
78 M= 28.0 g/mol
79 R= 0.082 atm L/mol K
80 T= 295.2 K
81
82 (nN2)Lab = 3,917.0 mol N2
83
84 P= 180.0 atm
85 VN2= 40 L
86 M= 28.0 g/mol (nN2)gas cylinder = 297.5 mol N2
87 R= 0.082 atm L/mol K
88 T= 295.2 K
89

Figure 2.4: Calculation of the number of moles of oxygen and nitrogen.

In this way, the final oxygen concentration can be calculated in the laboratory after the nitrogen in
the bottles has leaked. In addition, the IF function in Excel can be used:
=IF(logic_test;[true_if_value];[false_if_value])
12 2 Balances in systems without chemical reaction

A text message that “warns” of the health risk can be related to the threshold value that is set
(Figure 2.5):

A B C D E F G H I
91
92 (nO2)2
93 (xO2)2 = = 0.197
(nO2)2 + (nN2)2
94 19.66 % No health risk
95
96

Figure 2.5: Calculation of the oxygen concentration and application of the Excel SI function.

G94: =IF(E94 < C32; “There is a risk to health”; “no health risk”). The threshold value of 19.5%
is defined in cell C32.

In complex sheets it may be of interest to introduce rules in some cells that allow “alerting” a dis-
crepancy between the physical meaning and the mathematical result; for example, the existence of
negative values in variables that represent mass flows.
In this problem, the alert would be related to the potential risk, in such a way that values above the
threshold would have a “green” icon or otherwise a “red” icon. Thus, to introduce a rule in cell E94
where it is calculated as the result of the final percentage of oxygen (Figure 2.4), proceed as follows:
i. Select the cell in which to enter the rule, that is, E94.
ii. Conditional Format > New rule.
iii. In the display of format style select the option “set of icons.” In the icon style you will choose
“3 semaphores with frame.”
iv. In the type choose formula.
v. In the value you enter 19.6 and 19.5 to set the condition of each icon.

Questions/simulations:
i. Design calculation: The mass balance allows us to simulate design/operation situations. Thus,
if in this laboratory increased from 2 to 3 gas cylinder of nitrogen, we would have a potentially
dangerous situation if there were a complete leak of the nitrogen confined within them. For ex-
ample, if the value of 3 is entered in the cell G27, this would result in an oxygen concentration
of 19.12% and therefore a health risk (the “red” icon in the cell would be shown).

Example 2.2: A river with 357 mg/L of a contaminant and a flow of 10 m3/s receives an agricultural
discharge of 1.5 m3/s carrying 2,000 mg/L of that contaminant. The contaminating compound dis-
solves quickly and evenly in the river water. Downstream, water is extracted for consumption from
an urban nucleus, where it is previously mixed with water from another source so that the final
content of the contaminant does not exceed 400 mg/L. What should be the mixing ratio of the
source water with the river water?

Solution:
Step 1: Flowchart with identification and enumeration of streams (Figure 2.6)
 2.3 Heuristic rules for the solution of problems on mass balance 13

A B C D E F G H I
11 Solution:
12 1) Diagram and data representation
13
14
15
16
17 1 3 7
18
19
20 4
21
22 2
23 5 Water source
24
25 Agricultural area
26 Legend
27 6 Data
28 Calculations
29 Urbanization Solutions
30
31
32 Streams
33 1 2 3 4 5 6 7
34 Flow 10.0 1.5 m3/s
35 [Pollutant] = cc 357 2,000 0.0 400 mg/L
36

Figure 2.6: Scheme of the process data representation.

Step 2: Basis of calculations

The objective of this problem is the calculation of the q5/q4 ratio; therefore, the final value will not
depend on the quantity selected as the calculation base. In this case, in the first instance a value
of 5 m3/s will be chosen for the flow of water that will finally be supplied to the urban nucleus, q6.

Step 3: Definition of system boundaries and formulation of the mass balances

In this problem, the most suitable systems to define the balances would correspond to the points
of mixing (mixer) and division (divider) of streams (Figure 2.7).

45
46 System 2
47 System 1
48
49
50 1 3 7
51
52
53 4
54
55
56 2 5 Water source
57
58 Agricultural area
59
60
System 3
6
61
62 Urbanization
63

Figure 2.7: Definition of control volumes.

If you consider “system 1” to define the overall balance you can calculate the value of q3. Applying
the global balance (eq. (2.9c)) and taking into account that density can be considered constant and
equal in all streams:
14 2 Balances in systems without chemical reaction

ðq · ρÞinput =
ðq · ρÞoutput ) q1 + q2 = q3

qinput =
qoutput
Consequently, the value of q3 = 10 + 1.5 = 11.5 m3/s.
Applying the component balance (eq. (2.11)) the value of the salt concentration in stream 3
will be determined:
q1 · ðcsalt Þ1 + q2 · ðcsalt Þ2
q1 · ðcsalt Þ1 + q2 · ðcsalt Þ2 = q3 · ðcsalt Þ3 ) ðcsalt Þ3 =
q3
The value of the concentration will be

q1 · ðcsalt Þ1 + q2 · ðcsalt Þ2 ð10 · 357Þ + ð1.5 · 2000Þ mg

ðcsalt Þ3 = = = 571.3
q3 11.5 L
When considering the system “2” and “3” we formulate a system of 3 linearly independent equations
with 3 unknown variables, where two of them are adequate for the final objective of the problem:

– System “”

Overall balance Parameters Coded Equation

q3 = q4 + q7 x = q x1 + x2 = q3
x = q

– System “”

Overall balance

q4 + q5 = q6 x = q x1 + x3 = q6

Component balance – outlet

q4 · ðcsalt Þ4 = q6 · ðcsalt Þ6 ðcsalt Þ4 · x1 = q6 · ðcsalt Þ6

Step 4: Solving the simultaneous equations

In a first stage, a copy of the “3 variables” sheet from the “Appendix D_Inversion Matrix” (see
Appendix D) to the book where the solution to the problem is being elaborated. Both sheets are then
“connected” with the input of the coefficients as data (for those not dependent on the problem data)
or as a formula (when dependent on the problem data; Figure 2.8).

A B C D E F G H I
1 Solving simultaneous equations
2
3 Matrix inversion method
4
5 3-Variables
6
7
8 ai1 ai2 ai3
9 E1: 1.0 x1+ 1.0 x2+ 0.0 x3 = 11.50
10 E2: 1.0 x1+ 0.0 x2+ 1.0 x3 = 5.00
11 E3: 571.3 x1+ 0.0 x2+ 0.0 x3 = 2000.00
12
Figure 2.8: Spreadsheet with the solution of the system of linear equations from Example 2.2.
 2.3 Heuristic rules for the solution of problems on mass balance 15

For example,
B9: = 1,0 (coefficient).
I9: = ‘Example 2.2ʹ!F77 (is entered as a formula since it depends on the data of the problem).

When you finish entering the coefficients, the calculation of the solution will be automatically pro-
duced, which we can, in turn, connect to the main sheet of the problem (Figure 2.9a, b).

(a) A B C D E F G H I J K L
37 Step 4: The solution is obtained by the matrix multiplication of A–1 and B
38
39 x1 3.50 Note: A matrix formula must be specified to obtain
40 X = x2 = 8.00 the terms {=MMULT(array 1;array 2)}
41 x3 1.50
42
43
44 Results: x1 = 3.50
45 x2 = 8.00
46 x3 = 1.50
43

(b) A B C D E F G H I
110 4) Solution of independent linear equations
111
112 To obtain the solution of the problem we must consider the solution of a system of 3 independent linear
113 equations that is defined in the spreadsheet: “Calculations-Example 2.2”
114
3
115 x1=q4= 3.50 m /s
116 x2=q7= 8.00 m3/s
117 x3=q5= 1.50 m3/s
118
119 Ratio of pure water to river water
120 q5
121 q4= 0.428
122 42.8 %
123

Figure 2.9: (a) System solution using the reverse matrix method. (b) Solution of the problem.

Accordingly,
D115: = ‘Calculations-Example 2.2ʹ!E44
D116: = ‘‘Calculations-Example 2.2ʹ!E45
D117: = ‘‘Calculations-Example 2.2ʹ!E46

Consequently, the solution to the problem will be 42.8% in the flow ratio.

Questions/simulations:
i. Effect of the calculation basis: The result of the problem (relation between streams) does not
depend on the value of the calculation base. Thus, if another value is entered in cell C39, for
example, 3.5 m3/s, the final value will not change even if the flow values vary.
ii. Effect of an overload: If the concentration in the agricultural waste is increased by 25%, there-
fore, the concentration would be 2,500 mg/L (cell C35), and the value of the ratio would be
59.1%. Obviously, it will be necessary to increase the flow from the water source in order to
maintain the same characteristics of the water that reaches the urbanization.
16 2 Balances in systems without chemical reaction

2.4 Recirculation, purge or bypass

2.4.1 Recirculation/recycle and purge streams

In many operations and to improve the conversion of the process into reversible re-
actions or to recover specific components of the product stream such as solvents, it
is necessary to introduce a scheme that considers the possibility of recirculation. A
recirculation/recycle stream is simply a flow that is taken from the discharge of a
unit (it may or may not have the same concentration as the product stream) and
returned as feed to a unit located upstream in the process (Figure 2.10). From a
mathematical point of view, it is necessary to pose the balance equations to the
whole system, to each process block and to the mixing point.

Figure 2.10: Recycle, purge and bypass streams in a process.

The purge stream is defined as the flow separated from the system, typically corre-
sponding to a fraction of the recirculation stream, in order to remove certain sub-
stances that would otherwise accumulate inside the system. This is done by
balancing the entire system around each block at the mixing point and at the purge
extraction point.
A recirculating unit can be viewed as a process of three units: mixer, system
and a stream divider (Figure 2.11).
 2.4 Recirculation, purge or bypass 17

Mixer Divider

System

Recirculation

Figure 2.11: Diagram of a process with recirculation.

The mixer is a device within which two or more streams are joined together to
form a single main stream (Figure 2.12). As the mixing is carried out solely on the
basis of the flow, the main stream has a flow equal to the sum of the flows of each
of the streams.

A, xA

D=A+B+C
B, xB D, xD A · xA + B · xB + C· xC
xD =
D
C, xC

Figure 2.12: Overall balance and component balance in a stream mixer.

A divider is a device within which the input flow is divided into two or more
streams. As this division is made only as a function of flow, the composition of all
the streams into which the mainstream is divided will be identical (Figure 2.13).

B, xB

A=B+C+D
A, xB C, xc xA = xB = xc = xD

D, xD

Figure 2.13: Balance in a stream divider.

There are three ways or types of recirculation so that raw materials that have not
been used (reacted in a chemical reactor, absorbed in an absorption tower, etc.) can
be recycled upstream in a process:
1. Separate and purify the output stream and recirculate them at the beginning of
the process.
2. Partially recirculate the output stream using a purge stream to avoid accumulations.
3. Partially recirculate the output stream without considering a purge stream.
18 2 Balances in systems without chemical reaction

Example 2.3: The biogas generated in the anaerobic digestion of sludge from a wastewater treat-
ment plant, which contains 74% CH4 and 26% CO2 (percentages by volume), is to be used in a co-
generation system. Its previous conditioning consists of two absorption columns (Figure 2.14) by
recirculating methanol as an extractive separating agent (consider that for the purposes of the pro-
cess it is nonvolatile; therefore, it is not found in any of the gas streams of the process units). In
the absorption column T-102, it is possible to extract 90% of the CO2 from the stream 3: (i) recircu-
lation flow (stream 4), (ii) flow of stream 3 and molar fraction of CO2 and (iii) fractional extraction of
CO2 expressed as absorbed moles/moles in the feed.

99% CH4
2 N2
1% CO2 5
CO2

4
T-101 T-102

6 N2

Biogas 1 CH3OH
50 kmol/h
74% CH4 0.5% CO2
26% CO2

Figure 2.14: Process of conditioning biogas prior to its use in a cogeneration system.

Solution:
Step 1: Flowchart and stream table
The statement of the problem already has the flow diagram; therefore, it is only necessary to indi-
cate and enumerate the data of molar flow and molar fraction of each of the streams. Two aspects
should be highlighted: (i) the % by volume coincides with the % molar and (ii) the composition of
stream 4 is 0.5% CO2 and, therefore, 99.5% CH3OH.

     

Flow rate . kmol/h

CH . . . % molar

CO . . . % molar

CHOH . . % molar

N . . % molar

Step 2: Basis of calculations

The calculation basis will be the feed flow rate: n1 = 50 kmol/h.
 2.4 Recirculation, purge or bypass 19

Step 3: Definition of system boundaries and formulation of the mass balances

– If the absorption column T-101 is considered as the control volume to define the balance of
CH4, the value of n2 can be calculated. Applying the component balance (eq. (2.10b)),
ðxCH4 Þ1 · n1 0.74 · 50 kmol
ðxCH4 Þ1 · n1 = ðxCH4 Þ2 · n2 ) n2 = = = 37.37
ðxCH4 Þ2 0.99 h

If you consider the CO2 balance and the overall balance, you will get two equations with three
unknown variables:

CO Balance Unknown parameters Coded equation

x = n
ðxCO2 Þ1 · n1 + ðxCO2 Þ4 · n4 = ðxCO2 Þ2 · n2 + ðxCO2 Þ3 · n3
x = (xCO )
x = n
x1 · x2 − ðxCO2 Þ4 · x3 + ðxCO2 Þ2 · n2 − ðxCO2 Þ1 · n1 = 0

Overall Balance

n1 + n4 = n2 + n3 x1 − x3 + n2 − n1 = 0

– The third equation is obtained from the CO2 balance by considering the absorption column
T-102 as the control volume, taking into account the efficiency of the CO2 recovery of this
column:

ðxCO2 Þ3 · n3 = ðxCO2 Þ4 · n4 + ðxCO2 Þ5 · n5

) ð1 − ηÞ · ðxCO2 Þ3 · n3 = ðxCO2 Þ4 · n4
ðxCO2 Þ5 · n5 = η · ðxCO2 Þ3 · n3

If this last equation is coded,

ð1 − ηÞ · x1 · x2 − ðxCO2 Þ4 · x3 = 0

From these balances we have obtained a system of three independent nonlinear equations with
three unknown variables, which will allow us to calculate the objectives of the problem.

Step 4: Solving the system of nonlinear equations

As noted in Appendix E on solving systems of nonlinear equations, the application of Excel Solver
tool is a suitable technique to obtain the solution to a system of nonlinear equations (Figure 2.15).

A B C D E F G H
106 4) Solution of independent linear equations
107
108 The Excel Solver tool is applied to solve the system of 3 nonlinear equations
109
110 xk
111 1 1 292.8 –0.0001792
112 2 0.048 0.00
113 3 280.2 0.0017547
114 2
115 Sum of squares 3.111E-06
116 (objective function)
117 3
118
119

Figure 2.15: Definition of the balance sheet and solution of Example 2.3.
20 2 Balances in systems without chemical reaction

Therefore, it is now possible to respond to each of the sections of the problem:

a. recirculation flow rate (stream 4): n4 = 280.2 kmol/h,
b. flow of stream 3 and molar fraction of CO2:

n3 = 293.8 kmol=h

ðxCO2 Þ3 = 0.048

c. fractional extraction of CO2 expressed as absorbed moles/moles in the feed: 97.12%

ðxCO2 Þ3 · n3 − ðxCO2 Þ4 · n4
= 0.9712
ðxCO2 Þ1 · n1

Example 2.4: The galvanizing industry has been one of the first for which a BREF2 document has
been defined, where the best available techniques (BAT) are collected for each sector under study,
due to the degree of pollution of the effluents. One of the BATs defined in this document is the
increase in the internal recycling of baths (with a high metal content) until they get more ex-
hausted. Thus, in a given metal surface treatment facility, there is a problem with its discharge
effluent due to the high concentration of zinc and nickel. A process is proposed (Figure 2.16) where
recirculation streams play a key role in the final effectiveness of the process.

W (H2O 100%)
R21

P1 P2
F 1 2 3 D

R32
P0

Figure 2.16: Zn and Ni recovery process in a galvanizing industry to apply in Example 2.4.

Table 2.1 lists the concentrations of several of the streams, all of which contain water. Calculate
(in L/h) the flow rate of the recycling stream R32.

2 Best available techniques reference document: https://eq.europa.eu/jrc/en.

 2.4 Recirculation, purge or bypass 21

Table 2.1: Data from the design process streams for the
recovery of Zn and Ni in the galvanizing industry (Example 2.4).

Stream Zn (g/L) Ni (g/L)

F . .
P . .
P . .
R . .
D . .

Solution:
Step 1: Flowchart and stream table
The statement of the problem already has the flow diagram; therefore, it is only necessary to indi-
cate the flow and concentration of each of the streams.

Stream

F P P P W D R R

Flow rate L/h

Zn . . . . . . g/L

Ni . . . . . . g/L

Step 2: Basis of calculations

The feed flow rate shall be taken as the basis for calculation: qF = 1 L/h.

Step 3: Definition of control volumes and formulation of the mass balances

In problems with recirculation it is often appropriate that one of the control volumes encompass
recirculation; therefore, from a black box perspective the recirculation variable will not be reflected
in the balances. Obviously, another of the control volumes to consider will be that in which the
recirculation stream is reflected as its input or output.
Equations (2.9c) and (2.11) will be applied for the overall balance and component balance, re-
spectively, taking into account that density can be considered constant and equal in all streams.

– Control volume encompassing all  units

Overall balance Unknown Coded equation

qF + qW = qP0 + qD x1 = qW x1 − x2 − x3 = − qF
x2 = qP0
x3 = qD

Component balance: Zn

qF ðcZn ÞF = qP0 ðcZn ÞP0 + qD ðcZn ÞD ðcZn ÞP0 x2 + ðcZn ÞD x3 = qF ðcZn ÞF

Component balance: Ni

qF ðcNi ÞF = qP0 ðcNi ÞP0 + qD ðcNi ÞD ðcNi ÞP0 x2 + ðcNi ÞD x3 = qF ðcNi ÞF

22 2 Balances in systems without chemical reaction

– Control volume corresponding to unit “”

Overall balance

qW + qP2 = qR32 + qD x4 = qP2 x1 − x3 + x4 − x5 = 0

x5 = qR32

Component balance – Zn

qP2 ðcZn ÞP2 = qR32 ðcZn ÞR32 + qD ðcZn ÞD ðcZn ÞD x1 − ðcZn ÞP2 x4 + ðcZn ÞR32 x5 = 0

Consequently, a system of five linear equations has to be solved to calculate the flow rate of the
recirculation stream R32.

Step 4: Solving the system of equations

Application of the matrix inversion method
First, a copy of the “5 variables” sheet from the ““Appendix_D_Matrix Inversion” file (see Appendix D)
to the book where the solution to the problem is being elaborated. Both sheets are then “connected”
with the input of the coefficients as data or as a formula (Figure 2.17):
B9: = 1.0 (entered as a number, as it does not depend on the data in the problem statement).
D10: = ‘Example 2.4ʹ!C70 (is entered as a formula since it depends on the data of the problem).

A B C D E F G H I J K L M
1 Solving simultaneous equations
2
3 Matrix inversion method
4
5 5-Variables
6
7
8 ai1 ai2 ai3 ai4 ai5
9 E1: 1.00 x1+ –1.00 x2+ –1.00 x3+ 0.00 x4+ 0.00 x5 = –1.00
10 E2: 0.00 x 1+ 190.10 x2+ 0.05 x 3+ 0.00 x4+ 0.00 x5 = 100.00
11 E3: 0.00 x1+ 17.02 x2+ 1.00 x 3+ 0.00 x4+ 0.00 x5 = 10.00
12 E4: 1.00 x1+ 0.00 x2+ –1.00 x 3+ 1.00 x4+ –1.00 x5 = 0.00
13 E5: 0.00 x1+ 0.00 x2+ 0.05 x 3+ –3.50 x4+ 4.35 x5 = 0.00
14

Figure 2.17: Connection of sheet containing the data of the problem with the solution of the system
of linear equations of Example 2.4.

When you finish entering the coefficients, the calculation of the solution will be automatically pro-
duced, which we can, in turn, connect to the main sheet of the problem (Figure 2.18a, b).
Thus, D122: = ‘Calculations-IM-Example 2.4ʹ! E58. Consequently, the recirculation stream R32
has a flow rate of 1.83 L/h.

Application of the Gauss–Seidel iterative method

Similarly, a copy of the sheet “5 variables” from the file ““Appendix_D_Gauss Seidel” (see Appendix D)
is made to the book where the solution to the problem is being elaborated. Both sheets are then “con-
nected.” The value of three significant figures is entered in cells Q13, R13, S13, T13 and U13 to consider
the maximum error in the calculation.
When you finish entering the coefficients will automatically produce the calculation of the
solution that we can, in turn, connect to the main sheet of the problem (Figure 2.20b), where
E122: = ‘Calculations-GS-Example 2.4ʹ!U32.
 2.4 Recirculation, purge or bypass 23

(a)
A B C D E F G H I J K L
45 Step 4: The solution is obtained by the matrix multiplication of A–1 and B
46
47 x1 0.577 Note: A matrix formula must be specified to obtain
48 x2 0.526 the terms {=MMULT(array 1;array 2)}
49 X = x3 = 1.052
50 x4 2.365
51 x5 1.891
52
53
54 Result: x1 = 0.577
55 x2 = 0.526
56 x3 = 1.052
57 x4 = 2.365
58 x5 = 1.891
(b) 59 J
A B C D E F G H I
110 4) Solution of independent linear equations
111 To obtain the solution of the problem we must consider the solution of a system of 5 linear equations.
112 To visualize the difference in the calculation we will apply the direct method of matrix inversion ("Calculations-MI-Example 2.4")
113 and the iterative method of Gauss-Seidel ("Calculo-GS-Example 2.4")
114 MI GS
115 = 0.577 0.577 L/h
116 = 0.526 0.526 L/h
117 = 1.052 1.052 L/h
118 = 2.365 2.363 L/h
119 = 1.891 1.889 L/h
120

Figure 2.18: (a) System solution using the matrix inversion method. (b) Solution of the problem.

Questions/simulations:
i. Accuracy of calculation: The Gauss–Siedel iterative method is less precise than the reverse
matrix method, but more universal in its application.
ii. Effect of recirculation: If the concentration of Zn at the output (stream D) is to be reduced to
0.05 g/L (cell G70), the flow rate of the recirculation stream must be increased to 1.89 L/h; the
value of flow rate that can be varied operationally.
iii. Feed/recirculation ratio: There is a proportional ratio between supply and recirculation R32 so
if the inlet flow (calculation basis) is increased by 5 times (5 L/h in cell C75); the value of R32
will be 5*1.83 = 9.15 L/h.
iv. Function between the final concentration of Zn and the recirculation ratio: For each value of Zn
in the stream D a value of the recirculation ratio (qR32/qF) is obtained. By representing both
values (Figure 2.19), a trend line can be obtained, which in this case is of the linear type.

2.00
y = –1.2244x + 1.952
1.95
R2 = 1
1.90
qR32/qF

1.85

1.80

1.75

1.70
0.00 0.05 0.10 0.15 0.20
[Zn] (g/L)

Figure 2.19: Relationship between the final concentration of Zn and the recirculation ratio.
24 2 Balances in systems without chemical reaction

2.4.2 Bypass stream

A derivation (or “Bypass”) consists of dividing a mainstream into two others: one
undergoes the physical or chemical transformation and the other is mixed with the
stream resulting from the transformation. The bypass stream is fed back directly to
a subsequent stage at the so-called mixing point to obtain a desired final composition.
The purpose of this flow is to avoid an overload of some process units in relation to
their initial design capacity and/or to control the composition of the mixed stream.
Accordingly, it is often used in cases where only a small change in the supply stream is
desired because from a control point of view, it is easier to control a large change in a
small portion of the fluid than a small change in a large stream.

Example 2.5: Fresh orange juice contains on average 12% solids in aqueous solution (percentage in
mass). To reduce relocation costs, juice is concentrated before packing and then reconstituted
upon arrival at its destination. The concentration process is carried out in specially designed evap-
orators that operate with short residence times and lower atmospheric pressures to reduce losses
of flavor and aroma components present in very small quantities, which are very volatile and heat
sensitive. Since it is very difficult to avoid losses in these traces, a common practice is to concen-
trate the juice a little more than necessary, and then add a small amount of fresh juice to the con-
centrate to obtain a product with a better aroma and taste. If the bypass stream is 10% of the feed
and the evaporator outlet contains 80% solids in solution, calculate the water evaporation rate and
the composition of the final product if fresh feed is 10,000 kg/h.

Solution:
Step 1: Flowchart and stream table (Figure 2.20)

4 Water

Steam

Evaporation 1 Fresh
3
chamber juice

Condensation Concentrated
chamber 5 6
juice

Condensate

Figure 2.20: Process scheme.

 2.4 Recirculation, purge or bypass 25

Stream

     

Flow rate , k/h

Solids . . %

Step 2: Basis of calculations

The fresh feed flow rate shall be taken as the calculation basis: m1 = 10,000 kg/h.

Step 3: Definition of control volumes and formulation of the mass balances

Equations (2.9b) and (2.10a) will be applied for the overall balance and component balance,
respectively:

– Control volume at the bypass valve

Bypass Unknown

m2 = f · m1 ( f is the derived fraction) m

Overall balance

m1 = m2 + m3 m

Component balance – stream divider

w1 = w2 = w3 w and w

– Control volume in the evaporation chamber

Component balance – solids

ðwsolidos Þ3 · m3 = ðwsolidos Þ5 · m5 m

Overall balance

m3 = m4 + m5 m

– Control volume in the mixing valve of the streams

Overall balance

m2 + m5 = m6 m

Component balance

ðwsol Þ2 · m2 + ðwsol Þ5 · m5 = ðwsol Þ6 · m6 (wsol)

Step 4: Solving the system of equations

Since these are equations of a single unknown parameter, the corresponding equation can be en-
tered directly into each cell (Figure 2.21).
26 2 Balances in systems without chemical reaction

A B C D E F G H I J
16 Solution:
17 Legend
18 Data
19 7,594 kg/h Calculations
20 Solutions
21 4 Water
22
23
24 9,000 kg/h 10,000 kg/h
Steam
25 0.13 0.13
26
Evaporation Fresh
27 3 1
chamber juice
28
29 1,000 kg/h
30 2 0.13
31 f= 0.10
32 Condensation Concentrated
33 chamber 5 6
juice
34
35 1,406 kg/h 2,406 kg/h
36 Condensate 0.80 0.52
37
38
39 The evaporation rate:
40
41
Evaporate water
42 · 100 = ·100 = 96.43 %
Input water
43
44

Figure 2.21: Solution of the mass balances.

Accordingly:
G: = I*G E: = (E*E)/E
E: = I−G D: = E−E
G: = I I: = G + E
E: = I I: = (G*G + E*E)/I

Questions/simulations:
i. Effect of the calculation basis: If the value of the calculation basis is changed, the results of
the total mass flows will change, but the concentration and the evaporation ratio will not
change. Test in cell I24 with a value of 20,000 kg/h.
ii. Effect of the bypass stream: The value of the fraction of fresh feed that is derived has a direct
effect on the final solids concentration that is achieved. Thus, for a factor of 0.12 (cell G31) the
concentration is reduced to 0.48. However, it has no effect on the evaporation ratio.

2.5 Air–water balance

The air–steam water system is the most frequently used of all two-phase systems.
Its study is important in the design and operation of air conditioning systems, re-
frigeration towers, dehumidifiers and, in general, in any industrial process where it
is necessary to control the water vapor content of the air.
 2.5 Air–water balance 27

2.5.1 Absolute and relative humidity

The composition of a given wet air sample can be described in several different
ways, for example, in terms of the moles of dry air and water vapor present in the
mixture or in terms of their molar fractions.
Specific humidity: Specific humidity, also called absolute or simply humidity, is
defined as the quotient between the masses of water vapor and dry air (eq. (2.12a)):
steam mass mv
$= = (2:12a)
dry air mass ma

It can also be expressed as a function of partial pressures and molecular weights by

applying the equation of ideal gases to eq. (2.12b):
 
Mv · pv 18 pv pv
$= = · = 0.622 · (2:12b)
M a · pa 28.93 P − pv P − pv

Relative humidity: It is defined as the quotient between the mole fraction of water
vapor in a given humid air sample and the mole fraction of water vapor in a humid
air sample saturated at the same temperature and pressure as the mixture (eq. (2.13)):
 
yv  pv 
$r = = (2:13)
yv, sat T, P pv, sat T, P

Both specific and relative humidity can be measured experimentally, with the hygrom-
eter being the instrument capable of measuring the degree of humidity of the air or
other gas.

Dew point
An important aspect of humid air behavior is that partial condensation of water
vapor can occur when the temperature is reduced. A gas is saturated with vapor at
a determined temperature (referred to as dew temperature) when an infinitesimal
decrease in temperature causes vapors condensation.

2.5.2 Psychometric diagrams

Psychrometric diagrams or humidity charts (Figure 2.22) provide graphical repre-

sentation of various characteristic properties of humid air:
– Dry bulb temperature (°C) indicated on the abscissa axis refers to the tempera-
ture measured by a common thermometer.
– Moisture content (specific humidity (kg of water vapor per kg of dry air)) is rep-
resented on the ordinate axis.
– Relative humidity (%) corresponds to the exponential curves.
28 2 Balances in systems without chemical reaction

– Spray temperature: Since the dew point is the state in which the mixture is satu-
rated by cooling it under constant vapors pressure, the dew temperature of a
given humid air state can be determined by tracing a constant specific humidity
line to the saturation line (100% relative humidity). The dew and dry bulb tem-
peratures coincide for the states above the saturation curve.
– Wet bulb or saturation temperature (Tbh) is the dynamic equilibrium tempera-
ture obtained on a water surface when the heat transfer rate by convention to it
is equal to the rate of transfer of matter leaving such a surface. It is measured in
an ordinary glass liquid thermometer whose bulb is surrounded by a cloth
moistened with water. The constant temperature lines run from the upper left
side to the lower right side of the diagram.
– Specific volume (m3/kg dry air): The lines of constant volume also go from the
left side to the right side but have a greater slope.
– In addition, in this type of diagram the specific enthalpy of the humid air (kJ/kg
dry air) is added, whose lines coincide approximately with the temperature
lines of the humid bulb.

Relative humidity (%)

100 75 25
ir)

0.020
ry a

30
gd
J/k

)
(°C
y (k

re

Moisture content (kg/kg dry air)

tu
alp

ra
nth

pe
em
ce

nt
cifi

tio

0.9
Spe

ra
tu

0
sa

0.010
20
or
ulb

Volume
tb

(m3/kg dry air)

We

0
0.7
8

0.000
0 25 50
Dry bulb temperature (°C)

Figure 2.22: Psychometric diagram.

 2.5 Air–water balance 29

Example 2.6: Timber boards used in construction should be dried from 18% (by weight) moisture to
1% by circulating hot air over them. The inlet air is at 55 °C and has a relative humidity of 20%. The
air at the exit of the tray dryer has a temperature of 47 °C and a relative humidity of 90%. How
many m3 of dry air (measured under normal conditions) would be needed per ton of wood?

Solution:
Step 1: Flowchart and stream table (Figure 2.23)

Wood
Figure 2.23: Diagram of the tray dryer.

The data of the problem is:

Stream

  Initial Final
Wood
Moisture (% weight)  

Air
Temperature (°C)  
Relative moisture (%)  

Using the psychrometric diagram, the specific or absolute moisture of the air is obtained from the
dry bulb temperature and the relative moisture (Figure 2.24): 0.020 and 0.060 kg water per kg dry
air for stream 1 and 2, respectively.
30 2 Balances in systems without chemical reaction

Relative humidity (%)

90% 20%

Moisture content (kg/kg dry air)

0.060

0.020

47 55
Dry bulb Temperature (°C)

Figure 2.24: Specific or absolute moisture knowing the dry bulb temperature and relative
moisture.

Step 2: Basis of calculations

The load of 500 kg of wood to the tray dryer shall be considered as the basis for calculation.

Step 3: Definition of control volumes and formulation of the mass balances

Equation (2.10a) corresponding to the component balance shall be applied in the only control vol-
ume of the system, that is, the tray dryer:

– Balance of dry material in wood boards Unknown

ðwdry mass Þinitial · minitial = ðwdry mass Þfinal · mfinal Mass of the wet wood at the end: mfinal

– Water balance in the tray dryer

ðwH2 O Þinitial · minitial + $1 · m1 = ðwH2 O Þfinal · mfinal + $2 · m2 Mass of dry air: m = m

Step 4: Solving the system of equations

Since these are equations of a single unknown, the corresponding equation can be entered directly
into each cell (Figure 2.25). Accordingly,
F35: = E35*((1−(E38/100))/((1−(F38/100))))
B24: = ((((E38/100)*E35)−((F38/100)*F35))/(H22−B30)/E35)*1000
 2.6 Study of the nonstationary state 31

A B C D E F G H I J
10 Solution:
11 LEGEND
12 Data
13 Calculations
14 Solutions
15 Stream 2
16 Dry air 4,293 kg/t wood
17 3,334 m /t (c.n.)
18 Wet air 4,551 kg/t wood
19 T 47.0 °C
20 P 1.0 atm
21 ϖr 90.0 %
22 ϖ 0.060 kg H O/kg dry air
23 Stream 1
24 Dry air 4,293 kg/t wood
25 3,334 m /t (c.n.)
26 Wet air 4,379 kg/t wood
27 T 55.0 °C
28 P 1.0 atm
29 ϖr 20.0 %
30 ϖ 0.020 kg H O/kg dry air
31
32
33
34 Initial Final
35 Wet wood 500.0 414.1 kg
36 Dry mass 410.0 410.0 kg
37 H O 90.00 4.14 kg
38 Humidity 18.0 1.0 % (weight)
39

Figure 2.25: Solution of the mass balances.

To obtain the volume of dry air (m3) in normal conditions (0 °C and 1 atm) it is enough to apply the
law of ideal gases (PV = n R T). The result of the problem is 3,334 m3 per ton of wood:
B25: = ((B24*0.082*273.15)/(28.84*$B$28))

2.6 Study of the nonstationary state

In this case the flows and operating conditions will vary over time, and so we have
to operate with the full expression of the balance. The procedure of solving matter
balances in these systems is analogous to the one already defined, but with the con-
sideration of two additional important aspects: the formulation of the equation in
nonstationary regime and the solution of the same; that is to say, our objective will
be to transfer the problem in one or more differential equations of the form:

dx
= f ðx, tÞ (2:14)
dt

Therefore, to solve this type of equations it is necessary to know the initial conditions
or some value of x for a known time. The stages to follow will be the following:
1. Represent a diagram and place the known data in it.
2. Choose dependent and independent variables, taking into account that time is
an independent variable.
32 2 Balances in systems without chemical reaction

3. Specify the initial conditions or the value of x for a time t.

4. Establish the necessary balances and solve the differential equations.

No internal generation
A fairly common situation corresponds to the study of homogeneous systems where
there is a variation in the concentration of one of the components over time due to
dilution, absorption phenomena and so on; in these cases when applying eq. (2.5a)
it is necessary to take into account:
ð ð ð
 
ci !v ·!
d
n · dA + · ci · dV = G · dV (2:15)
dt
A V V
Ð
– The term generation is null: V G · dV = 0.
– The concentration ci is uniform, due to being a perfectly homogenized system,
Ð dc Ð
for all the volume and the areas of input and output: dtd V ci · dV = dti V dV =
d
ðc · V Þ.
! i !
dt
– v · n = < v >, the vector representative of the input area has the same direction
that ! v (although the sense is the same in the output but inverse in the input):
ð
v ·~
ci ð~ nÞdA = ½hvici Aoutput − ½hvici Ainput
A

Therefore, the balance equation is simplified to eq. (2.15):

d
½hvici Aoutput − ½hvici Ainput + ðci · V Þ = 0
dt
d
½q · ci output − ½q · ci input + ðci · V Þ = 0 (2:16)
dt

Example 2.7: A tank contains 75 L of a salt solution in water, in which 5.2 g of salt are dissolved.
The water enters the tank with a flow rate of 4.5 L/min and the output stream has the same flow
rate. If the mixture in the tank is adequate to achieve uniformity in salt concentration at all times,
how much salt will remain in the tank after 42 min? Assume that the density of the input water, the
dissolution in the tank and the output stream are equal to each other.

Step 1: Flowchart with stream table (Figure 2.26)

Step 2: Definition of dependent and independent variables

As previously indicated, in this type of problem, time should always be considered as an indepen-
dent variable. The salt content in the tank or its concentration can be considered as a dependent
variable.

Step 3: Initial or contour conditions

At initial time the amount of salt in the tank is 5.20 g, that is, a salt concentration of 0.069 g/L.
 2.6 Study of the nonstationary state 33

A B C D E F G H I J
14 Solution:
15 Step 1. Flowchart and stream table
16
17 LEGEND
18 Data
19
1 2 Calculations
20 Solutions
21
22
23 V
24
25
26
27 Stream Unit Initial conditions
28 1 2 Volume 75 L mi0 5.20 g
29 Flow rate (q) 4.50 4.50 L/min ci0 0.07 g/L
30 Concentration (c ) 0.00 ???

Figure 2.26: Flowchart and data representation.

Step 4: Establishing the balances and solving the system of equations

The component balance is the one defined in eq. (2.42), in which it must be taken into account that
the input is exclusively water and the volume in the tank is constant, from which a first-order differ-
ential equation will be obtained where the variables ci and t (Figure 2.27).

A B C D E F G H
41 4) Balances
42
43 Nonstationary matter balance without generation applied to salt concentration:
44
45 d
[q·ci]salida – [q·ci]entrada + (ci·V ) = 0
46 dt
47
48 As the volume in the tank is constant and the input is only water:
49
50 dci
[q·ci]salida + V =0
51 dt
52
53 reordering the terms of the equation;
54 dci q t q
– ·t
55 ∫ = – ∫ dt ci = ci0 · e V
56 ci V 0
57
58
59 Therefore, for 42 min
60
61 Ci0 = 5.58E–03 g/L Mi = ci ·V = 0.418 g
62

Figure 2.27: Definition of the mass balance and resolution of Example 2.7.
34 2 Balances in systems without chemical reaction

2.7 Proposed problems

2.7.1 Balances to units and systems

2.1 The conventional method of separation of ethyl alcohol from an ethanol–water

mixture is by distillation. However, the highest concentration that can be ob-
tained in the distillate is 95% by volume of alcohol, because ethanol and
water form a mixture with a constant boiling point, called azeotrope. In order
to purify the alcohol, it is necessary to add a third component that forms an
azeotrope of minimum boiling point with water. Industrially one of the most
employed is benzene. It is desired to obtain 1,850 kg/h of ethyl alcohol by
azeotropic distillation from a feed stream containing 42% (by weight) of
alcohol from an ethanol–water mixture. It is estimated that the distillate will
contain 76% benzene, 23% water, with the remaining 1% ethanol (all percen-
tages by weight). Pure ethanol is obtained from the bottoms. Calculate (a)
flow rate of feed, benzene and distillate (b) the efficiency of the column repre-
sented as the ratio of ethanol lost in the distillate to the value fed.
Solution: (a) 4,686, 8,981 and 11,817 kg/h, respectively; (b) 6.0%.

2.2 A stream of 1,000 mol/h of hydrocarbons with the following composition (%

molar): 20% propane, 30% isobutane, 20% isopentane and 30% pentane;
separated into two fractions by distillation. The distillate contains all the
propane entering the unit, as well as 80% of the isopentane and with an iso-
butane composition of 40%. The stream from the bottoms must contain all
the pentane that is fed to the unit. Calculate the stream compositions of top
and bottom of the column.
Solution: Top: 33.30% C3, 40.00% i-C4 and 26.64% i-C5; bottom: 14.96% i-C4,
75.11% C5 and 9.95% i-C5.

2.3 There is a system of two distillation columns arranged in series to separate a binary
mixture formed by the generic components denoted by A and B (Figure P2.3).
Calculate the flows and compositions of streams 3, 5 and 7.
Solution: (3) 60 kg/h and 23.3% A; (5) 90 kg/h and 25.6% A; (7) 60 kg/h and
8.3% A.
 2.7 Proposed problems 35

E-101 E-102
40 kg/h 30 kg/h
2 6
T-101 90% A 60% A
T-102

100 kg/h
50% A 1 5

4
30 kg/h
30% A

3 7

Figure P2.3

2.4 In a wastewater treatment plant (WWTP) there are three tanks for the preparation
of a suitable coagulant solution (Figure P2.4). Calculate the concentration in
each tank (perfectly mixed and in stationary state), where the flows are ex-
pressed in L/s.

400 mg/s
Q13 = 40

200 mg/s

Q12 = 80
V-101 Q33 = 120

Q21 = 20 V-103
Q23 = 60

V-102

Figure P2.4

Solution: c1 = c2 = 4 mg/L; c3 = 5 mg/L.

36 2 Balances in systems without chemical reaction

2.5 A reverse osmosis plant has been installed with three membrane separation units
connected in series without recirculation (Figure P2.5) to obtain water of a purity
(less than 25 ppm -in weight of NaCl) such that it can be used as boiler feed. Sea
water containing 3.5% by weight of NaCl is used as a feed. The membrane mod-
ules of 40 m2 work at 75 atm and reach a flow of 0.4 m3/m2 d when the permeate
pressure is 1.8 atm. A value of 75% is considered as a safety factor.

RO-101 V-102

3
RO-102 7

2
5 RO-103

4
V-101

Figure P2.5

If each membrane module has a 96% rejection of the salt that has been fed,
determine:
(a) The water recovery factor expressed as mH2O permeate after the third unit
divided by mH2O in the feed.
(b) The flow of seawater that must be fed to the installation to obtain
5,000 m3/d.

Notes
i. A concentration of 25 ppm is equal to 0.0025% by weight.
ii. Effect of the safety factor

½%Saltoperation = Fsafety · ½%Saltequilibrium

iii. Osmotic pressure data for sea salt and sodium chloride solutions at 40 °C
have been published by Stoughton and Lietzke (1965).
 2.7 Proposed problems 37

Posmotic Salts Posmotic Salts

(atm) (% weight) (atm) (% weight)

. . . 

. . . 

. . . 

. . . 

. .

iv. The osmotic pressure is equal to the pressure of the retained minus the
pressure in the permeate

Solution: (a) 48.2%; (b) 120 kg/s.

2.6 If the water flows between each of the vessels of the drinking water treatment
plant are known (Figure P2.6), determine the chlorine concentration in each
by means of the corresponding balances.

180 g/s QA = 67 m3/s

QB = 36 m3/s
QC = 161 m3/s
A
740 g/s 3.85 kg/s 4.72 kg/s
(QA, cA)

C D E

710 g/s
(QC, cC) (QD, cD) (QE, cE)

(QB, cB)

Figure P2.6

Solution: cA = 2.69; cB = 19.72; cC = 10.12; cD = 30.11; cE = 48.11 (all in ppm).

2.7.2 Balances with recirculation, bypass and/or purge

2.7 A nitrogen oxide absorber is fed by a fresh feed stream with a volume composi-
tion of 49% NO2, 49% NO3 and 2% CO2, mixed with a recycled stream from the
volume composition output of 45% NO2, 45% NO3 and 10% CO2, with half of the
38 2 Balances in systems without chemical reaction

incoming NO2 and NO3 being separated in the absorber. From the outlet stream,
a part is recycled at the inlet and the rest is purged. Taking as a base calculation
100 mol/h of mixture entering the absorption tower, calculate:
(a) Recycled moles.
(b) Purged moles.
(c) If the packing of the column is changed, the separation efficiency in-
creases to 65%. What would be the recirculation molar flow rate?

Solution: (a) 40.79 mol/h; (b) 11.84 mol/h; (c) 21.79 mol/h.

2.8 In a process to concentrate 1,000 kg of orange juice containing 12.5% by weight

of solids, the juice is filtered giving 800 kg of liquid and 200 kg of wet pulp.
The filtrate is concentrated in an evaporator to obtain an evaporated juice with
58% solids. About 200 kg of wet pulp is taken out of the evaporator and mixed
with the evaporated juice to improve the taste. This final juice has 42% solids
by weight. Calculate:
(a) The concentration of solids in the filtered juice.
(b) Kilograms of final concentrated juice.
(c) The concentration of solids in the juice stream.
(d) Evaluate the effect of the concentration of solids in the final juice with
the quantity produced. Consider that it increases from 42 to 50%.
(e) Evaluate the effect of the concentration of solids in the final juice on the
concentration of solids in the recirculation stream. Analyze the same case
when going from 42 to 50%.

Solution: (a) 7.1%, (b) 297.6 kg/h, (c) 34.2%; (d) the variation is inversely pro-
portional, given that this 19% increase also means a 19% reduction in the
quantity produced, given that it drops from 297.6 to 250 kg/h; (e) in this case
the proportional variation, given that it goes from 34.2 to 48%.

2.9 Figure P2.9 shows the flow diagram of a stationary process for the recovery of
crystalline potassium chromate (K2CrO4) from an aqueous solution of this salt.
About 4,500 kg/h of a solution containing 1/3 K2CrO4 in mass is combined
with a recirculation flow containing 36.36% K2CrO4; the combined flow is fed
to an evaporator. The concentrated flow out of the evaporator contains 49.4%
K2CrO4; this flow feeds a crystallizer, where it cools (precipitation of K2CrO4
crystals occurs from dissolution) and then filters out. The filtrate consists of
K2CrO4 crystals and a solution containing 36.36% K2CrO4; the crystals repre-
sent 95% of the total filtrate mass.
Calculate:
(a) Quantity of water extracted in the evaporator.
(b) The production rate of crystalline K2CrO4.
 2.7 Proposed problems 39

(c) Ratio between the kilograms of flow recycled per kilogram of fresh feed.
(d) The feed rates at which the evaporator and crystallizer must be designed.

Evaporation 2
chamber

Condensation
chamber 7

5 6

Figure P2.9

Solution: (a) 2,950.7 kg/h; (b) 1,471.8 kg/h; (c) 1.25; (d)10,113.8 kg/h and
7,183.1 kg/h.

2.10 In biotechnological processes it is common to concentrate the product after

the fermentation stage in order to reach a level of purity suitable for market-
ing (Figure P2.10). Thus, the production of vitamin B12 by Streptomyces (see

1 5

2 4

Figure P2.10
40 2 Balances in systems without chemical reaction

figure) requires an initial stage of centrifugation followed by filtration to reach

97% vitamin concentration. Calculate the mass flow of product stream and
recirculation:

Stream B Vitamin Water

 % %

 – %

 % %

 % %

 . kg/kg water

Solution: Based on a calculation of 1,000 kg/h of fermentation broth in stream

1, the results would be 185.6 and 201.5 kg/h for the product stream and recircu-
lation, respectively.

2.11 One of the strategies for providing the Mediterranean basin with drinking water
has been the implementation of various seawater desalination plants. Figure
P2.11 reflects a basic scheme of its operation, where the quality of the desired
drinking water should not exceed 475 ppm of salt. If you consider a design flow
rate of 1,000 kg/h of seawater (stream 1), calculate:
(a) Brine flow.
(b) Production of drinking water.
(c) Recirculating brine fraction.

V-101 V-102
6

1
4

Figure P2.11
 2.7 Proposed problems 41

Stream Salt

 %

 %

  ppm

 .%

Solution: (a) 567.5 kg/h; (b) 432.5 kg/h; (c) 58.5%.

2.12 A distillation column (Figure P2.12) separates 5,000 kg/h from a mixture of
benzene (45%) and toluene (55%). The distillate contains 95.5% benzene,
and the glue stream has a concentration of toluene of 96.2%. The distillate
stream entering the condenser has a flow rate of 3,500 kg/h. If a fraction of
the distillate, once condensed, returns to the distillation column as reflux,
calculate the ratio of reflux or recirculation of the column.

3
2
T-101
E-102
V-101
V-102
1
4
E-101
P-101A/B

5
E-103

Figure P2.12

Solution: 55.8%.

2.13 A continuous evaporation–crystallization system operates in stationary mode ac-

cording to the scheme shown in Figure P2.13. The concentrations of the streams
are as follows:
i. Stream 1: 22% (by weight) from KNO3.
ii. Stream 3: 54% (by weight) of KNO3.
42 2 Balances in systems without chemical reaction

iii. Stream 5: The crystals separated in the crystallizer have 3.8 kg of water/
100 kg total.
iv. Stream 6: 0.63 kg KNO3/kg water

Calculate: (a) kilograms of water evaporated/h in the evaporator; (b) mass

flow rate (kg/h) of streams 3 and 6.

Evaporation
2
chamber

Condensation
chamber 6

Figure P2.13

Solution: (a) 7,713.1 kg/h; (b) m3 = 8,574.1 kg/h and m6 = 6,287.2 kg/h.

2.14 The depleted bath of a galvanizing industry contains 5.35% (by weight) of Cr. Part
of it is recovered (94%) in a treatment unit (maximum capacity of 5,200 kg/h),
while the wastewater poor in Cr is treated prior to discharge. If the flow from the
plant exceeds 5,200 kg/h, a bypass of the Cr recovery unit is activated and directly
diverted to the wastewater treatment plant (WWTP) (Figure P2.14).
Evaluate:
(a) If the flow to the system is 6,500 kg/h, calculate the flow rate of the
wastewater to the WWTP, and the mass fraction of Cr in this stream.
(b) Obtain the equation that represents the mass fraction of Cr at the input of
the WWTP as a function of the flow of the stream of Cr to be recovered.
Make a representation of its evolution between 1,000 and 20,000 kg/h of
raw water to be treated.
 2.7 Proposed problems 43

Recovery
stream
3

Setpoint

WWTP
1 2
Depleted Wastewater
bath
6
4
5

Figure P2.14

Solution: 6,238.5 kg/h and 1.38%.

2.15 A biogas contains (by volume) 96% CH4 and 4% SH2, the use of which implies a
reduction to values less than 0.1%. Therefore, an amine absorption (molecular
mass of 112 g/mol) is designed in a closed circuit thanks to a second column with
steam entrainment (Figure P2.15). The SH2 between stream 2 and 4 is in equilib-
rium: KHenry = 20 KPa at a total pressure of 120 kPa. The concentration in weight
of stream SH2 in stream 4 and 6 is: 0.021% and 6.1%, respectively. Calculate the
flows and compositions of all streams for a feed stream of 15,000 kg/h.

T-101 T-102

6
2

1 4 Steam
5

96% vol CH4

4% vol SH2

Figure P2.15

Solution: n3 = 116.3 kmol/h; (xSH2)3 = 0.308; n4 = 80.5 kmol/h.

44 2 Balances in systems without chemical reaction

2.16 A particular industry must prevent the discharge of a pollutant, C, through

a three-step separation process (Figure P2.16). The m8/m7 ratio is 3, the m6/m5
ratio is 1 and the ratio of compound A to B in stream 6 is 4 to 1. Calculate the
composition of the stream flow 4, bypass and the percentage of each of the com-
ponents in it.

xA = 0.50 xA = 0.17
xB = 0.23 xB = 0.10
xC = 0.27 25 kg/h
xC = 0.73
2 5 7

T-101 T-102 T-103

3 8

250 kg/h 1 xA = 0.70

6 xB = 0.30
xA = 0.50
xB = 0.20
xC = 0.30 4

Figure P2.16

Solution: 32.5 kg/h, xA = 0.484, xB = 0.312 and xC = 0.204.

2.17 The extraction of vegetable oils generally uses hexane as a solvent. Due to its tox-
icity potential, it is necessary to design process lines that incorporate the best
available techniques, so that hexane can be used in a “closed” circuit and, there-
fore, minimize the feed of fresh hexane. The case study consists of using sun-
flower oil (Figure P2.17) using 1,800 kg/h of crushed sunflower seeds (10.3% oil
and the rest of solids) as feed, which together with hexane (2.85 kg of hexane/kg
of sunflower) allows the oil to be effectively separated in the extraction column
(T-101). The output of the extractor passes through a filter (F-101). The precipitate
contains 76.8% by weight of solids, and the rest of oil and hexane (both com-
pounds maintain the same proportion as in the output stream of the extraction
column). The cake is conditioned so that it can be used as a food supplement in
the formulation of animal feed (based on the principles of circular economy). The
filtered stream is fed to a vacuum evaporator, where the oil is separated and the
hexane is recovered for recirculation after condensation. Calculate:
 2.7 Proposed problems 45

(a) Sunflower oil yield (kilograms of oil/kilograms of seeds in feed).

(b) Feeding pure hexane per kilogram of sunflower.
(c) The degree of recirculation of the hexane.
(d) Composition of the suspension leaving the extraction tower and the cake
after filtration.

Hexane
8
E-101
E-102
T-101
F-101
Evaporation
Seeds 1 chamber
6 E-103
Condensation
chamber
3
5
Solid cake 7
4
Oil
Hexane 2

Figure P2.17

Solution: (a) 9.35%; (b) 0.26 kg C6H14 per kg of seeds; (c) 9.90 kg C6H14 recir-
culated per kilogram C6H14 fresh; (d) stream 4: 6,930 kg/h, 2.7% oil, 23.3% sol-
ids and 74% C6H14; stream 5: 2,102.3 kg/h, 0.8% oil, 76.8% solids and 22.4%
C6H14.

2.7.3 Balances in the air–water balance

2.18 In order to condition the air in an office building during the winter, 1,500 m3 of
humid air at 101.3 kPa and 25 °C and with a dew point of 12.5 °C are introduced
into the process. The air leaves the process at 98 kPa and a dew point of 59.5 °C.
How many kilograms of water vapor are added to each kilogram of moist air en-
tering the process?

Solution: 0.145 kg water/kg humid air.

2.19 Soils contaminated with recalcitrant organic compounds can be treated with hot
air and water vapor to release contaminants. If 45 m3 of air at 95 °C and 99.2 kPa
with a dew point of 32 °C are introduced into the soil, and in the soil the air is
cooled to 16 °C at a pressure of 108 kPa, what fraction of the water in the gas at
95 °C is separated by condensation in the soil?

Solution: 66.62%.
46 2 Balances in systems without chemical reaction

2.20 A granular solid (250 kg/h) with a moisture of 2.4 kg H2O/kg of dry matter
should be dried until its moisture is 1.5 kg H2O/kg dry matter (Figure P2.20).
For this purpose, fresh air with a specific humidity of 0.015 kg H2O/kg dry air
is introduced as backward stream in the dryer, while the air entering the unit
(after joining the recirculation stream) has a relative humidity of 20% and a
temperature of 55 °C. If the air outlet temperature is 95 °F and the relative
humidity is 85%, calculate:
(a) The amount of wet fresh air to be supplied to the dryer.
(b) The amount of humid air entering the dryer.
(c) The fraction of the recirculated air with respect to that entering the dryer.

Air

7 4

Solids
1

5
Air 2 Solids

Figure P2.20

Solution: (a) 4,478 kg/h;(b)6,750 kg/h;(c)34.3%.

2.21 An aqueous suspension with 10% (by weight) of solids is introduced into a vac-
uum rotary filter, where a cake with 60% (by weight) of water is obtained. This
cake then enters a rotary dryer from which it comes out with a moisture content
of 0.09 kg of water/kg of dry solid. If the process has been designed for a
throughput of 1,000 kg/h, calculate:
(a) Amount (kilograms) of water removed in the filter.
(b) Amount (kilograms) of dry air to be introduced into the dryer.
(c) Fraction of the recirculated air with respect to that entering the dryer.
 2.7 Proposed problems 47

Data: Characteristics of humid air

Stream Relative humidity (%) Dry bulb temperature

Fresh air %  °F

Dryer input %  °F

System output %  °F

Solution: (a) 750 kg/h; (b) 28,200 kg/h; (c) 50.75%.

2.22 It is desired to filter 1,500 kg of a suspension containing 12.5% by weight of

CaCO3 in a vacuum rotary filter. The cake that is taken out of the filter con-
tains 58% water. This cake is placed in a dryer and dried until it has a mois-
ture content of 8.75 kg H2O/100 kg CaCO3. If the humidity of the fresh air
entering the dryer is 0.002 kg of water/kg of dry air and the humidity of the
air leaving the dryer is 0.017 kg of water/kg of dry air, calculate:
(a) The amount of water removed in the filter and in the dryer (in kilograms).
(b) The amount of moist air entering the dryer (in kilograms).
(c) If part of the air from the dryer to the outlet is recirculated to it, the result-
ing stream would have an absolute humidity of 0.005 kg of water/kg of
dry air. In this case the moisture content is reduced to 7.55 kg H20/100 kg
CaCO3. Calculate the kilograms of humid air entering the dryer and the
amount of water removed from the dryer.

Solution: (a) 1,053.6 and 242.5 kg/h; (b) 16,200.5 kg/h; (c) 20,499.7 kg of dry
air/h and 244.8 kg of water/h.

2.23 The transport of sludge from a wastewater treatment plant (WWTP) is one of the
important costs to be taken into account in its management, so it is necessary to
significantly reduce the percentage of water from them prior to transport. For this
purpose, a two-stage process is designed: filtration and drying. A WWTP produ-
ces 3,200 kg of wet sludge per day with 3% by weight of dry sludge entering a
vacuum rotary filter. The cake that is taken out of the filter contains 45% water.
This cake is placed in a dryer from which it comes out with a moisture content of
8.5 kg H2O/100 kg dry sludge. The humidity of the fresh air entering the dryer is
0.002 kg of water per kg of dry air and the humidity of the air leaving the dryer is
0.018 kg of water/kg of dry air. It is possible to recirculate part of the air from the
dryer (the resulting stream would have an absolute humidity of 0.005 kg of
water/kg of dry air). In this case the moisture content is reduced to 7.10 kg H20/
100 kg dry sludge. If the transport cost is 0.15 €/kg wet sludge, which is the differ-
ence in annual cost and therefore savings between both operating conditions.
48 2 Balances in systems without chemical reaction

Solution: Annual cost without recirculation 7,223 €/year and with recircula-
tion 7,130 €/year and, therefore, a saving of 103 €/year.

2.24 One of the principles of the circular economy is to achieve maximum efficiency
of a process, that is, the complete transformation of raw materials into products
without the generation of waste, for example, by defining closed-loop systems
for the separating agents. A 10,000 kg/feed of flax seed (Linum usitatissimum) is
processed in three stages (Figure P2.24). The feed contains (% weight): 35.0%
protein, 27.1% carbohydrates, 9.4% fiber and ash, 10.5% moisture and 18% oil.
In the first stage, the flax is macerated and pressed to extract the oil, obtaining
oil streams and pressed pulp that still contains 6% oil. In the second stage the
pressed paste is treated with hexane (2.85 kg of hexane in stream 6 per load in
stream 1) to obtain a linen extract stream (containing 0.5% oil and 0.1% hexane)
and an oil–hexane stream. Finally, the extract is dried to obtain a product with
8% humidity by weight. Calculate:
(a) The kilograms of flax paste that comes out of the first stage.
(b) The kilograms of flax extract obtained in the second stage.
(c) The kilograms of final dry matter and % by weight of protein in the dry
product.

Hexane
V-101
1 E-101
E-102
2
5
7
Evaporation
chamber
E-103

3 4 Condensation
chamber

T-101 Air:
6 Relative humidity, 41.5% 10
Temperature, 30 °C 11
8
760 mmHg
Air:
Relative humidity, 50%
Hexane 9 Temperature, 21.1 °C
760 mmHg

Air: 13
Temperature, 37.8 °C Dry product
12
Dew point, 34.4 °C 8% H2O
750 mmHg

Figure P2.24

Solution: (a) 8,723.4 kg; (b) 8,249.5 kg; (c) 7,825.5 kg and 44.7% of protein.
 2.7 Proposed problems 49

2.7.4 Mass balances in nonstationary state

2.25 Water is pumped, with a flow rate of 325 L/min, to a cylindrical tank of 2.75 m in
diameter. Water flows through a pipe from the tank with a flow rate that depends
on the height of the liquid (h) in the tank, which complies with the following
ratio:

qoutput = a · h

where
– flow rate is expressed in L/min;
– the height in m;
– a is an empirical coefficient.

Graphically represent the evolution of the liquid height in the tank over time.
Calculate the height of the water in the tank after 60 min of operation, if the
initial height of the water is half a meter and the empirical coefficient has a
value of 185.
Solution: 1.56 m.

2.26 A compound A is dissolved in water at a rate proportional to the product of the

amount of compound remaining undissolved, mA, by the difference between
the mass fraction of the saturated solution, (wA)sat, and the actual concentration
of the solution at that time, wA. In an experiment, 12.5 kg of compound A with
70 kg of pure water has been initially arranged, observing that after 3.5 h
1.88 kg of A were dissolved. Data: (wA)sat is 0.311.
Graphically represent the evolution of the dissolved amount of A, nA, and
the undissolved amount, mA, over time. Determine also the dissolved quantity
of compound A after 12 h.
Solution: 5.01 kg.
3 Balances in systems with chemical reaction

When considering the modeling of systems with chemical reaction, it is necessary

to take into account the controlling “mechanism” of the reaction (Figure 3.1). Three
controlling factors are addressed in this chapter: (1) stoichiometry, (2) equilibrium
and (3) kinetics.

Figure 3.1: Limiting mechanisms in the modeling of a chemical reaction from the point of view of
mass balances.

3.1 Stoichiometry

In 1792 the German chemist J.B. Richter defined the law of proportional equivalents,
which can be expressed by saying that the weight of substance A that is combined
with a certain quantity of another substance B is the same that would be combined
with a substance C that enters in combination with the same quantity of substance
B. Richter called this new field of research stoichiometry (from the Greek στοιχειον,
stoicheion, “element” and μετρον, metric, “measure”).
In 1799 Proust formulated the law of defined proportions: “when two elements
react to form a compound, they always do so in a constant weight relationship.” In
1808 Dalton published another ponderal law, the so-called multiple proportions: if
from the combination of two elements several compounds can arise, it is fulfilled

https://doi.org/10.1515/9783110624304-003
52 3 Balances in systems with chemical reaction

that, while the weight of one remains constant, the weights of the other vary ac-
cording to a simple numerical relationship.
These laws led Dalton to define his atomic theory in 1803. Their essential postu-
lates are as follows:
1. Chemical elements consist of individual atoms that are indivisible.
2. Chemical compounds are formed by the union of atoms of different elements in
proportions of simple integers.

According to Dalton’s theory, the elements are conserved in a chemical reaction

and, therefore, balances in weight can be taken, both elementary and global. Thus,
the chemical equation provides both quantitative and qualitative information for
calculating the quantities of substances that are combined in a chemical process.
For example, the reaction of ammonia synthesis

N2 + 3H2 ! 2NH3

tells us which are the stoichiometric relationships (once balanced). In this case, for
each mole of nitrogen we can obtain two moles of ammonia, for which you will
have to react with 3 moles of hydrogen. The relationships obtained from the numer-
ical coefficients of the chemical equation are the stoichiometric coefficients.

3.1.1 Algebraic formulation

For the chemical reaction of ammonia synthesis, if we call A1≡N2, A2≡H2, A3≡NH3,
it can be represented:

A1 + 3A2 ! 2 A3

It is convenient to write all chemical compounds on the same side of the equation,
and give the negative sign to those that are reactants and positive to the products.
Therefore, the direct and inverse reaction could be expressed as follows:

2A3 − 3A2 − A1 = 0 A1 + 3A2 − 2 A3 = 0

The numbers 2, −3, −1 (direct reaction) and 1, 3, −2 (reverse reaction) are called stoi-
chiometric coefficients (α) and the natural way of writing these reactions would be
the following:
X
3  
αj · Aj = α1 · A1 + α1 · A1 + α3 · A3 = 0 (3:1)
j=1

Equation (3.1) can be generalized to “w” compounds, so that

 3.1 Stoichiometry 53

X
w  
αj · Aj = 0 (3:2)
j=1

where αj represents the stoichiometric coefficients (positive value for the products
and negative value for the reactants) and Aj are each of the compounds.
The general notation of writing of a chemical reaction can easily be extended to
simultaneous reactions. Let us consider the synthesis reaction of methanol:

CO + 2H2 ! CH3 OH

with the secondary reaction:

CO2 + H2 ! H2 O + CO

If we call A1≡CH3OH, A2≡CO, A3≡H2, A4≡CO2 and A5≡H2O, both reactions can
be written:

Reaction 1: A1 − A2 − 2A3 =0
Reaction 2: A2 − A3 − A4 + A5 = 0

where α11 = α22 = α25 = 1, α12 = α23 = α24 = −1, α21 = α14 = α15 = 0 and α13 = −2.
Therefore, in a compact form it could be represented:
X
5  
αji · Aj = 0 (3:3)
j=1

If instead of five compounds there were “w” and instead of two reactions there were
“h,” the way to represent the system of equations would be
X
w  
αji · Aj = 0 i = 1, 2, ...., h (3:4)
j=1

Example 3.1: The adjustment of biological reactions can be more complex due to the formation of
biomass, where the resolution of a system of linear equations corresponding to the balances of the
chemical elements is necessary. The ANAMMOX3 process is a biological process consisting of the
anaerobic oxidation of ammonium ion to nitrogen gas according to the reaction:4

NH4+ + α1 NO2− + α2 HCO3− + α3 H + ! N2 + α4 NO3− + α5 CH2 O0.5 N0.15 + α6 H2 O

This reaction is carried out by Planctomycetes bacteria with a nitrification capacity (NO3−/NO2− ) of
0.225.

3 ANAMMOX, acrónimo de ANAerobic AMMonium Oxidation.

4 Jetten et al. (2009). Critical Reviews in Biochemistry and Molecular Biology, 44(2–3):65–84.
54 3 Balances in systems with chemical reaction

Solution:
Elementary balances:

N: 1 + α1 = 2 + α4 + 0.15α5
H: 4 + α2 + α3 = 2α5 + 2α6
O: 2α1 + 3α2 = 3α4 + 0.5α5 + α6
C: α2 = α 5

Coefficient balance:

1 − α 1 − α2 + α 3 = − α4
Nitrification capacity:

α4
= 0.225
α1
Resolution of the mass balances:
For solving the system of linear equations, the method of matrix inversion is applied (see Appendix
D), with the results shown in Figure 3.2.

A B C D E F
57 Step 3: Solution
58 α1 1.311
59
α2 0.108
60
61 X= α3 = 0.125
62 α4 0.295
63 α5 0.108
64
α6 2.008
65

Figure 3.2: Stoichiometric coefficients to adjust the reaction.

Example 3.2: One of the most commonly used physicochemical parameters in the characterization
of the organic matter content of wastewater is the chemical oxygen demand (COD). This is defined
as the amount of oxygen necessary for a complete oxidation of organic matter. The calculation of
the theoretical COD for an organic compound can be obtained from the adjustment of the complete
oxidation reaction to CO2 and H2O:

Cx Hy Oz + α1 O2 ! α2 CO2 + α3 H2 O
where stoichiometric coefficients would be:

1
α1 = ð4x + y − 2zÞ
4
α2 = x
y
α3 =
2
 3.1 Stoichiometry 55

Consequently, the theoretical COD would be obtained as follows:

 
8ð4x + y − 2zÞ mg O2 mgCOD
CODT = or
ð12x + y + 16zÞ mg Cx Hy Oz mg Cx Hy Oz
With this in mind, calculate:
a. The concentration, expressed as g COD/L, of wastewater composed of 2 g/L glucose,
1,500 ppm acetic acid, 1,800 ppm propionic acid and 0.5 g/L butyric acid.
b. If the flow of wastewater was 500 m3/d, what would be the equivalent number of inhabitants
of a city with a similar organic load.5

Solution:
For the calculation of (a) it is necessary to first know the CODT for each of the compounds pres-
ent in the wastewater, applying the equation of the reaction adjustment of the complete oxida-
tion (Figure 3.3).
D38: = 8*(4*D34 + D35−2*D36)/(12*D34 + D35 + 16*D36) [CODT value for glucose]

The values for acetic acid, propionic acid and butyric acid are calculated analogously in cells E38,
F38 and G38. The concentration value (in g COD/L) is calculated in cells F46, F47, F48 and F49; the
sum of which (cell F50) makes it possible to determine the CODT value of wastewater:
F46: = D46*E46 [g COD/L for glucose]
F50: = SUM(F46:F49) [CODT value of the wastewater]

Since the organic load of a wastewater is defined as the product of flow by concentration (expressed
in terms of COD), (b) is calculated as follows:
   
OL Q dL · gCOD
L 5 · 105 × 7.367
p.e. =  =   = = 61, 392
gCOD
60 dp.e. gCOD
60 dp.e. 60

3.1.2 Conversion

When a chemical reaction takes place, the quantities of the components that ex-
isted initially change (increasing or decreasing) and, in the end, different quantities
are obtained from those that existed initially. In order to measure the evolution of
the reaction, different variables have been defined, both intensive and extensive,
referring to some of the components or independent of them.
If Nj is the number of moles of Aj at any time, Njo is the number present in an
arbitrary determined time and if the composition only changes due to the chemical
reaction, the molar conversion is defined according to eq. (3.5):

5 Directive 91/271/EEC (https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=CELEX%3A31991L0271)

concerning urban waste water treatment plays a major role in the management of urban waste water
and in the protection of receiving surface waters and the aquatic environment. The Directive states
that 1 p.e. (population equivalent)’ means the organic biodegradable load having a five-day biochemi-
cal oxygen demand (BOD5) of 60 g of oxygen per day.
 A B C D E F G H I J K L
56

28 Solution:
29 (a) Calculation of the theoretical COD of the wastewater
30 Calculation of the theoretical COD of each of the compounds
31
32 Compound Glucose Acetic acid Propionic acid Butyric acid Legend
33 Empirical formula C6H12O6 C2H4O2 C3H6O2 C4H8O2 Data
34 C: 6 2 3 4 Calculations
35 H: 12 4 6 8 Solution
36 O: 6 2 2 2
37
38 CODT: 1.067 1.067 1.514 1.818 mg O2/mg CxHyOz
39 g O2/g CxHyOz
40
41 Calculation of the CODT of the waste water 8(4x + y – 2z)
42 CODT =
(12x + y + 16z)
43
44 Compound Concentration CODT Concentration
3 Balances in systems with chemical reaction

45 (g/L) (g/g) (g COD/L)

46 Glucose 2.0 1.067 2.133
47 Acetic acid 1.5 1.067 1.600 gCOD g . gCOD
=
48 Propionic acid 1.8 1.514 2.724 L L g
49 Butyric acid 0.5 1.818 0.909
50 7.367
51

Figure 3.3: Calculation of the CODT of each compound and of the residual water.
 3.1 Stoichiometry 57

Nj − Njo
X= (3:5)
αj

which has the same value for the “S” components. From eq. (3.5) we obtain the
quantity of component at a given time:

Nj = Njo + αj · X (3:6)

The molar conversion, X, is an extensive variable, measured in moles, and its main
property is that it is a variable that depends exclusively on the reaction and not on
the choice of any arbitrary Aj compound.
If there are several reactions, a molar conversion can be defined for each of
them Xi. If Xi is the conversion of the reaction i, this reaction would increase (or
decrease) the number of moles of the compound Aj by an amount of αij Xi:
X
Nj = Njo + αji · Xi (3:7)
i

The equations are also valid for dynamic systems, where it is normal to use molar
flows, n, instead of quantities. So, for a reaction:

nj − njo
X= (3:8a)
αj

nj = njo + αj · X (3:8b)
In the rest of the chapter the equations will be expressed with the terminology of
the molar quantity, N, which is logically equivalent for dynamic systems with molar
flows, n.

3.1.2.1 Intensive conversion

If the volume remains constant, we can divide eq. (3.6) by V for a single reaction:

Nj Njo X
= + αj ·
V V V (3:9)
cj = cjo + αj · ξ

where ξ is the intensive conversion of the reaction (moles/volume) and cjo is the
composition of the component Aj in the initial conditions.

3.1.2.2 Degree of Conversion

For a given reaction scheme the degree of conversion of a given component, Ak (always
reactant), can be defined as the number of moles that have reacted of that component
for each mole of reactant present in the initial mixture. The definition applies to both
static and dynamic systems. In the former, the initial mixture should be understood for
58 3 Balances in systems with chemical reaction

a reaction time t = 0, and in the latter, the initial mixture should be understood at the
input of the system.
The conversion degree symbol is usually provided with a subscript that refers to
the key component or component for which it was defined, although in the case of sys-
tems in which a single reaction takes place, the subscript is usually not considered,
although it must be made very clear to which component or chemical species it refers.
Therefore, if we work with quantity of moles (N):

Nko − Nk
ζk = (3:10)
Nko

Therefore,

Nk = Nko ð1 − ζ k Þ (3:11)

If the density of the system remains constant throughout the process (this hypothe-
sis is valid for most liquid reactions and gas reactions where the number of prod-
ucts is equal to the number of moles of reactants, i.e., when ∑αj = 0), expression
(3.11) can be divided by the volume:

Nk Nko
= ð1 − ζ k Þ ) ck = cko ð1 − ζ k Þ (3:12)
V V

The degree of conversion, ζ, is an intensive magnitude and refers to one component

(reactant) and therefore does not have to be the same for all reactants. In any case
it is evident that its value can oscillate between 0 (null conversion) or 1 (complete
conversion).
In the reaction,

αk Ak + αj Aj + αe Ae = 0

where Ak and Aj are the reactants, it must be fulfilled that

 
ðNko − Nk Þ Njo − Nj
=
αk αj

Substituting the value of Nk for the value obtained in eq. (3.11), the expression for
the calculation of Nj is obtained from the degree of conversion:
αj
Nj = Njo − Nko · ζ k · (3:13)
αk

If in addition the volume remains constant, dividing expression (3.13) by the volume:
αj
cj = cjo − cko · ζ k · (3:14)
αk
The above relationships are equally valid for molar flows.
 3.1 Stoichiometry 59

3.1.2.3 Relationship between molar conversion and degree of conversion

From eqs. (3.6) and (3.13) it must be fulfilled that
αj
αj · X = − Nko · ζ k ·
αk

The relationship between the molar conversion, X, and the degree of conversion, ζk,
is therefore immediately deduced:

Nko
X= − · ζk (3:15)
αk

3.1.3 Limiting reactant and excess

It is said that Ak is a limiting reactant is the one that is in less quantity than that of
stoichiometric proportion, that is, to say:
   
Nko  Njo 
 <  (3:16)
α  α 
k j j = 1, 2, ..., S

Generally, the degree of conversion refers to the limiting reactant.

It is said that a reactant is in excess on the limiting reactant if it is found in
greater quantity than that which would correspond to it stoichiometrically. Excess
is defined as

Njo =αj − Nko =αk

%Aj = · 100 (3:17)
Nko =αk

Example 3.3: The empirical formula of gasoline is approximately C7H15 and has a specific weight of
750 Km/m3. If all the carbon is emitted in the form of CO2 when burned calculate:
a. For a Euro 4 car – whose average consumption is 10 L per 100 km – that travels about
300,000 km before being scrapped, how much carbon will it emit during its useful life?
b. If the car weighs 1,800 kg and travels 25,000 km/year, what is the relationship between the
emitted carbon sink and the weight of the vehicle?
c. If vehicles were subject to the Kyoto protocol and therefore had to access the carbon market
(average cost of the Tm of CO2 of 20 euros), what would be the annual cost and the cost per
liter consumed?
d. If you switched to a car that complies with the Euro 5 Directive, with an average consumption
of 7.5 L per 100 km, what would be the reduction in emissions that would be achieved in its
useful life?
e. If an electricity company were to accept as carbon credits the subsidy on the purchase of Euro
5 vehicles to remove old vehicles from circulation, how much should it be willing to pay to
incentivize its owners to purchase a new vehicle?
60 3 Balances in systems with chemical reaction

Solution:
Step 1: Scheme of the process with identification of data
The reaction that takes place in the car:

43 15
C7 H15 + O2 ! 7CO2 + H2 O
2 2
If we call A1 ≡ C7H15, A2 ≡ O2, A3 ≡ CO2, A4 ≡ H2O the reaction can be expressed:

15 43
A4 + 7A3 − A2 − A1 = 0
2 2
It is worth noting:
i. The limiting reactant will be the fuel since the amount of air is at least stoichiometric, that is,
k = 1.
ii. Conversion rate equal to 1 (full conversion).
iii. In this problem it is necessary to use molecular masses, since many of the sections the emis-
sions are needed.

Step 2: Basis of calculations

The basis of calculation shall be the mileage of the vehicle.

Step 3: Definition of control volumes and formulation of the mass balances

In this case, the only volume is the vehicle where the mass balances with chemical reactions are
raised, which corresponds to the application of eqs. (3.11) and (3.13):
Balance for the limiting reactant: N1 = N1o · ð1 − ζ 1 Þ
α
Balance for CO2: N3 = N3o − N1o · ζ 1 · α3
1

Step 4: Solving the system of equations

The calculations for section (a) are shown in Figure 3.4.

A B C D E F G H I
23 Solution:
24 Scheme of the process and identification of the data:
25 LEGEND
26 Degree of conversion: 1 Data
27 Calculations
28 Feed Products Solution
29 Flow rate:
30 A1 A2
31 Compound: C7O15 CO2
32 Molecular weight 99 44 g/mol
43 15
33 C7H15 + O 7CO2 + H O Stoichiom. Coef. -1 7
34 4 2 2 2
35
36 (a) Carbon emissions
37 Euro 4
38 Distance: 3,00,000 km Fuel: 30,000 L
39 Consumption: 10.0 L per 100 km 22,500 kg
40 10.0 km/L
41 Specific gravity: 750.0 kg/m3
42 Output Input
43 A1: Gasoline 0.00 kmol N10 = 227.3 kmol
44 A3: CO2 1,590.91 kmol
45 N1 = 70,000.00 kg
46 N2 = 70.00 Tm
47
48 As C: 19,090.9 kg
49 19.1 Tm
50

Figure 3.4: Calculation of the composition of the combustion gases.

 3.1 Stoichiometry 61

H44: = –(G43*$F$26*($F$33/$E$33)) [moles of CO2 formed; the initial amount of CO2 is 0]

H45: = D44*$F$32 [from the molecular weight of CO2, its value in weight can be obtained]
H48: = –($H$47*$C$31*(C37/$C$34)) [from the weight of C in the CO2 molecule, the kg of C
can be obtained]
For the calculation of section (b), it is sufficient to replace the value of 300,000 km by 25,000 km
and the value obtained by dividing it by 1,800 kg. The result is 0.88.
Section (c) is obtained directly by multiplying the annual tons of CO2 produced in section (b) by
the value of 20 €, that is, 116.67 €. If this value is divided by the liters of annual fuels (2,500 L/year),
the cost would be 5 cents per liter.
Section (d) implies changing the value of the consumption, by a value of 7.5 km per 100 km, which
will allow the vehicle to travel 13.3 km per liter. In this case, the kg of CO2 that would be formed would
be 52,500 kg; therefore, the emission reduction would be: 70,000–52,500 = 17,500 kg. This reduction
would entail a cost (section e) of €350, which should be the subsidy provided by the electricity company.

Example 3.4: In a boiler, propane is burned as fuel in the presence of air. Determine the molar com-
position (dry and wet basis) of the combustion products if the operating conditions are as follows:
a. 100% conversion and supply of stoichiometric air.
b. 100% conversion and supply of enriched air (23% oxygen) in stoichiometric quantities.
c. 100% conversion and 20% excess air.
d. 90% conversion and 20% excess air.

Solution:
Step 1: Flowchart with identification of data
The flow diagram is very simple as it is a single unit (furnace) where propane is burned (Figure 3.5).

3 Combustion
Products

C3H8+5O2 → 3CO2 + 4H2O

Air 2 1 C3H8

Figure 3.5: Process scheme.

If we call A1≡C3H8, A2≡O2, A3≡N2, A4≡CO2, A5≡H2O the reaction can be expressed as follows:

4 A5 + 3A4 − 5 A2 − A1 = 0
62 3 Balances in systems with chemical reaction

The degree of conversion will vary for each section. As far as stream data is concerned, it is worth
noting:
i. The limiting reactant will be the fuel (stream 1) since the amount of air is at least stoichiomet-
ric, that is, k = 1.
ii. The average air composition can be assimilated to 21% oxygen and 79% molar nitrogen; there-
fore, the nitrogen flow at the furnace inlet, stream 2 – indicated by the subindex outside the
 
parentheses, will be ðn3 Þ2 = ðn2 Þ2 · 0.79
0.21 .
iii. The number of moles of oxygen at the inlet will depend on the excess to be considered with
respect to the fuel (for stoichiometric conditions the value of the excess will obviously be
zero). The equation applied is (3.17)
 
ðn2 Þ2 =α2 − ðn1 Þ1 =α1 α2 %A2
% A2 = · 100 ) ðn2 Þ2 = ðn1 Þ1 1 +
ðn1 Þ1 =α1 α1 100

Step 2: Basis of calculations

The basis of calculation shall be the fuel flow: (n1o)1 = 100 mol/h.

Step 3: Definition of control volumes and formulation of the mass balances

In this case, the only control volume is the furnace where the mass balances with chemical reac-
tions are raised, which corresponds to the application of eqs. (3.11) and (3.13) in molar units.
Balance for the limiting reactant: ðn1 Þ3 = ðn1 Þ1 · ð1 − ζ 1 Þ
    α
Balances for all other reactants and products: nj 3 = nj 2 − ðn1 Þ1 · ζ 1 · α j
1
Balance for inerts (N2): ðn3 Þ3 = ðn3 Þ2

Step 4: Solving the system of equations

The composition of the combustion gases for section (a) is presented in Figure 3.6.
H21: = H47*(1−C31) [limiting reactant])
H22: = B47–($H$47*$C$31*(C35/$C$34)) [oxygen moles]
H23: = B48 [moles of nitrogen, inert in reaction]
H24: = –($H$47*$C$31*(C37/$C$34)) [moles of CO2 formed, value at input is zero]
H25: = –($H$47*$C$31*(C38/$C$34)) [moles of H2O formed, the value at the input is zero]

In cells H26 and H27 the moles of products are added, whether or not the quantity of H2O is taken
into account, since both quantities are necessary for the calculation of the percentage on a dry or
wet basis of the combustion gases composition of the furnace:

molcomponent
% on a dry matter: %DM = · 100
total molwithout H2 O

molcomponent
% on a wet basis: %w.b. = · 100
total mol

Questions/simulations:
i. Effect of the calculation base: If the calculation basis is changed, the concentration of the com-
bustion products will not change. Thus, if cell H47 is changed to 25 mol/h, the same values
will be obtained in the percentage of each of the compounds.
ii. Enriched air (section b): If enriched air is used, cell C47 with a value of 23, the amount of N2
will be lower and the relative concentrations of the other gases will increase.
iii. Simulation of boiler operation: Sections (c) and (d) of the problem correspond to different
boiler operating conditions. For its calculation it is enough to replace in cell C31 the degree of
advance of the reaction and in cell B49 the excess of air that is used.
 A B C D E F G H I J K
18 Solution:
19 Legend:
20 Data mol/h % dry matter % wet basis
21 Calculations C3H8: 0.0 0.0 0.0
22 Solutions O2: 0.0 0.0 0.0
23 3 N2: 1881.0 86.2 72.9
24 CO2: 300.0 13.8 11.6
25 H2O: 400.0 15.5
26 Subtotal (–H2O): 2181.0
27 Total: 2581.0 100.0 100.0
28
29 Reaction data: Limiting reactant equation:
30
31 Degree of conversion: 1.0 (n1)3 = (n1)1(1 – ζ1)
32
33 Code Stoichiometric coef.
34 Equation for other reactants and products
C3H8: k=1 –1
35 O2: j=2 –5 αj
36 (nj)3 = (nj)2 – (n1)1ζ1
N2: j=3 0 C3H8+5O2→3CO2+4H2O α1
37 CO2: j=4 3
38 H2O: j=5 4
39
40
41
42
43
44
45
46 mol/h % mol
47 O2: 500 21.0 C3H8: 100.0 mol/h
48 N2: 1,881.0 79.0 2 1
49 Excess(%): 0.0 Basis of calculations
3.1 Stoichiometry

Figure 3.6: Calculation of the composition of the combustion gases.

63
64 3 Balances in systems with chemical reaction

Example 3.5: Figure 3.7 shows part of the methanol production process with a stoichiometric CO
and H2 feed (stream 1) to achieve a step conversion in the reactor (R-101) of 27.5%. In the separa-
tion tower (T-101) all the methanol formed comes out as a product, with a maximum stream of 0.5%
H2 from which the tower is fed. The recirculation ratio is 7.0. Calculate the overall conversion,
molar flow and composition of all streams.

1 T-101

CO H2

3
4 Products
R-101

CO + 2H2 → CH3OH

Figure 3.7: Methanol production process.

Solution:
Step 1: Flowchart with identification of data
Reaction data: If we call A1≡CO, A2≡H2, A3≡CH3O, the reaction can be expressed:

A3 − 2A2 − A1 = 0
CO being the limiting reactant (in this case since both reactants are in stoichiometric ratio, H2
could also be considered); therefore, k = 1 and a degree of conversion of 0.275.

Process data:
i. The recirculation ratio, r = (ntotal)5/(ntotal)1 = 7.0.
ii. Hydrogen in product stream, φ = 0,005:
ðn2 Þ4 = φ · ðn2 Þ3
Step 2: Basis of calculations
The flow rate of CO feed shall be considered as the calculation basis: (n1)1 = 100 mol/h; therefore,
the quantity of hydrogen (stoichiometric) will be (n2)1 = 200 mol/h.

Step 3: Definition of control volumes and formulation of the mass balances

To calculate the molar flow of the components in each stream (obviously, this will allow the imme-
diate calculation of the molar fraction), eq. (2.10b) for the component balance without chemical re-
action and eqs. (3.11) and (3.13) for the mass balances with chemical reactions will be applied:
 3.1 Stoichiometry 65

– Volume control to the mixing point of the feed and recirculation

CO balance ðn1 Þ1 + ðn1 Þ5 = ðn1 Þ2

H balance ðn2 Þ1 + ðn2 Þ5 = ðn2 Þ2

ðntotal Þ5 ðn1 Þ5 + ðn2 Þ5
Recirculation ratio r= = n
ðntotal Þ1 ð total Þ1
– Control volume corresponding to reactor R-

CO balance (limiting reactant) ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ

α2
H balance ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 · α1

CHOH balance α3
ðn3 Þ3 = − ðn1 Þ2 · ζ 1 · α1
(stream  does not contain methanol)

– Control volume for separation column T-

CO balance ðn1 Þ3 = ðn1 Þ4 + ðn1 Þ5

ðn2 Þ3 = ðn2 Þ4 + ðn2 Þ5

H balance and recovery
ðn2 Þ4 = φ · ðn2 Þ3

CHOH balance ðn3 Þ3 = ðn3 Þ4

Step 4: Solving the system of equations

From the above equations, the system is defined by six linearly independent equations:

Equations Unknowns Coded equations

½1 ðn1 Þ1 + ðn1 Þ5 = ðn1 Þ2 x = (n) ½1 x1 − x3 = ðn1 Þ1

½2 ðn2 Þ1 + ð1 − φÞðn2 Þ3 = ðn2 Þ2 x = (n) ½2 x2 − ð1 − φÞ · x5 = ðn2 Þ1
ðntotal Þ5 ðn1 Þ5 + ð1 − φÞðn2 Þ3 x = (n) ½3 x3 + ð1 − φÞ · x5 = r · ðntotal Þ1
½3 r = = x = (n)
ðntotal Þ1 ðntotal Þ1 ½4 ð1 − ζ 1 Þx1 − x4 = 0
x = (n) α2
½4 ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ ½5 ζ 1 · x1 − x2 + x5 = 0
α2 x = (n) α1
½5 ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 · α3
α1 ½6 ζ 1 · x1 + x6 = 0
α3 α1
½6 ðn3 Þ3 = − ðn1 Þ2 · ζ 1 ·
α1

First, a copy of the “6 variables” sheet from the “Appendix_D_Linear_Equations” (see Appendix D) to
the book where the solution to the problem is being elaborated. Both sheets are then “intercon-
nected” with the introduction of the coefficients of the linear equations as data or as a formula when
related to the spreadsheet of the problem (Figure 3.8):
B11: = 0 (entered as a number, since it does not depend on the data in the problem statement).
B12: = (1-’Example 3.5ʹ!C42) (introduced as a formula by relating it to the spreadsheet where
the data on the problem are indicated).
66 3 Balances in systems with chemical reaction

A B C D E F G H I J K L M N O
1 Solving simultaneous equations
2
3 Matrix inversion method
4 6-Variables
5
6
7
8 ai 1 ai 2 ai 3 ai 4 ai 5 ai 6
9 E1: 1.00 x1+ 0.00 x2+ –1.00 x3+ 0.00 x4+ 0.00 x5+ 0.00 x6 = 100.0
10 E2: 0.00 x1+ 1.00 x2+ 0.00 x3+ 0.00 x4+ –0.995 x5+ 0.00 x6 = 200.0
11 E3: 0.00 x1+ 0.00 x2+ 1.00 x3+ 0.00 x4+ 0.995 x5+ 0.00 x6 = 2100.0
12 E4: 0.725 x1+ 0.00 x2+ 0.00 x3+ –1.00 x4+ 0.00 x5+ 0.00 x6 = 0.0
E
13 5 : –0.550 x1+ 1.00 x2+ 0.00 x3+ 0.00 x4+ –1.00 x5+ 0.00 x6 = 0.0
14 E6: –0.275 0.00 0.00 0.00 0.00 1.00 = 0.0

Figure 3.8: Connection of sheet containing the data of the problem with the solution of the system
of linear equations of Example 3.5.

When you finish entering the coefficients you will automatically get the calculation of the solution
that we can, in turn, transfer to the corresponding cells in the main spreadsheet of the problem
(Figure 3.9).

Questions/simulations:
i. Effect of the degree of conversion or step conversion in the reactor (R-101): The overall conver-
sion depends to a large extent on the recirculation system with separation. Thus, if a (more
expensive) catalyst change were to take place that would allow a step conversion of 30% (cell
C42), the overall conversion would not change.
ii. Separation efficiency in tower T-101: If the separation efficiency is reduced so that the output
stream is 1% H2 (cell L40), two effects occur: (a) the purity of the methanol is reduced and (b)
the overall conversion is reduced to 90%.

3.1.4 Multiple reactions: yield and selectivity

For multiple reactions the molar conversion of each of them, Xi, is defined so that
the equation that relates the initial and final moles for all the components of the
reaction corresponds to eq. (3.18):
X
h  
Nj = Njo + αji · Xi (3:18)
i=1

In moles per unit of time,

X
h  
nj = njo + αji · Xi (3:19)
i=1

Similarly, it is necessary to define intensive conversion for each of them, to obtain

the concentration of each of the components of the reaction:
 A B C D E F G H I J K L M
35 Solution:
36 Legend
37 Data mol/h zi Process parameters
38 Calculations CO : 246.7 0.117
39 Solution H2: 1,853.3 0.883 r= 7.0
40 Total: 2,100.0 1.000 ȹ= 0.005
41 Reaction data: Global conversion 95.3 %
42 Degree of conversion: 0.275
43 5
44 CO: k=1 –1 mol/h zi
45 H2: j=2 –2 CO : 346.7 0.14
46 CH3OH: j=3 1 H2: 2,053.3 0.86
47 Total: 2,400.0 1.00
48 2
49
50
51
1
52 T-101 mol/h zi
53 CO: 4.7 0.043
54 H2: 9.3 0.085
55 CH3OH: 95.3 0.872
56 mol/h
CO H2 109.3
zi Total: 1.000
57 A1: CO: 100.0 0.333
58 A2: H2: 200.0 0.667
59 Total: 300.0 1.000 3
60 4 Products
61 R-101
62 mol/h zi
63 CO + 2H2 → CH3OH CO: 251.4 0.114
64 H 2: 1,862.6 0.843
65 CH3OH: 95.3 0.043
66 Total: 2,209.3 1.000
67
3.1 Stoichiometry

Figure 3.9: Solution to Example 3.5.

67
68 3 Balances in systems with chemical reaction

Xi
ξi = − (3:20)
V
X
h  
cj = cjo + αji · ξ i (3:21)
i=1

If the degree of conversion were used, the moles of the limiting reactant (3.11) and
of the other reactants and products (3.13) would be calculated by
 X h 
Nk = Nko 1 − ζ ki (3:22)
i=1

Xh  
αji
Nj = Njo − Nk0 i · ζ ki · (3:23)
i=1
αki

For both single and multiple reactions, the performance of an Aj product is defined,
always with reference to the limiting reactant Ak as

kmol Aj output αk Njo − Nj αk

Rj = · = · (3:24)
kmol Ak input αj Nko αj

The selectivity of an Aj product is a term usually used only in multiple reaction sys-
tems. It is usually defined as

kmol Aj generated αk Njo − Nj αk

Sj = · = · (3:25)
kmol Ak that reacted αj Nko − Nk αj

Being Ak, the limiting reactant from which Aj can be obtained.

Example 3.6: In the combustion chamber of a boiler, propane is introduced with 200% excess air.
If 80% is converted to carbon dioxide and 10% to carbon monoxide, calculate the composition of
the combustion gases on a dry and wet basis.

Solution:
Step 1: Flowchart with identification of data
The flow diagram is identical to Example 3.4 (Figure 3.5) except that two reactions take place in this
case:
C3 H8 + 5O2 ! 3CO2 + 4H2 O
7
C3 H8 + O2 ! 3CO + 4H2 O
2
If we call A1≡C3H8, A2≡O2, A3≡N2, A4≡CO2, A5≡H2O, A6≡CO the reactions can be expressed:

4A51 + 3A41 − 5A21 − A11 = 0

7
3A62 + 4A52 − A22 − A12 = 0
2
where α11 = −1, α21 = −5, α41 = 3, α51 = 4, α12 = −1, α22 = −3,5, α52 = 4 and α62 = 3.
 3.1 Stoichiometry 69

The degree of conversion will vary for each section. As far as stream data is concerned, it is
worth noting:
i. The limiting reactant will be the fuel (stream 1) since the amount of air is in excess; therefore,
k = 1 for both reactions.
ii. The average air composition can be assimilated to 21% oxygen and 79% molar nitrogen; there-
fore, the nitrogen flow at the furnace inlet, stream 2 – indicated by the subindex outside the
 
parentheses, will be ðn3 Þ2 = ðn2 Þ2 · 0.79
0.21 .
iii. The amount of moles of oxygen at the inlet will depend on the excess considered over the fuel.
Equation (3.17) is applied to each of the reactions to obtain the number of moles of oxygen in
stream 2:
   
α21 α22 % A2
ðn2 Þ2 = + · ðn1 Þ1 · 1 +
α11 α12 100
Step 2: Basis of calculations
The basis of calculation shall be the fuel flow: (n1o)1 = 100 mol/h.

Step 3: Definition of control volumes and formulation of the mass balances

In this case, the only control volume is the furnace where the mass balances with chemical reactions
are raised, which corresponds to the application of eqs. (3.22) and (3.23) in molar units:
Balance for the limiting reactant: ðn1 Þ3 = ðn1 Þ1 · ð1 − ζ 11 − ζ 12 Þ
    α α
Balances for all other reactants and products: nj 3 = nj 2 − ðn1 Þ1 · ζ 11 · α j1 − ðn1 Þ1 · ζ 12 · α j2
11 12
Balances for inerts: (N2): ðn3 Þ3 = ðn3 Þ2

Step 4: Solving the system of equations

The composition of the combustion gases is presented in Figure 3.10:
H12: = I43*(1−C54−H54) [limiting reactant])
H13: = B38–($I$43*$C$54*(C58/$C$57))−($I$43*$H$54*(H58/$H$57 [oxygen moles]
H14: = B39 [moles of nitrogen, inert in reaction]
H15: = –($I$43*$C$54*(C60/$C$57) [moles of CO2 formed, value at input is zero, in the first
reaction]
H16: = –($I$43*$H$54*(H60/$H$57)) [moles of CO2 formed, value at input is zero, in the second
reaction]
H17: = –($I$43*$C$54*(C61/$C$57))−($I$43*$H$54*(H61/$H$57)) [moles of H2O formed, the
value at the input is zero in both reactions]

In cells H18 and H19 the moles of products are added, whether or not the quantity of H2O is taken
into account, since both quantities are necessary for the calculation of the percentage on a dry or
wet basis of the combustion gases composition of the furnace:

molcomponent
% on a dry matter: %DM = · 100
total molwithout H2 O
molcomponent
% on a wet basis: %wet basis = · 100
total mol
 70
3 Balances in systems with chemical reaction

Figure 3.10: Calculation of the composition of the combustion gases (multiple reactions).
 3.2 Chemical equilibrium in systems with chemical reactions 71

3.2 Chemical equilibrium in systems with chemical reactions

3.2.1 Chemical equilibrium with gas-phase reactions

Most reactions are, to some extent, reversible, acting in both directions at once.
When the reaction rates are the same, the reaction is said to have reached equilib-
rium, and the equilibrium constant of the reaction, K, can be defined by eq. (3.26):

aA + bB ! cC + dD

acC · adD − ΔG
o
K= = e RT (3:26)
aaA · abB

where
– a, activity
– ΔGo, standard Gibbs free energies of formation6
– R, constant of ideal gases
– T, temperature.

The standard Gibbs free energy of a reaction is defined as

X
S
ΔG0 = αj · G0j (3:27)
j=1

As Goi energy is a property of the pure species i in its standard state at fixed pres-
sure, it depends only on the temperature, and both the free Gibbs energy exchange
standard of a reaction and the equilibrium constant will also be unique functions of
its temperature.
Starting from Gibbs’ dependence of free energy on temperature, eq. (3.28)7 sig-
nals the effect of temperature on the equilibrium constant. If the reaction is exother-
mic, ΔHo < 0, the equilibrium constant decreases as the temperature increases. In
contrast, the value of K increases with T for an endothermic equation:

d ln K dðΔG0 =RT Þ ΔH 0
=− = (3:28)
dT dT RT 2
Taking into account the definition of activity (as the quotient of the fugacity of species
j and the value of the fugacity of the standard state, ^fj see Section 2.5 of Chapter 2) and
of the fugacity coefficient (relationship between fugacity and pressure, ϕ ^ ):
j

^f ^ · pj
ϕ
j j
aj = o = (3:29)
fj fjo

6 J. Willard Gibbs (1839–1903): American chemist.

7 Commonly referred to as the van’t Hoff equation, in honor of Jacobus van’t Hoff (1852–1911)
72 3 Balances in systems with chemical reaction

If Dalton’s law applies

^ · yj · P
ϕ j
aj = (3:30)
fjo

Equation (3.30) can be simplified for ideal gases (usually at sufficiently low pres-
sures or sufficiently high temperatures) as indicated in eq. (3.31), as it is verified:
i. Fugacity in its standard state is equal to its pressure, fjo = Po.
ii. The standard state for a gas is the ideal state of pure gas at the pressure of the
standard state P° of 1 atm.
iii. The fugacity coefficient is 1:

yj · P
aj = = yj · P (3:31)
Pjo

By replacing this definition of activity in the definition of the equilibrium constant

(3.26):

ycC · ydD c + d − a − b
K= ·P (3:32)
yaA · ybB

Considering the algebraic formulation of a chemical reaction, the general expres-

sion that defines the equilibrium for gas phase reactions would be
X
w  
ln K = αj ln yj · P (3:33)
j=1

Example 3.7: One of the reactions involved in the production of hydrogen is as follows:
COðgÞ + H2 Oðv Þ ! CO2ðgÞ + H2ðgÞ

Calculate the degree of conversion in the equilibrium as well as the molar fraction of each compo-
nent with a stoichiometric feed. The pressure is atmospheric, and the temperature is 500 K, for
which the standard Gibbs free energy is −20.784,63 J/mol.
Solution:
Step 1: Flowchart with identification of data
The flow diagram is very simple as it is a single unit where hydrogen is produced (Figure 3.11).
If we call A1≡CO, A2≡H2O, A3≡CO2, A4≡H2, the direct reaction can be expressed as

A4 + A3 − A2 − A1 = 0
As far as stream data is concerned, it is worth noting:
i. The limiting reactant will be CO, that is, k = 1.
ii. In equilibrium the eq. (3.33) should be verified:
ln K = α1 lnðy1 · PÞ + α2 lnðy2 · PÞ + α3 lnðy3 · PÞ + α4 lnðy4 · PÞ

Step 2: Choice of the calculation base

The calculation basis shall be the flow rate of CO in the input stream: (n1)1 = 100 mol/h.
 3.2 Chemical equilibrium in systems with chemical reactions 73

3 CO2
H2

CO + H2O ⇆ CO2+H2

H2O 2 1 CO

Figure 3.11: Scheme of the process.

Step 3: Definition of control volumes and formulation of the mass balances

In this case, the only control volume is the unit where the mass balances with chemical reaction
are raised, which corresponds to the application of eqs. (3.11) and (3.13) for molar flows with the
degree of equilibrium conversion.
Balance for the limiting reactant: ðn1 Þ3 = ðn1 Þ1 · ð1 − ζ eq Þ
    α
Balances for all other reactants and products: nj 3 = nj i − ðn1 Þ1 · ζ eq · α j
1

Step 4: Solving the system of equations

The idea is to solve a nonlinear equation (equilibrium condition) as a function of the degree of con-
version that determines the molar fractions obtained from the mass balance with chemical reac-
tion. This nonlinear equation will be solved by the “Goal Seek” technique (see Appendix C), for
which a spreadsheet should be developed where the target function will be the difference between
the actual value of K and the value obtained in the iteration of the calculation as a function of the
degree of conversion (Figure 3.12).
The molar flow and composition in the output stream is obtained from the mass balance with
chemical reaction (cells H15:I18). So, for the CO:
H15: = I41*(1−C25) [limiting reactant in the output stream]
I15: = H15/$H$19 [mole fraction of CO in the output stream]

The estimate of the equilibrium constant from the equilibrium conversion (cell C25) is calculated in
cell I32:
I32: = C28*LN(I15*I31) + C29*LN(I16*I31) + C30*LN(I17*I31) + C31*LN(I18*I31)

The actual value of the equilibrium constant is calculated in cell B23 from eq. (3.26):
B23: = EXP(−1*B21/(B22*B20))
The problem will be solved as soon as the value of the real equilibrium constant and the estimated
equilibrium constant are equal, that is, the objective function of cell I35:
I35: = LN(B23)−I32

When considering the function “Goal Seek” it will be specified the following:
– Target cell: I35
– With a value of 0
– To change the cell: C25 (equilibrium conversion)
 A B C D E F G H I J K
74

12 Solution
13 Legend mol/h yi
14 Data
CO: 7.59 0.0379
15 Calculations H2O: 7.59 0.0379
16 Solution
17 3 CO2: 92.41 0.4621
18 H2: 92.41 0.4621
19 Reaction data: Total: 200.0 1.0000
20 T= 500 K
21 ΔG0T = –20,784.63 J/mol Limiting reactant equation: (n1)3 = (n1)1 (n–ζeq)
22 R= 8.314 J/mol K
23 K= 148.4 Equation for other reactants and products
24
25 Equilibrium conversion: 0.9241 αj
26 (nj)3 = (nj)i – (n1)1ζeq
α1
27 Code Stoichiometric coef.
28 CO: k=1 –1
29 H2O: j=2 –1
30 CO2: j=3 1 Conditions of the equilibrium
31 H2: j=4 1
32 P= 1.0 atm
33 InK = 4.9999E+00
34 CO(g) + H2O(v) ⇆ CO2(g) + H2(g)
3 Balances in systems with chemical reaction

35 Function objective
36
37
f(ζeq)= 4.7596E–05
38
39
40 Basis of calculations
41 mol/h
42 H2O: 100.0
43 Excess(%): 0.0 CO: 100.0 mol/h
44 2 1 CO2: 0.0 mol/h
45 α ⎡ ⎛ %A2⎞⎤ H 2: 0.0 mol/h
46 (n20 )2 = α 2 (n10 )1 ⎢1+ ⎜ ⎟⎥
47 1 ⎣ ⎝ 100⎠⎦

Figure 3.12: Calculation of the equilibrium conversion.

 3.2 Chemical equilibrium in systems with chemical reactions 75

Automatically the result of the problem will be obtained, where 0.9241 being the degree of conver-
sion in the equilibrium. A rule with icons has been inserted in the cell, such that if the convergence
value was negative, a red traffic light would be obtained.

Questions/simulations:
i. Excess in one of the reactants: If an excess of water vapor is introduced, for example, 50% in cell
B43, and the “Find Target” function is reapplied, the conversion to equilibrium will be 0.9872. If
an excess of water vapor is introduced, for example, 50% in cell B43, and the “Find Target” func-
tion is reapplied, the conversion to equilibrium will be 0.9872. This data is explained by the prin-
ciple of Le Châtelier; the balance has been displaced in the sense of the direct reaction.
ii. Presence of products in the feed: If an amount of carbon dioxide is present in the feed stream
(e.g., 25 mol/h in cell I42), the conversion to equilibrium would obviously be lower (0.9152).

Example 3.8: Analyze the appropriate P and T conditions, from a thermodynamic point of view, to
define the operating conditions of a reactor where ethanol is produced from ethylene hydration
with a steam/ethylene feed ratio of 4:

C2 H4 ðgÞ + H2 OðgÞ ! C2 H5 OHðgÞ

Data: (a) ΔG = 6,730.02 J/mol at 145 °C; (b) ΔGO = 20,021.36 J/mol at 250 °C; (c) consider the
O

operating pressure of 20 and 40 atm.

Solution:
Step 1: Flowchart with identification of data
The flow diagram is similar to Example 3.7, since it is a single unit, the reactor.
If we call A1 ≡ C2H4, A2 ≡ H2O, A3 ≡ C2H5OH, the direct reaction can be expressed as

A3 − A2 − A1 = 0
As far as stream data is concerned, it is worth noting:
i. The limiting reactant will be C2H4, that is, k = 1.
ii. In equilibrium the eq. (3.33) should be verified:

ln K = α1 lnðy1 · PÞ + α2 lnðy2 · PÞ + α3 lnðy3 · PÞ

Step 2: Basis of calculations
The calculation basis will be the flow rate of C2H4 in the input stream: (n1)1 = 100 mol/h.

Step 3: Definition of control volumes and formulation of the mass balances

In this case, the only control volume is the unit where the mass balances with chemical reaction
are raised, which corresponds to the application of eqs. (3.11) and (3.13) for molar flows with the
degree of equilibrium conversion:  
Balance for the limiting reactant: ðn1 Þ3 = ðn1 Þ1 · 1 − ζ eq
    α
Balances for all other reactants and products: nj 3 = nj i − ðn1 Þ1 · ζ eq · α j
1

Step 4: Solving the system of equations

The idea is to solve a nonlinear equation (equilibrium condition) as a function of the degree of conver-
sion that determines the molar fractions obtained from the mass balance with chemical reaction. This
nonlinear equation will be solved by the “Goal Seek” technique (see Appendix C), for which a spread-
sheet must be developed where the target function will be the difference between the actual value of
K and the value obtained in the iteration of the calculation as a function of the degree of conversion.
Figure 3.13 shows the results obtained for a temperature of 145 °C and a pressure of 20 atm.
 76

A B C D E F G H I J K
16 Solution:
17 Legend
18 Data mol/h yi
19 Calculations C 2H4: 31.09 0.0721
20 Solution H2O: 331.09 0.7680
21 C2H5OH: 68.91 0.1599
3
22 Reaction data: Total: 431.1 1.0000
23 T= 145 °C
24 418.15 K
25 ΔG0T = 6,730.02 J/mol Limiting reactant equation: (n1)3 = (n1)1 (n–ζeq)
26 R= 8.314 J/mol K
27 K= 0.14430 Equation for other reactants and products
28
29 Equilibrium conversion: 0.689 α
(nj)3 = (nj)i – (n1)1ζeq
30 α
31 Code Stoichiometric coef.
32 C2H4: k=1 -1
33 H2O: j=2 -1 Conditions of the equilibrium
34 C2H5OH: j=3 1
35 P= 20.0 atm
36 lnK = –1.9359E+00
C2H4(g) + H2O(g) ⇆ C2H5OH(g)
37
3 Balances in systems with chemical reaction

38 Function objective
39 f(ζeq)= 1.3758E–05
40
41
42
43
44
45 mol/h
46 H2O: 400.0 2 1 C2H4: 100.0 mol/h
47 rH O/C H : 4.0
2 2 4
48

Figure 3.13: Calculation of the equilibrium conversion.

 3.2 Chemical equilibrium in systems with chemical reactions 77

The molar flow and composition in the output stream is obtained from the mass balances with
chemical reaction in cells H19:I21. So, for C2H4:
H19: = I46*(1−C29) [limiting reactant in output stream]
I19: = H19/$H$22 [mole fraction of C2H4 in output stream]

The estimate of the equilibrium constant from the equilibrium conversion (cell C29) is calculated in
cell I36:
I36: = C32*LN(I19*I35) + C33*LN(I20*I35) + C34*LN(I21*I35)

The actual value of the equilibrium constant is calculated in cell B27 from eq. (3.26):
B27: = EXP(−B25/(B24*B26))

The problem will be solved as soon as the value of the real equilibrium constant and the estimated
equilibrium constant are equal, that is, the objective function of cell I39:
I39: = LN(B27)−I36

When considering the function “Goal Seek” it will be specified:

– Target cell: I39
– With a value of 0
– To change the cell: C29 (equilibrium conversion)

The result of the problem will be obtained automatically, 0.689 being the degree of conversion in
the equilibrium. A rule with icons has been inserted in the cell, such that if the convergence value
was negative, a red traffic light would be obtained.
By entering the pressure and temperature data in the corresponding cells and applying the
“Find Target” function, the following results will be obtained:

T(cell B) K(cell B) P(cell I) ζeq(cell C)

−
 °C .·  atm .
.·−  atm .

 °C .·−  atm .

.·−  atm .

In this reaction when the temperature increases the K decreases and consequently the conversion.
As the pressure increases, so does the conversion. Because of this, thermodynamic considerations
suggest that the operating pressure should be as high as possible (no phase change) and the tem-
perature as low as possible.

Example 3.9: The synthesis of Haber−Bosch8 for ammonia made it possible to obtain this com-
pound in large quantities for the production of fertilizers, explosives and so on:

N2 ðgÞ + 3H2 ðgÞ ! 2NH3ðgÞ K = 0.05

A 220 atm catalytic reactor with unreacted nitrogen and hydrogen recirculation is used, previously
separated in a condenser (Figure 3.14). Stream 4 contains 98% ammonia and 5% nitrogen and hy-
drogen present in stream 3. Calculate the degree of conversion in equilibrium as well as the mole
fraction of each component with a fresh 1/3 N2/H2 feed.

8 Fritz Haber (1868–1934): German chemist. Carl Bosch (1874–1940): German engineer and chemist.
78 3 Balances in systems with chemical reaction

cw

3 E-104 V-101

4 NH3
P-101A/B

R-101
N2 1 2

Figure 3.14: Flowchart of NH3 production.

Solution:
Step 1: Flowchart with identification of data
Reaction data:
If we call A1≡N2, A2≡H2, A3≡NH3 the reaction can be expressed as
2A3 − 3A2 − A1 = 0
with N2 being the limiting reactant (in this case, since both reactants are in stoichiometric relation, H2
could also be considered); therefore, k = 1. In addition, eq. (3.33) should be verified in the equilibrium:

ln K = α1 lnðy1 · PÞ + α2 lnðy2 · PÞ + α3 lnðy3 · PÞ

Process data:
Condenser recovery of φ1 = 0.005, φ2 = 0.005, φ3 = 0.98,

ðn1 Þ4 = φ1 · ðn1 Þ3
ðn2 Þ4 = φ2 · ðn2 Þ3
ðn3 Þ4 = φ3 · ðn3 Þ3
Step 2: Basis of calculations
The feed flow rate of N2 shall be taken as the calculation basis: (n1)1 = 100 mol/h; hence the quan-
tity of hydrogen (stoichiometric) will be (n2)1 = 300 mol/h.

Step 3: Definition of control volumes and formulation of the mass balances

To calculate the molar flow of the components in each stream (obviously, this will allow the imme-
diate calculation of the molar fraction), eq. (2.10b) for the component balance without chemical re-
action and eqs. (3.11) and (3.13) for the mass balances with chemical reaction will be applied:

– Volume control to the mixing point of the feed and recirculation

Balance for N ðn1 Þ1 + ðn1 Þ5 = ðn1 Þ2

Balance for H ðn2 Þ1 + ðn2 Þ5 = ðn2 Þ2

Balance for NH ðn3 Þ5 = ðn3 Þ2

 3.2 Chemical equilibrium in systems with chemical reactions 79

– Control volume corresponding to reactor R-

Balance for N (limiting reactant) ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ

α2
Balance for H ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 · α1
α3
Balance for NH ðn3 Þ3 = ðn3 Þ2 − ðn1 Þ2 · ζ 1 · α1

– Control volume for separation column T-

ðn1 Þ3 = ðn1 Þ4 + ðn1 Þ5
N balance and recovery
ðn1 Þ4 = φ1 · ðn1 Þ3
ðn2 Þ3 = ðn2 Þ4 + ðn2 Þ5
H balance and recovery
ðn2 Þ4 = φ2 · ðn2 Þ3
ðn3 Þ3 = ðn3 Þ4 + ðn3 Þ5
NH balance and recovery
ðn3 Þ4 = φ3 · ðn3 Þ3

Step 4: Solving the system of equations

It is about solving in a combined way the nonlinear equation that defines the equilibrium condition
as a function of the degree of conversion that in turn defines the flows and molar fractions that are
obtained when solving the balances of matter with chemical reaction (in this case it supposes a
system of six linearly independent equations).

Equations Unknowns Coded equations

½1 ðn1 Þ1 + ð1 − φ1 Þðn1 Þ3 = ðn1 Þ2 x = (n) ½1 x1 − ð1 − φ1 Þ · x4 = ðn1 Þ1

½2 ðn2 Þ1 + ð1 − φ2 Þðn2 Þ3 = ðn2 Þ2 x = (n) ½2 x2 − ð1 − φ2 Þ · x5 = ðn2 Þ1
  x = (n)  
½3 1 − φ3 ðn3 Þ3 = ðn3 Þ2 ½3 x3 − 1 − φ3 · x6 = 0
½4 ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ x = (n) ½4 ð1 − ζ 1 Þx1 − x4 = 0
α2 x = (n) α2
½5 ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 · x = (n) ½5 ζ 1 · x1 − x2 + x5 = 0
α1 α1
α3 α3
½6 ðn3 Þ3 = ðn3 Þ2 − ðn1 Þ2 · ζ 1 · ½6 ζ 1 · x1 − x3 + x6 = 0
α1 α1

To solve the linear equations, proceed in the same way as Example 3.5. The nonlinear equation
will be solved by applying the Solver function (see Appendix C), for which a spreadsheet must
be prepared where the objective function will be the difference between the real value of K and
the value obtained in the iteration of the calculation as a function of the degree of conversion
(Figure 3.15).
When considering the function “Solver” it will be specified:
– Target cell: K61
– With a value of 0
– Changing cells: C50
– Restrictions: C50 ≥ 0 and C50 ≤ 1

Automatically the result of the problem will be obtained, with the degree of conversion in equilib-
rium of 0.8737.
 A B C D E F G H I J K L M
80

35 Solution:
36
37 mol/h yi
38 Legend N2: 14.38 0.2334
39 Data H2: 43.13 0.7003
40 Calculations NH3: 4.08 0.0662
41 Solution Total: 61.59 1.0000
42
43 Process parameters
44 ȹ1= 0.005 5
45 ȹ 2= 0.005
46 ȹ3= 0.980 cw
47 r= 0.154 mol/h yi
48 N2: 0.07 0.0004
49 Reaction data H2: 0.22 0.0011
50 Degree of conversion: 0.8737 NH3: 199.86 0.9986
51 3 V–101 Total: 200.14 1.0000
K= 0.05 E–104
52 N2: k=1 –1
53 H2: j=2 –3 4
54 NH3: j=3 2
55 P–101A/B
56
57 N (g) + 3H2(g) ⇆ 2NH (g) mol/h yi Conditions of the equilibrium
2 3
3 Balances in systems with chemical reaction

58 N2: 14.45 0.0552 P= 220 atm

59 H2: 43.35 0.1656 InK = –2.9957E+00
60 NH3: 203.93 0.7792 Function objective
61 Total: 261.74 1.0000 f(ζeq)= –4.3517E-07
62
63 mol/h yi R–101
64 N2: 100.00 0.2500 mol/h yi
65 H2: 300.00 0.7500 1 2 N 2: 114.38 0.2478
66 Total: 400.00 1.0000 H 2: 343.13 0.7434
67 NH3: 4.08 0.0088
68 Total: 461.59 1.0000
69

Figure 3.15: Spreadsheet for combined resolution of matter balances with chemical reaction and equilibrium condition.
 3.2 Chemical equilibrium in systems with chemical reactions 81

Example 3.10: H2 is typically produced by reforming natural gas with steam over a catalyst at atmo-
spheric pressure in the range of 700–1,000 °C:

CH4ðgÞ + H2 Oðv Þ ! COðgÞ + 3H2ðgÞ

COðgÞ + H2 Oðv Þ ! CO2ðgÞ + H2ðgÞ

Calculate the degree of conversion in the equilibrium as well as the mole fraction of each compo-
nent with a feed of 6 mol/h of CH4 and 5 mol/h of H2O. The value of the equilibrium constant under
these conditions is 0.54 and 2.49 for the first and second reaction, respectively.

Solution:
Step 1: Flowchart with identification of data
The flow diagram is identical to Example 3.5, except that two reactions take place in the unit.
If we call A1 ≡ CH4, A2 ≡ H2O, A3 ≡ CO, A4 ≡ H2, A5 ≡ CO2, the direct reactions can be ex-
pressed as
3A4 + A3 − A2 − A1 = 0
A5 + A4 − A3 − A2 = 0
In the equilibrium eq. (3.33) should be verified for reaction A and B:

ln KA = ½α1 lnðy1 · PÞ + α2 lnðy2 · PÞ + α3 lnðy3 · PÞ + α4 lnðy4 · PÞA

ln KB = ½α2 lnðy2 · PÞ + α3 lnðy3 · PÞ + α4 lnðy4 · PÞ + α5 lnðy5 · PÞB
Step 2: Basis of calculations
The calculation basis will be the feed flow rates (n1)1 = 6 mol/h and (n2)2 = 5 mol/h.
Step 3: Definition of control volumes and formulation of the mass balances
In this case, the only control volume is the unit where the mass balances with chemical reaction
are raised, which corresponds to the molar conversion application, eq. (3.19), for each of the reac-
tion components.

Step 4: Solving the system of equations

Therefore, it is a question of solving two nonlinear equations (equilibrium condition) as a function of
the molar conversion that defines the molar fractions obtained from the mass balance with chemical
reaction. This nonlinear equation will be solved by applying the Solver function (see Appendix E), for
which a spreadsheet should be developed where the objective function will be the difference be-
tween the actual value of K and the value obtained in the iteration of the calculation as a function of
the molar conversion (Figure 3.16).
When considering the function “Solver” it will be specified:
– Target cell: J39
– With a value of 0
– Changing cells: H34:H35
– Restrictions: H34 ≥ 0 and H35 ≥ 0

Automatically the result of the problem will be obtained, being the molar conversions in equilib-
rium 2.4219 and 0.8422.

Questions/simulations:
i. Importance of initial values for iteration: A higher molar conversion of the main reaction than the
secondary reaction is considered. A first set of values would be (0.8 and 0.2). The result is not
 A B C D E F G H I J K
82

17 Solution:
18 Legend
19 Data
20 Calculations mol/h yi
21 Solution CH4: 3.578 0.2258
22 H2O: 1.736 0.1096
2
23 CO: 1.580 0.0997
24 8.108 0.5117
CH4(g) + H2O(v) ⇆ CO(g) + 3H2(g) H2:
25 Co(g) + H2O(v) ⇆ CO2(g) + H2(g) CO2: 0.842 0.0532
26 Total: 15.844 1.0000
27
28 Reaction data (A):
29 KA = 0.54
30 Code Stoichiometric coef.
31 CH4: j=1 –1
32 H2O: j=2 –1 Conditions of the equilibrium
33 CO: j=3 1 (Molar conversion) P= 1.0 atm
34 H2: j=4 3 x A= 2.4219 InKA = –6.1611E–01
35 x B= 0.8422 InKB = 9.1234E–01
36 Reaction data (B): Function objective
3 Balances in systems with chemical reaction

37 KB = 2.49 f1(X)= –7.4767E–05

38 Code Stoichiometric coef. f2(X)= –5.7446E–05
39 CO: j=3 –1 8.8901E–09
40 H2O: j=2 –1
41 CO2: j=5 1
42 H2: j=4 1
43
44 CH 4: 6.0 mol/h
1
45
46 mol/h
47 H2O: 5.0 2
48
49

Figure 3.16: Calculation of equilibrium conditions.

 3.2 Chemical equilibrium in systems with chemical reactions 83

valid as it leads to negative values of the water molar fraction. However, if the initial set is (1.0 and
0.2), the correct value of the equilibrium molar conversion and the composition in it is obtained.

mol/h yi
CH4: 2.000 0.1053
H4O: –1.204 –0.0634
CO: 1.796 0.0945
H 2: 14.204 0.7476
CO2: 2.204 0.1160
Total: 19.000 1.0000

ii. Extensive nature of molar conversion: The molar conversion is an extensive property; it depends
on the mass. Thus, if the amount at the reactor inlet is 60 and 50 moles for methane and water
vapor, respectively, using Solver with the initial values obtained with a previous feed leads us
to the calculation of xA = 24.2194 and xB = 8.4218, but the mole fraction of the components in
the equilibrium will not vary, since the equilibrium constant does not depend on X.

3.2.2 Acid–base reactions

If the reaction takes place in an aqueous phase, the value of the activities of most
chemical species can be considered approximately equal to the value of the concen-
trations; therefore, the expression for the equilibrium constant (eq. 3.26) would be
expressed as follows:

aA + bB ! cC + dD

acC · adD ½Cc · ½Dd

K= ffi (3:34)
aaA · abB ½ Aa · ½Bb

A specific case of chemical equilibrium of reactions in aqueous phase corresponds

to acid–base reactions. The dissociation or ionization constant is the equilibrium
constant that refers to the process of dissociation into ions that many molecules
suffer when dissolved in water. In acid–base reactions it is denoted by Ka, so that,
for example, for acetic acid:

CH3 COOH ! CH3 COO − + H +

½CH3 COO − ½H + 
Ka = (3:35)
½CH3 COOH

Due to the high values of Ka the acidity constant is usually expressed by a logarith-
mic measure of the acidity constant, pKa, such that

pKa = − log Ka , Ka = 10 − pKa (3:36)

84 3 Balances in systems with chemical reaction

The higher the pKa value (Table 3.1), the smaller the extent of dissociation. Acids
with pKa values less than −2 are said to be strong acids; a strong acid is almost
completely dissociated in aqueous solution to the extent that the concentration of
the undissociated acid is undetectable.

Table 3.1: pKa values for various acids.

Acid Formula pKa pKa pKa

Nitric acid HNO −.

Hydrochloric acid HCl <
Sulfuric acid HSO < .
Phosphoric acid HPO . . .
Arsenic acid HAsO . .
Citric acid CHOH(COOH) . . .
Acetic acid CHCOOH .
Carbonic acid HCO . .
Hydrogen sulfide HS . .
Hypochlorous acid HOCl .
Ammonium ion NH+ .
Silicic acid HSiO . .

Polyprotic acids are acids that can lose more than one proton. The dissociation con-
stant for the first proton can be indicated as Ka1, the dissociation constants of suc-
cessive protons as Ka2 and so on. Phosphoric acid, H3PO4, is an example of
polyprostide acid that can lose three protons:

H3 PO4 ! H2 PO4− + H + pKa = .

H2 PO4− ! HPO4− 2 + H + pKa = .
HPO4− 2 ! PO4− 3 + H + pKa = .

The basicity constant or the ionization constant of the base can be established in
the same way as the bases:

BðacÞ + H2 OðlÞ ! BH ð+acÞ + OHð−acÞ

½BH +  · ½OH − 
Kb = (3:37a)
½B

pKb = − log Kb (3:37b)

Weak bases have small Kb values (<1) for example, ammonia (NH3), ethylamine
(C2H5NH2) and aniline (C6H6NH2).
The relationship between the acidity and basicity constant of a conjugated
acid–base is equal to the ionization product or water ionization constant:
 3.2 Chemical equilibrium in systems with chemical reactions 85

Ka · Kb = Kw = 10 − 14 (3:38)

It is defined as the degree of ionization or dissociation (αa/b) as the relationship be-

tween the concentration of the ionized species in the state of equilibrium and the
concentration of the species without ionizing:

½A −  ½BH + 
αa = , αb = (3:39)
½AH0 ½B0

Example 3.11: The concentration of CO2 in the atmosphere before the Industrial Revolution was
275 ppm.9 If the accumulation of CO2 in the atmosphere continues at the rate of the first decade
of the twenty-first century, according to data from the Mauna Loa10 Observatory, by the middle of
this century it will be close to 500 ppm.11 Calculate the pH of rainwater (neglect the effects of any
other gas) at 25 °C before the Industrial Revolution and its possible value in the middle of this
century. Note: Henry’s constant value for CO2 is 0.033363 mol/L atm and the water dissociation
constant 25 °C is 10−14.

Solution:
Step 1: Flowchart with identification of data

CO2

T = 25°C
P = 1 atm
KW = 10–14 a 25°C
pKa1 = 6.35 (Table 3.1)
KH = 0.033363 mol/L atm

9 IPCC – Intergovernmental Panel on Climate Change: www.ipcc.ch.

10 http://www.esrl.noaa.gov/gmd/obop/mlo/
11 The twitter account @CO2_earth follows the world’s latest data on atmospheric CO2, almost in
real time. An example of tweet.
86 3 Balances in systems with chemical reaction

Step 2: Basis of calculations

The calculation base corresponds to the concentration of CO2 in the atmosphere before the indus-
trial revolution (275 ppm) and the forecast for the middle of the twenty-first century (500 ppm).
Step 3: Definition of control volumes and formulation of the mass balances.
Two simultaneous processes occur in the water drop: (i) water dissociation and CO2 dissolution.

(i) water decoupling (ii) CO decoupling

H2 O ! H + + OH − CO2ðaqÞ + H2 O ! H2 CO3 ! H + + HCO3−
HCO3− ! H + + CO3− 2

If you consider load neutrality in raindrops, you must comply that

½H +  = HCO3− + 2 CO3− 2 + ½OH − 

where the coefficient “2” that multiplies the concentration of the carbonate ion is due to the fact
that it has two negative charges per mole. However, since rain has a slightly acidic pH, the balance
is displaced to the formation of bicarbonate ion; therefore,

½H +  = HCO3− + ½OH − 
If the concentration of OH− is defined as a function of the water dissociation constant:

KW = ½H + ½OH −  ) ½H +  = HCO3− +
KW
½H + 

 1=2
½H +  = ½H +  HCO3− + KW
The concentration of bicarbonate ion can be expressed as a function of the equilibrium constant
Ka1 corresponding to the dissolution of CO2:

½H +  HCO3−  h i 1=2
Ka1 = 10 − pKa1 = h i ) ½H +  = Ka1 CO2ðaqÞ + KW
CO2ðaqÞ

Henry’s law relates the partial pressure of CO2 in the gas phase to its concentration in the liquid
phase (eq. (2.21)):
h i  1=2
pCO2 = KH · CO2ðaqÞ ) ½H +  = Ka1 · KH · pCO2 + KW

Step 4: Solving the system of equations

This problem is about solving an equation with an unknown, the concentration of CO2 in the atmo-
sphere (Figure 3.17), where the partial pressure of CO2 can be calculated from the concentration by
applying Dalton’s Law:

pCO2 = P · xCO2 = cCO2 · 10 − 6

First row:
B49: = A49*10^−6
C49: = ($C$42*$C$43*B49 + $C$40)^0,5
D49: = −1*LOG10(C49)
 A B C D E F G H I
37 4) Solving the equations
38
39
PCO2 = PT . xCO2 = CCO2.10–6
40 Kw 1.00E–14
41 pKa1 6.35
42 Ka 4.47E–07 [H+] = (Ka[KH . PCO2] + KW)½
43 KH 0.033363 mol/L atm
44 pH = –log[H+]
45
46
47 CO2 (aq) pCO2 [H+] pH 6.00
48 (mg/L) atm (mol/L)
49 250.0 2.50E–04 1.933E–06 5.71
50 275.0 2.75E–04 2.027E–06 5.69 5.75
51 300.0 3.00E–04 2.117E–06 5.67
52 325.0 3.25E–04 2.203E–06 5.66
pH 5.50
53 350.0 3.50E–04 2.286E–06 5.64
54 375.0 3.75E–04 2.366E–06 5.63
55 400.0 4.00E–04 2.444E–06 5.61 5.25
56 425.0 4.25E–04 2.519E–06 5.60
57 450.0 4.50E–04 2.592E–06 5.59
58 475.0 4.75E–04 2.662E–06 5.57 5.00
250 300 350 400 450 500
59 500.0 5.00E–04 2.732E–06 5.56
60 [CO2(aq)] (ppm)
61
62

Figure 3.17: Evolution of the pH of rainwater as a function of the concentration of CO2.

3.2 Chemical equilibrium in systems with chemical reactions
87
88 3 Balances in systems with chemical reaction

The rest of the rows are obtained with the “copy” and “paste” functions. The result does not indi-
cate that the pH would be reduced from 5.69 to 5.56, when a CO2 concentration of 500 ppm is
reached in the atmosphere.

Example 3.12: Water is usually disinfected with chlorine gas, forming hypochlorous acid (HOCl),
which is partially ionized to form ions of hydrogen and hypochlorite. The amount of HOCl depends
on the pH. Calculate:
a. The portion of hypochlorous acid as a function of pH.
b. Which portion would be hypochlorous acid for a pH of 6 and 10?
c. At what pH should water be maintained so that at least 95% of the added chlorine is in the
form of hypochlorous acid?

Solution:
Step 1: Scheme of the process and data representation

T = 25°C
P = 1 atm
Pka1 = 7.6 (Table 3.1)

HOCl ⇆ OCl– + H+

Step 2: Basis of calculations

The calculation basis corresponds to the pH, which will be the independent variable from which the
portion of hyplochloric acid in the wastewater will be established.

Step 3: Definition of control volumes and formulation of the mass balances

The fraction of hypochlorous acid in the system is defined as

½HOCl 1
α½HOCl = =
½HOCl + ½OCl −  1 + ½OCl − =½HOCl
The quotient between ion concentration and acid can be expressed as a function of the dissociation
constant:
½OCl − ½H +  ½OCl −  Ka 10 − pKa
Ka = 10 − pKa = ) = =
½HOCl ½HOCl ½H +  ½H + 

Taking into account the definition of pH:

½OCl −  10 − pKa
pH = − log½H +  ) = = 10ðpH − pKa Þ
½HOCl 10 − pH
½H +  = 10 − pH
Consequently, the fraction of hypochlorous acid as a function of pH and pKa:

1
α½HOCl =
1 + 10ðpH − pKa Þ
 3.2 Chemical equilibrium in systems with chemical reactions 89

Step 4: Solving the system of equations

This problem is about solving an equation with an unknown, the fraction of hypochlorous acid
(Figure 3.18), which decreases as the pH increases, that is, to basic pH.

A B C D E F G H I
38
39 1
40 α[HOCl] =
41
1+10( pH − pKa) 1.0
42
43 pH αNH3 αNH3(%)
0.8
44 4.0 9.997E-01 99.97
45 5.0 9.975E-01 99.75
0.6
46 6.0 9.755E-01 97.55

α(NH3)
47 7.0 7.992E-01 79.92
0.4
48 8.0 2.847E-01 28.47
49 9.0 3.829E-02 3.83
50 10.0 3.965E-03 0.40 0.2
51 11.0 3.979E-04 0.04
52 0.0
12.0 3.981E-05 0.00
53 4 5 6 7 8 9 10 11 12
54 pH
55
56

Figure 3.18: Portion of hypochlorous acid as a function of pH.

First row:
C44: = 1/(1 + 10^(B44-$C$20)) [In cell C20, which is expressed as absolute direction, the
value of the dissociation constant is indicated]
D44: = C44*100

The rest of the rows are obtained with the “copy” and “paste” functions. The value of the hypochlo-
rous acid fraction for pH 6 and 10 is 97.55 and 0.40%, respectively.
If we consider the pH as a dependent variable and the fraction as an independent variable
(Figure 3.19), we obtain that the pH necessary for the fraction to be 95% is 6.32:
0 1
1 @ 10 − pKa A
α½HOCl = ) pH = − log
1 + 10ðpH − pKa Þ α
1 −1
½HOCl

3.2.3 Solubility product

The solubility product (Kps) of a compound is the product of the molar (equilibrium)
concentrations of the constituent ions, each elevated to the potency of the stoichio-
metric coefficient in the equilibrium equation:
Aa Bb ! aA + bB

Kps = ½ Aa ½Bb (3:40)

90 3 Balances in systems with chemical reaction

A B C D E F G H
69
70 αNH3 pH 8.0
71 90.0 6.65 7.5
72 91.0 6.60
73 92.0 6.54 7.0
74 93.0 6.48

pH
75 94.0 6.41 6.5
76 95.0 6.32 6.0
77 96.0 6.22
78 97.0 6.09 5.5
79 98.0 5.91
80 5.0
81 90 92 94 96 98
82
83 Fraction (%)
84
85

Figure 3.19: Portion of hypochlorous acid as a function of pH.

The value of Kps indicates the solubility of a compound, and so the lower the value,
the less soluble the compound will be (Table 3.2).

Table 3.2: Solubility product values for various compounds.

Compound Equilibrium equation Kps at  °C

Silver bromide AgBr ! Ag + + Br − .·−

Calcium carbonate CaCO3 ! Ca2 + + CO23 − .·−
Zinc carbonate ZnCO3 ! Zn2 + + CO23 − .·−
Silver chloride AgCl ! Ag + + Cl − .·−
Calcium fluoride CaF2 ! Ca2 + + 2F − .·−
Aluminum phosphate AlPO3 ! Al3 + + PO34 − .·−
Aluminum hydroxide AlðOHÞ3 ! Al3 + + 3OH − .·−
Calcium hydroxide CaðOHÞ2 ! Ca2 + + 2OH − .·−
Iron (III) hydroxide FeðOHÞ3 ! Fe3 + + 3OH − .·−
Lead (II) hydroxide PbðOHÞ2 ! Pb2 + + 2OH − .·−
Barium sulfate BaSO4 ! Ba2 + + SO24 − .·−
Calcium sulfate CaSO4 ! Ca2 + + SO24 − .·−
Calcium sulfate PbSO4 ! Pb2 + + SO24 − .·−
Silver iodide AgI ! Ag + + I − .·−

Table 3.3 lists different expressions between the solubility and the solubility prod-
uct of a compound, depending on its empirical formula.
The solubility product plays an important role in precipitation reactions, which
occur when dissolutions of soluble salts are mixed to form an insoluble product
called precipitate. Fractionated precipitation consists of adding an ion that forms
 3.3 Kinetic aspects: reaction rate 91

Table 3.3: Relationship between solubility and solubility product.

Type of compound Example Expression of Kps

AB NiSðsÞ ! Ni2ðac+ Þ + S2ðac− Þ Kps = Ni2 + S2 − = s · s = s2

AB Ag2 SO4ðacÞ ! 2Agð+acÞ + SO24ð−acÞ Kps = ½Ag + 2 SO24 − = ð2sÞ2 · s = 4s3

MgðOHÞ2ðacÞ ! Mg2ðac+ Þ + 2OHð−acÞ

2
AB Kps = ½Mg2 +  OH − = s · ð2sÞ2 = 4s3

FeðOHÞ3ðacÞ ! Fe3ðac+ Þ + 3OHð−acÞ

3
AB Kps = ½Fe3 +  OH − = s · ð3sÞ3 = 27s4

insoluble salts with two or more ions between those present in the solution. For se-
lective precipitation to occur, Kps values must have sufficiently different values.

3.3 Kinetic aspects: reaction rate

The stoichiometric equation tells us in what proportion the reactants intervene in a

given process. On the other hand, the reaction may have a greater or lesser degree
of conversion, depending on the thermodynamics of the process and the time in
which the reactants are kept in contact under favorable reaction conditions. In
these cases, it is necessary to know the reaction time to obtain the determined con-
version; once the thermodynamic data are known, we need information about the
rate of the reaction and about the effects that modify it. This is the subject of chemi-
cal kinetics.
Thus, the term generation will depend on the rate of intensive reaction, which
is defined for a component Aj (reactant or product) as the “number of moles” of
that species that react (disappear or form) per unit of time and per unit of volume.
The general expression of the kinetic equation:

Gi = ri · V
1 dNi dCi
ri = − =−
V dt dt

3.3.1 Integrated equations of reaction rate

Order 0
The rate of the reaction does not depend on the concentration; it is equal to the
kinetic coefficient, k:
92 3 Balances in systems with chemical reaction

ðC ðt
dC
r= − = k ) dC = − kdt ) dC = − k dt
dt C0 o

therefore,

C = C0 − k · t (3:41)

The mean time is defined as the time in which the concentration is half of the initial
one:

C0 C0
C= ) t1=2 = (3:42)
2 2·k

Order 1
The reaction rate is directly proportional to the concentration, r = kC:

C
ln = −k·t o C = C0 · e − k · t (3:43)
C0

The expression for the mean time for a reaction of order 1:

ln 2
t1=2 = (3:44)
k

Order 2
The reaction rate is directly proportional to the square of the concentration, r = kC2:
1 1
= +k·t (3:45)
C C0

The expression for the mean time for a reaction of order 2:

1
t1=2 = (3:46)
k · C0

Figure 3.20 represents the relationship between concentration and time by reaction
order, that is, eqs. (3.41), (3.43) and (3.45).

C 1
C ln
C0 C0
C0

1 k
–k –
k 1
C0

Figure 3.20: Representation of concentration versus time for reactions of order 0, 1 and 2.
 3.3 Kinetic aspects: reaction rate 93

3.3.2 Factors influencing reaction rate

3.3.2.1 Temperature
An increase in temperature (Figure 3.21) leads to an increase in reaction rate. The
Arrhenius12 equation relates the value of the kinetic coefficient to temperature (3.47):
Ea Ea
k = A · e − RT o ln k = ln A − (3:47)
RT

– where k, kinetic coefficient;

– A, factor that takes into account the frequency of collisions;
– Ea, activation energy (J/mol);
– R, constant of ideal gases (8.31 J/K mol);
– T, temperature (K).

Ln k
Ea1 > Ea2 > Ea3
Ln A
Ea3
E Ea2
– a1
R

1/T Figure 3.21: Representation of the Arrhenius equation.

For two given temperatures T1 and T2 of the same reaction, the relationship between
their kinetic coefficients verifies that

k2 Ea 1 1
ln = − (3:48)
k1 R T1 T2

3.3.2.2 Catalysts
Catalysts are substances that modify the rate of a chemical reaction without being
consumed during it (Figure 3.22). Positive catalysts reduce the activation energy
and, therefore, increase the reaction rate. Negative catalysts (or inhibitors) increase
the activation energy, thus slowing down the reaction rate.
Catalysis is defined as homogeneous when the reactants and the catalyst are in
the same phase, and as heterogeneous if the reactants are in one phase (gaseous or
liquid) and the catalyst in another phase (normally solid).

12 Svante August Arrhenius (1859–1927): Swedish chemist.

94 3 Balances in systems with chemical reaction

Energy
(kJ) Ea original

Ea c < Ea o

Reagents Ea catalysis

Products
Figure 3.22: Energy diagram for a reaction with
Advance of the reaction and without the presence of a catalyst.

For example, Fenton catalysis is a well-known and very good representative of

homogeneous catalysis, which has been shown to be more efficient in terms of oper-
ating costs for the degradation of a wide range of organic compounds at low and
high concentrations. The Fenton reaction starts with an electron transfer process, in
which ferrous iron (Fe2+) reacts with hydrogen peroxide (H2O2) to form ·OH (eq. 3.49),
so that it oxidizes organic matter, ideally resulting in complete mineralization to car-
bon dioxide (CO2) and water (H2O). The ferric iron (Fe3+) is then reduced to Fe2+ by
H2O2, forming a hydroperoxyl radical (·OOH) (eq. 3.50).

Fe2 + + H2 O2 ! Fe3 + + OH + H + (3:49)

Fe3 + + H2 O2 ! Fe2 + + OOH + H + (3:50)

However, the conventional Fenton process has major drawbacks, the most notable
being the impossibility of viable separation of the homogeneous catalyst (Fe2+) from
the treated effluent and, therefore, the need for treatment of the ferric hydroxide
sludge produced. In this context, the cost associated with posttreatment can represent
up to 50% of the total operating costs. To overcome these impediments, we can use
the heterogeneous Fenton approach, using catalysts in solid phase that can be easily
separated from the effiuent. However, heterogeneous catalysts have only a small frac-
tion of iron on their surface, presenting slower reaction kinetics and mass transfer lim-
itations compared to homogeneous catalysts. The link between heterogeneous and
homogeneous catalysts can be accomplished using nanostructured materials.

Example 3.13: The following equation is used to calculate the level of oxygen (mg/L) in a river
below the discharge of a drain:
 
½O2  = 10 − 20 e − 0.15 · x − e − 0.5 · x
where x is the distance downstream in kilometers. Calculate:
a. The distance below the stream at which the oxygen level falls to a reading of 5 mg/L, at which
detrimental effects are produced for certain species such as trout and salmon.
b. The distance downstream at which oxygen is at a minimum. What is the concentration at that
location?
 3.3 Kinetic aspects: reaction rate 95

Solution:
The representation of the dissolved oxygen concentration (O2) with the distance (x)

12.0
10.0
8.0
[O2] (mg/L) 6.0
4.0
2.0 [O2]x = [O2]initial – a. (e–b.x – e–c.x)
0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0

x (km)

The distance in the river at which a value of 5 mg/L of oxygen will be observed can be obtained by
solving the nonlinear equation by applying the Newton–Raphson method (see Appendix C). To do
this, the derivative of the target function must be calculated:
 
f ð x Þ = ½O2 initial − a e − b · x − e − c · x − ½O2 x

df ð x Þ h i
= − a − b · e − bx + c · e − c · x
dx

where parameters [O2]initial, a, b and c are known parameters. The initial value of the iteration
would correspond to 0.1 (cell C53). The table for calculating the solution using Newton–Raphson is
shown in Figure 3.23. By introducing six significant figures, convergence is obtained from the five
iteration, with a value of 0.97623 km, that is, 976.2 m.
To obtain the distance at which the oxygen concentration will have a minimum value, the
Solver function (See Appendix D) is applied by entering as the target cell value the search for a
minimum. The results obtained are 1.643 mg/L at a distance of 3.44 km.

3.3.3 Application to Metabolic Engineering

Metabolic Engineering comprises a series of methodologies belonging to diverse dis-

ciplines that could be defined as the rational and directed improvement of the forma-
tion of a product, or a cellular property, through the modification of biochemical
reactions proper to the microorganism or the introduction of new biosynthetic routes.
Metabolic flow analysis (MFA) has become, since the 1990s, one of the most relevant
tools of Metabolic Engineering, which consists of defining the stoichiometry of each
of the most important reactions of a given metabolic network for the estimation of
flows by means of the corresponding mass balances. The first metabolic networks
consisted of 30–40 reactions, which, with the introduction of genomic aspects, in-
volve the handling of thousands of equations, but always under the same principle.
If one considers the metabolic network constituted by the biochemical reactions
indicated in Figure 3.24, the concentration of all metabolites and the flows through
all reactions can be represented by the following eight differential equations:
96 3 Balances in systems with chemical reaction

A B C D E F G H
50 Step 3: Introduction of Newton-Raphson's formula
51
Iteration (k) xK–1 f(xK–1) df(xK–1)/dx xK f(xk) εa(%)
52
53 1 0.10000 4.32E+00 –6.56E+00 0.75920 8.35E–01 8.68E+01
54 2 0.75920 8.35E–01 –4.16E+00 0.95981 5.86E–02 2.09E+01
55 3 0.95981 5.86E–02 –3.59E+00 0.97613 3.59E–04 1.67E+00
56 4 0.97613 3.59E–04 –3.55E+00 0.97623 1.37E–08 1.04E–02
57 5 0.97623 1.37E–08 –3.55E+00 0.97623 0.00E+00 3.96E–07
58 6 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
59 7 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
60 8 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
61 9 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
62 10 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
63 11 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
64 12 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
65 13 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
66 14 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00
67 15 0.97623 0.00E+00 –3.55E+00 0.97623 0.00E+00 0.00E+00

Figure 3.23: Application of the Newton–Raphson method for the calculation of the oxygen
concentration.

v7 A
R1 : A→B
v1
H R2 : B→C
B v2 R3 : C→F
v6 R4 : C→D
v3
E C F R5 : D+G →E
v5 R6 : E →B
D v4 R7 : E+H →A
G

Figure 3.24: Example of a metabolic network and its corresponding biochemical reactions.
Symbols: A, B and so on represent metabolites; vn represents metabolic fluxes or reaction rates.

d½ A d½ E 
= v7 − v1 = v5 − v6 − v7
dt dt
d½B d½ F 
= v1 − v2 + v6 = v3
dt dt
d½C d½G
= v2 − v3 − v4 = − v5
dt dt
d½D d½ H 
= v4 − v5 = − v7
dt dt
 3.3 Kinetic aspects: reaction rate 97

The solution of this system of differential equations implies knowing the relationship
between metabolic fluxes or reaction rates (v1, v2, . . . , vn) and the kinetic parameters
of the enzymes involved and the concentrations of the metabolites. The AFM applies
the steady-state principle, that is, it assumes that the concentrations of metabolites
in a biological system remain practically constant over time, and thus d[C]/dt = 0.
Mathematically, the problem is transformed from a system of differential equations
to a system of linear equations, which in its matrix form is represented as a function
of the stoichiometric coefficients of the reactions of the metabolic network.

R1 R2 R3 R4 R5 R6 R7 R1 R2 R3 R4 R5 R6 R7

d[A]/dt –v1 0 0 0 0 0 v7 A –1 0 0 0 0 0 1 0
V1
d[B]/dt v1 –v2 0 0 0 v6 0 B 1 –1 0 0 0 1 0 0
V2
d[C]/dt 0 v2 –v3 –v4 0 0 0 C 0 1 –1 –1 0 0 0 0
V3
d[D]/dt 0 0 0 v4 –v5 0 0 D 0 0 0 1 –1 0 0 0

d[E]/dt
= 0 0 0 0 v5 –v6 –v7
= V4 = 0
E 0 0 0 0 1 –1 –1
V5
d[F]/dt 0 0 v3 0 0 0 0 F 0 0 1 0 0 0 0 0
V6
d[G]/dt 0 0 0 0 –v5 0 0 G 0 0 0 0 –1 0 0 0
V7
d[H]/dt 0 0 0 0 0 0 –v7 H 0 0 0 0 0 0 –1 0

In general terms, the representation of the system to solve is:

S·!
v =0 (3:51)

where S is the stoichiometric matrix m x n, normally being m > n and therefore an

indeterminate system. Conversion to a given (m = n) or supradetermined (m < n) sys-
tem is achieved by incorporating thermodynamic and/or biological restrictions.
Restrictions can be divided into two groups: those that group metabolite intake and
excretion and those that limit flow through metabolic reactions in the system.
The incorporation of these restrictions allows transforming the system defined
by eq. (3.51) into a certain system (m = n) called metabolic balance equation, which
could be expressed as follows:

S·!
v =B (3:52)

where B is the matrix (1 x n) that includes both the reaction rates of measurable
fluxes and those corresponding to the metabolites in steady state. The positive val-
ues of r correspond to production and the negative values to consumption:
!
r
B=
0
98 3 Balances in systems with chemical reaction

Example 3.14: Calculate the reaction rates or metabolic fluxes of the following metabolic pathway,
taking into account that rs = −1 mmol/L min, rp1 = 0.3, rp2 = 0.5.

v5 P2
v1 v2 v4
S M1 M2 M3
v3
v6
P1 P3

Solution:
The reactions that define the metabolic pathway are as follows:

R1 : S ! M1 R4 : M2 ! M3
R2 : M1 ! M2 R5 : M3 ! P2
R3 : M2 ! P1 R6 : M3 ! P3

The matrix equation that defines the metabolic path implies a system of seven equations with six
unknowns (v1, v2, v3, v4, v5, v6), where three of the metabolites are M1, M2 and M3 and the steady-
state condition applies to them.

R1 R2 R3 R4 R5 R6

d[S]/dt –v1 0 0 0 0 0 –1 0 0 0 0 0 0
V1 rS
d[M1]/dt v1 –v2 0 0 0 0 1 –1 0 0 0 0 0
V2 0
d[M2]/dt 0 v2 –v3 –v4 0 0 0 1 –1 –1 0 0 0
V3 0
d[M3]/dt = 0 0 0 v4 –v5 –v6 = 0 0 0 0 1 –1 –1 = 0
V4
d[P1]/dt 0 0 v3 0 0 0 0 0 1 0 0 0 0
V5 rP1
d[P2]/dt 0 0 0 0 v5 0 0 0 0 0 0 1 0
V6 rP2
d[P3]/dt 0 0 0 0 0 v6 0 0 0 0 0 0 –11 rP3

The system has three degrees of freedom and therefore three restrictions need to be known. In this
case, the experimental data correspond to the consumption of substrate, S, and the production of
two products: P1 and P2. Thus, the metabolic balance equation (3.48) would be formed by the fol-
lowing determined system of six equations with six unknowns:

R1 R2 R3 R4 R5 R6

d[S]/dt –v1 0 0 0 0 0 –1 0 0 0 0 0 0 V1 1.324

d[M1]/dt v1 –v2 0 0 0 0 1 –1 0 0 0 0 0 V2 0

d[M2]/dt 0 v2 –v3 –v4 0 0 0 1 –1 –1 0 0 0 V3 0

= 0 0 0 v4 –v5 –v6
= =
d[M3]/dt 0 0 0 0 1 –1 –1 V4 0

d[P1]/dt 0 0 v3 0 0 0 0 0 1 0 0 0 0 V5 0.386

d[P2]/dt 0 0 0 0 v5 0 0 0 0 0 0 1 0 V6 0.501
 3.4 Proposed problems 99

Applying the inverse matrix method (Appendix D), the result of all metabolic flows can be obtained
(Figure 3.25).

A B C D E F G H I J K L M
1 Balance with chemical reaction: metabolic flow analysis
2
3
4 v5= 0.501 R1 : S → M1
5 v2= 1.324
P2
6 v4= 0.938 R2 : M1 → M2
7
8 S M1 M2 M3 R3 : M2 → P1
9 R4 : M2 → M3
10 v1= 1.324 P3
11 R5 : M3 → P2
12
P1
R6 : M3 → P3
13 v3= 0.386 v6= 0.437
14

Figure 3.25: Result of metabolic flow analysis for the route considered in Example 3.14.

3.4 Proposed problems

3.4.1 Stoichiometry

One reaction
3.1 A process industry discharges 800 m3/d of wastewater consisting of 1,600 ppm
benzene, 2,500 ppm phenol and 3 g/L ethanol. Calculate the number of equiva-
lent inhabitants of a city discharging urban wastewater with the same organic
load. If you choose to install an advanced oxidation system that removes 90%
of benzene and 95% of phenol, what would the equivalent number of inhabi-
tants be now?

Solution: (a) 228.552 h-eq; (b) 94.014 h-eq.

3.2 In a combustion process ammonia is burned to form nitric oxide with 90%
efficiency. Calculate:
(a) Composition of dry-basis combustion gas.
(b) NO moles produced per mole of oxygen consumed.
(c) If the boiler were properly maintained at 92% efficiency, what would be
the new composition of dry-base combustion gases?

Solution: (a) 1.72% NH3, 2.15% O2, 80.69% N2 and 15.44% NO; (b) 0.8;
(c) 1.38% NH3, 1.72% O2, 81.04% N2 and 15.86% NO.
100 3 Balances in systems with chemical reaction

3.3 Chlorine is the most commonly used conventional disinfectant in wastewater

treatment. For economic reasons as well as for reasons of safety in the stor-
age of chlorine gas, a system for producing chlorine gas from hydrochloric
acid and oxygen on site has been installed in an urban waste water treatment
plant. Calculate the composition of the reactor product stream if it is de-
signed to operate with 22% excess air and 72% efficiency:

Solution: 12.32% HCl, 5.50% O2, 50.49% N2, 15.84% Cl2 and 15.84% H2O.

3.4 The saponification reaction for obtaining soap from glycerin can be repre-
sented by the following reaction:

3NaOH + ðC17 H35 COOÞ3 C3 H5 ! 3C17 H35 COONa + C3 H5 ðOHÞ3

If the initial mixture consists of a solution of NaOH (10 kmol/m3) and glyceryl
stearate (2.5 kmol/m3), what value will the concentration of glycerin, sodium
hydroxide, sodium stearate and glyceryl stearate have when the conversion
rate, referred to NaOH, is 22%? What would happen if the conversion rate
were 90%?

Solution: 7.80, 1.77, 2.20 and 0.73 kmol/m3 of NaOH, glycerin, soap and stea-
rate, respectively; with the composition of the initial mixture it is not possible
to achieve this degree of conversion, since a negative value of the concentra-
tion in the output stream would be obtained.

3.5 To obtain barium in solution, the natural sulfate, barite, is melted with sodium
carbonate. For this purpose, a quantity of barite (barium sulfate and inert) is
melted with an excess of pure anhydrous sodium carbonate. The analysis of the
resulting mass is as follows: 11.3% BaSO4, 21.35% Na2CO3 and 26.70% Na2SO4.
Calculate:
(a) The degree of conversion of barium sulfate.
(b) The composition of the initial barite.
(c) The percentage of excess sodium carbonate.

Solution: (a) 79.52%; (b) 93.94% of BaSO4 and 6.06% of Inert; (c) 64.74%.

3.6 In a thermal power station, 5,000 tons/day of coal with a sulfur content of 1.2%
are burned. Its combustion generates SO2 (complete conversion), which is re-
moved 85% effectively by a dry gas cleaning system using CaCO3 to give rise to
CaSO4 and CO2. Calculate:
 3.4 Proposed problems 101

(a) The quantity of CaCO3 expressed as kg/Tm of coal.

(b) The daily emission of sulfur dioxide which is finally emitted into the atmo-
sphere (mt/d).
(c) If, as an environmental improvement action, it is decided to change the
raw material to a lignite containing 1.03% S, what would be the daily
emission of SO2?

Solution: (a) 31.90 kg CaCO3/Tm of coal; (b) 18.0 mt/d; (c) 15.5 mt/d.

3.7 The fresh feed of an ammonia synthesis reactor almost always contains small
quantities of nonreactive substances, such as Ar or CH4. These inert materials
do not condense and are therefore recirculated together with N2 and H2, which
are not consumed in the reaction. In order to avoid the concentration of inert
materials in the system, a continuous purge of the recirculation stream is car-
ried out according to the flow diagram:

N3, H2 and 12.5% I N2

5 6 H2
I
V-101
R-101 3
4 NH3

24.75% N2
74.25% H2
1% I 1
2

Figure P3.7

If the step conversion of N2 in the reactor is 25%, calculate:

(a) Global conversion.
(b) Ratio of purged moles per mole of fresh feed.
(c) Ratio of moles entering the reactor per mole of feed.
Solution: (a) 92.92%; (b) 0.08; (c) 4.07.

3.8 Ethylene and oxygen react in a multitubular reactor in the presence of an Ag-
based catalyst. The ethylene oxide corresponds to the only product of the main
reaction that is characterized by its easy dissolution in water, which allows it to
102 3 Balances in systems with chemical reaction

be separated effectively in an absorption column. The ethylene/air ratio in the

fresh feed is 1/10 and the conversion per step in the reactor is 50%.

V-101

8 H2O
R-101 4

T-101
C2H4
1
3
H2O
5
C2H4O
2
O2

Figure P3.8

Calculate:
(a) The overall conversion of the system if 60% of the gases leaving the ab-
sorption column are recirculated.
(b) The composition of the flue gases.
(c) If the catalyst is changed so that the conversion per step is 55%, what
would be the overall conversion?
(d) In addition, if it were decided to increase recirculation to 65% of the gases
leaving the absorption column, what would be the overall conversion?

Solution: (a) 71.4%; (b) C2H4 2.88%, O2 17.55%, N2 79.57%; (c) 75.3%; (d) 77.7%.

3.9 The basic process unit for methanol synthesis (see Example 3.5) works with a
stoichiometric feed of CO and H2 to achieve an overall conversion of 95.2% CO.
All the methanol formed comes out of the system as a product. No more than
1.95% CO and 0.45% H2 leaving the reactor continues in the product stream,
the rest is recycled. Calculate:
(a) Step-by-step conversion.
(b) The recirculation ratio.
(c) The composition of the products.

Solution: (a) 27.89%; (b) 7.88; (c) 4.38% CO, 8.76% H2 and 86.86% methanol.
 3.4 Proposed problems 103

3.10 Nylon is one of the most common polymers used as a fiber, which belongs to
the polyamide group. Nylon 6 is obtained from the monomer, caprolactam,
which is generated from the transposition of the cyclohexanone oxime. This
oxime (C6H10 = NOH) is synthesized by the photochemical reaction of cyclo-
hexane (C6H12) and nitrosyl chloride (NOCl):

C6 H12 + NOCl ! C6 H10 = NOH + HCl

For each mole of cyclohexane, 0.75 moles of NOCl and 0.15 moles of N2 enter
the system. The reactor conversion is 28% (based on the NOCl entering the re-
actor). The mole fraction of N2 in the recirculation stream must not exceed
0.38, as this would cause process problems.

V-101
5

7 NOCl
2 N2
P-101A/B
1 T-101
C6H12
NOCL
N2

3 C6H12
4 C6H10 = NOH
R-101 HCl

Figure P3.10

Calculate:
(a) The recirculation, purge and product flows per mole of cyclohexane fed.
(b) The molar composition of the product obtained.
(c) The overall conversion of the process to cyclohexane.
(d) Recirculation ratio: n6/n1.
(e) If due to temperature control problems in the reactor the step conversion
in the reactor were reduced to 22%, what would be the overall conversion
and recirculation ratio?

Solution: (a) 1.701, 0.395 and 1.505 mol/h, respectively; (b) C6H12 33.33%,
C6H10 = NOH 33.6%, HCl 33.6%; (c) 50.5%; (d) 0.9; (e) 50.5% and 1.31.
104 3 Balances in systems with chemical reaction

Multiple reactions
3.11 The composition (in volume) of a commercial propane (according to the technical
specifications indicated in the legislation – BOE of the year 2006) is the following:
1% CH4, 82% C3H8, 15% C4H10 and 2% CO2. The above-mentioned propane (with
a flow of 100 mol/h) is used to produce energy by combustion in a boiler, with
30% excess air. Assuming combustion is complete, calculate:
(a) The amount of air used.
(b) The composition of the flue gases on a wet basis.

Solution: (a) 3,154 mol/h; (b) 4.55% O2, 74.19% N2, 9.20% CO2 and 12.06% H2O.

3.12 About 5,000 m3/h, measured under normal conditions, of a dry gas of the
following composition (by volume) are burned in an oven: 50% CH4, 8% C2H6,
12% H2, 10% CO, 5% O2, 10% N2 and 5% CO2. Combustion is carried out with
25% excess enriched air of composition (in volume): 35% O2 and 65% N2. The
air is fed at 1 atm pressure and 112 °C. The combustion products leave the fur-
nace at 1 atm and 1,200 °C, with a CO2 and CO content at a molar ratio of 8/1.
Knowing that there is no H2, CH4 or C2H6 in the flue gas, calculate:
(a) The flow rate of enriched air fed m3/h.
(b) The flow rate of combustion gases produced in m3/h and their composi-
tion on a wet basis.
(c) If the excess enriched air is increased to 40%, the molar ratio of CO2 and
CO is 20/1. What is the conversion value of the initial CO?

Solution: (a) 33,745 m3/h; (b) 153,704 m3/h, 6.61% O2, 56.35% N2; 11.70% CO2,
1.46% CO and 23.87% H2O; (c) 64.3%.

3.13 The combustion of a lignite (elemental analysis: 90% C and 1.5% S) generates
SO2 in the combustion gases (complete conversion). Sulfur dioxide is removed
(95% efficiency) by the addition of magnesite (85% purity in MgCO3) 25% in
excess of that required for stoichiometric conditions. Calculate the kg of mag-
nesite required per ton of coal.

Solution: 58.13 kg/Tm.

3.14 The elimination of hydrogen sulfide from natural gas or biogas is very important,
since this flammable and colorless gas is highly toxic and corrosive, which is a
great disadvantage, as it makes it difficult to move the gas through pipes, its
storage in tanks and other metallic structures.
One of the possible elimination strategies consists of chemical oxidation
by means of oxygen using various catalysts, which allows the transformation
of sulfur into insoluble elemental sulfur that is separated in the liquid phase:
 3.4 Proposed problems 105

2H2 S + 3O2 ! 2SO2 + 2H2 O

2H2 S + SO2 ! 3S + 2H2 O
A biogas containing 3.5% (by weight) of S as H2S needs to be treated prior to
use in a boiler. For this purpose, 0.056 m3 of air (measured under normal con-
ditions) is consumed per m3 of biogas gas in the oxidation process. The average
density of biogas is 0.97 g/L under normal conditions. Consider that in the first
reaction 88% of O2 is converted and in the second 100% of SO2. Calculate:
(a) Quantity of elemental sulfur that can be obtained per m3 of treated gas.
(b) The quantity of H2S that the biogas expressed in mg/m3 will continue to
possess.
(c) If a state-of-the-art catalyst were to be used to obtain a 90.5% conversion in
the first reaction, what would be the concentration of hydrogen sulfide in
the treated biogas?

Solution: (a) 29.57 g S per m3/h; (b) 934.7 mg/m3; (c) 42.2 mg/m3.

3.15 A furnace is fed with pure sulfur and transforms 90% of the charge into oxides
(SO2 and SO3). After oxidation, the gas is introduced to a washing tower where
all the sulfur that did not react, 90% of SO3 and 40% of SO2, is absorbed in
water. An analysis of sulfur in the washing water leads to the conclusion that
10 kg/h of sulfur is separated. If the gases leaving the scrubber have the follow-
ing composition: 83% N2, 4% SO2, 1% SO3 and 12% O2; calculate:
(a) Kilograms of sulfur per hour entering the furnace.
(b) Excess air used necessary to obtain complete combustion of all sulfur
charged into the furnace.

Solution: (a) 13.70 kg/h; (b) 21.2%.

3.16 Formaldehyde (HCHO) is one of the key components in the formulation of ad-
hesives. Most of the formaldehyde currently on the market is obtained from
the oxidation of methanol, but there are numerous lines of work to obtain a
cost-effective route by direct oxidation from methane using a new generation
of catalysts:

CH4 + O2 ! HCHO + H2 O
CH4 + 2O2 ! CO2 + 2H2 O

A number of experiments have been carried out in a pilot installation; the data
for which are given below:
(a) The reactor feed contains equimolar amounts of methane and oxygen, re-
sulting in a global fractional methane conversion of 96%, and a fractional
formaldehyde yield of 92.5%. Calculate the molar composition of the flow
106 3 Balances in systems with chemical reaction

at the outlet of the reactor and the selectivity of formaldehyde production

with respect to carbon dioxide production.
(b) The outflow from the reactor contains (% molar): 46.0% HCHO, 1.5% CO2,
4% CH4 and the rest oxygen and water. To calculate the fractional conver-
sion of methane, the fractional yield of formaldehyde and the selectivity
of formaldehyde production with respect to carbon dioxide production.

Solution: (a) yCH4 = 0.0200, yO2 = 0.0025; yHCHO = 0.4625, yH2O = 0.4975, yCO2 =
0.0175, SHCHO/CO2 = 26.4 mol HCHO/mol CO2; (b) 93.14% methane conversion,
90.2% formaldehyde yield and a selectivity of 30.7 mol HCHO/mol CO2.

3.17 Phosphorus is prepared by heating in an oven a perfectly mixed mass of

Ca3(PO4)2, sand (SiO2) and coal. The amount of SiO2 used is 19.5% in ex-
cess of what is theoretically necessary for the combination with Ca to give
silicate and the carbon is 55.0% in excess of what is theoretically necessary
for the complete reaction of all the P2O5 generated in the obtaining of silicate.
Calculate:
(a) The percentage of composition of the initial load.
(b) The kilograms of P obtained per 100 kg load, assuming that the decompo-
sition of phosphate by silica is 92% and that the reduction of phosphorus
oxide released by carbon is completed by 75%.

Solution: (a) 50.7% Ca3(PO4)2, 35.3% SiO2 and 14.0% C; (b) 7.0 kg P per 100 kg
load.

3.18 A fuel derived from waste (RDF) has the following elemental composition (% by
weight): 87% C, 11% H, 1.4% S and the rest of non-combustible materials.
Calculate:
(a) The composition of the emission gas if the RDF is burned with 20% excess
air. Suppose complete combustion.
(b) The composition of the emission gas if the oil is burned with 20% excess
air and 5% of the carbon forms CO.

Solution: Complete combustion and % excess air

Compound % Wet base

O .
CO .
HO .
SO .
N .
 3.4 Proposed problems 107

Partial combustion and % excess air

Compound % Wet base

O .
CO .
HO .
SO .
N .
CO .

3.19 The elemental analysis of a biodiesel provides the following results: 5% H, 4% S,

65% C, 10% O, 16% inert. Assuming that all biodiesel is burned, calculate:
(a) The composition of the combustion gas if this occurs completely by adding
20% excess air.
(b) The composition of the combustion gas for 20% excess air, if only 80% of C
is oxidized to CO2, with 15% transformed into CO and 5% transformed into
black smoke.

Solution: Complete combustion and % excess air

Compound % Wet base

O .
CO .
HO .
SO .
N .

Partial combustion and % excess air

Compound % Wet base

O .
CO .
HO .
SO .
N .
CO .

3.4.2 Systems in equilibrium

Gas phase chemical equilibrium: a reaction

3.20 The following reversible reaction takes place in a stirred tank reactor:
2A + B ! C
108 3 Balances in systems with chemical reaction

which is characterized by the following equilibrium relationship

cC
K=
c2A· cB

Calculate the intensive conversion under the following conditions: K = 0.021,

cAo = 45 mol/L, cBo = 28.5 mol/L and cCo = 3 mol/L.

Solution: ξ = 17.717.

3.21 The decomposition of 2-propanol results in acetone and hydrogen by the

following reversible reaction:

ðCH3 Þ2 CHOHðgÞ ! ðCH3 Þ2 COðgÞ + H2ðgÞ

The change in free Gibbs energy under standard conditions is 3.05 103 J/mol.
Calculate the equilibrium conversion to 452 K and 0.5 atm pressure if the inlet
is 1 mol/h of 2-propanol.

Solution: 68.6%.

3.22 In the hydrogen economy, the water gas shift reaction (WGS), which allows
additional hydrogen to be obtained from gases from biomass energy recovery
processes such as gasification, has gained much interest. The reaction is re-
versible and exothermic:

COðgÞ + H2 OðgÞ ! H2 ðgÞ + CO2ðgÞ

Callaghan (2006)13 has defined the expression of the equilibrium constant as a

function of temperature for a range of 600–2,000 K:

2, 180.6
log10 Keq = − 2.4198 + 0.0003855 · T +
T

A gas enrichment system from a biomass gasifier consists of a fixed bed reactor
with a Fe/Cr catalyst where the WGS reaction takes place (at 350 °C and 1 atm
pressure) and an adsorption column (PSA) where all the CO2 and a majority of
the CO are separated to obtain a stream with high H2 and CH4 concentrations
that can be used as a substitute for natural gas (Figure P3.22). The reactor feed
stream is 20 Nm3/h wet gas with a dry to wet gas fraction of 0.4. Calculate:
(a) The equilibrium conversion of the WGS reaction.
(b) The CO recovery fraction in R-101.
(c) The dry base concentration of H2 and CH4 in stream 4.

13 https://web.wpi.edu/Pubs/ETD/Available/etd-050406-023806/unrestricted/ccallaghan.pdf
 3.4 Proposed problems 109

2
CO
3
CO2
40.8% H2 25 °C
25.4% CO
22.9% CO2
10.9% CH4

1 350 °C
1 atm
R-101 T-101 H2
4 0.2% CO

Figure P3.22: (The compositions are expressed in % volume on a dry basis.).

Solution: (a) 86.6; (b) 87.0% y (c) 85.5% H2 and 14.3% CH4.

Gas phase chemical equilibrium: multiple reactions

3.23 In high-temperature systems (e.g., volcanoes), there is a balance between the
amount of carbon dioxide and carbon monoxide, as well as the formation of
nitric oxide from oxygen and nitrogen. Calculate the composition of the equi-
librium mixture at 3,000 K and 1 atm if initially the system is composed of
1 kmol of CO2, 0.8 kmol of O2 and 0.5 kmol of N2. Data: KCO2/CO = 0.3273 and
KO2/NO = 0.1222.

Solution: 0.2675 CO2, 0.1448 CO, 0.3655 O2, 0.1900 N2, 0.0322 NO.

3.24 The following reversible reactions take place in an agitated tank reactor:

R1 : 2A + B ! C
R2 : A + D ! C

They are characterized by the following equilibrium relationships:

cC cC
K1 = K2 =
c2A · cB cA · cD

Calculate the intensive conversion under the following conditions: K1 = 3·10−4,

K2 = 3.7·10−2, cAo = 50 mol/L, cBo = 20 mol/L, cCo = 5 mol/L and cDo = 10 mol/L.

Solution: ξ1 = 3.337 and ξ2 = 2.677.

3.25 Ethylene and acetylene can be obtained from the catalytic dehydrogenation of
ethane:
110 3 Balances in systems with chemical reaction

R1 :C2 H6 ! C2 H4 + H2

R2 :C2 H6 ! C2 H2 + 2H2

The reactions develop at 1.160 K and 1 atm, reaching the equilibrium of the
compositions in gas phases:

Equilibrium constants

C2 H6 ! C2 H4 + H2 C2 H6 ! C2 H2 + 2H2

T (K) K (atm) T (K) K (atm)

. . . .

. . . .
. . . .
. . . .
. . . .
. . . .

In order to achieve a higher overall ethane conversion, the unreacted ethane is

recirculated after a separation system where a 95% ethane recovery fraction is
achieved.
For a reactor load of 100 mol/h, calculate:
(a) Conversion in each of the reactions.
(b) Composition at reactor output.

Solution: (a) ξ1 = 82.87 and ξ2 = 6.622; (b) C2H6:0.0536; C2H4: 0.4226; C2H2:
0.0338; H2: 0.4901.

Acid–base reactions
3.26 If ammonia, in the form of NH3 and NH4+, has a total concentration of 7.1·10−4 M
in a wastewater treatment plant. Calculate:
(a) Does it determine whether the nitrogen portion is in the form of ammonia
(and therefore potentially separable by a stripping process) as a function
of pH?
(b) If the pH of the wastewater rises to 10 and the partial pressure of ammonia
in the air is approximately 5·10−10 atm, what would be the equilibrium con-
centration of total nitrogen in the wastewater after the stripping process?
(c) The effectiveness of the stripping process.

Data: Henry’s constant value: log Ha = 0.22.

14 Brickwedde et al. (1946). Journal of Research 37:263–279.

 3.4 Proposed problems 111

Solution: (a) Ammoniacal proportion = 1/(1+10^(pKa-pH)); (b) 3.61·10−8 mol/L;

(c) 99.995%.

3.27 Hydrogen sulfide (H2S) can be separated by stripping by maintaining an adequate

pH in the process stream. Calculate which portion of hydrogen sulfide in the form
of H2S at pH 4.5 and 7.5.

Solution: 99.68 and 23.61%, respectively.

3.28 Calculate the pH of rainwater, assuming that the only one that affects it is the
absorption of atmospheric CO2. Assume that the CO2 concentration is 350 ppm,
and the temperature and pressure are 25 °C and 1 atm. Data: Henry’s law con-
stant for CO2 at 25 °C is 0.033363 mol/L atm.

Solution: 5.64.

3.29 One of the important aspects in the operation of anaerobic digesters, like
most processes that have biological reactions, is the pH. Thus, the acidifica-
tion of an anaerobic digester is one of the most common problems due to the
accumulation of volatile fatty acids generated in the process due to inhibition
of the methanogenic stage (methane formation). For this purpose, it is gener-
ally recommended to maintain an alkalinity value of at least 1.5 g/L CaCO3.
Alkalinity is a measure of the buffer capacity of the system, that is, a mea-
sure of the ability to absorb hydrogen ions produced by an acidification of the
system. This is defined by:

Alkðmol=LÞ = HCO3− + 2 CO23 − + ½OH −  − ½H + 

An anaerobic digester is operated under the following parameters: (i) pH = 7.5;

(ii) T = 25 °C; (iii) total inorganic carbon of 20 mmol/L. Determine whether or
not it is necessary to add bicarbonate to maintain the appropriate safety thresh-
old in alkalinity.

Solution: If bicarbonate needs to be added as the alkalinity is 0.94 mg CaCO3/L.

Solubility product
3.30 A dissolution of 0.15 M in NaCl, 0.10 M in NaBr and 0.22 M in NaI. To selectively
separate the different anions, add AgNO3. Determine:
(a) Which anion will precipitate first? Which second and which third?
(b) How much of the anion that precipitates first will remain in solution when
the second begins to precipitate and how much of the second will remain
when the third begins to precipitate?

Solution: (a) I−>Br−>Cl−; (b) I−: 1.46 10−5 M; Br−: 4.58 10−4 M
112 3 Balances in systems with chemical reaction

3.31 The chemical analysis of a certain water sample determines that each liter con-
tains among other species: 398 mg of calcium ion and 72.4 mg of sulfate ion. It
justifies why no calcium sulfate precipitate was observed in the water sample.
If 350 cm3 of a solution of 0.025 M sodium sulfate were added to 1 L of the
previous solution, would precipitate be observed?

Solution: Yes, precipitation of calcium sulfate would occur.

3.4.3 Kinetic controlled systems

3.32 The concentration of contaminating bacteria c in a lake decreases according to

the equation:

½Bacteriast = 75 · e − 1.5 · t + 20 · e − 0.075 · t

Determine the time required for the concentration of bacteria to be reduced to

15 using a graphical method and a numerical method.

Solution: (a) 4 h and (b) 4.016 h

3.33 We wish to know the metabolic flows of the network described in Figure P3.3315,
knowing that the consumption of substrates are: rS1 = 2.153 and rS2 = 2.961.

Solution: v1 = 2.153; v2 = 2.961; v3 = 2.961; v4 = 2.153; v5 = 0.404; v6 = 2.557;

v7 = 0.404.

15 “Co-factor pairs (e.g. ATP/ADP or NADH/NAD+) has coefficients with opposite and identical
signs in the stoichiometric equations. Therefore, only one of the two is included (always the same
for all reactions), to discard linearly dependent columns”
 3.4 Proposed problems 113

ATP ADP
NADH NAD+
S1
CO2
V1 S2
V2
ADP
ATP CO2
M1
V3 V4

NADH
ATP M2 NAD+ P1
ADP
V6
V5
CO2 P2

M3
ATP ADP
NADH

NAD+ P3

Figure P3.33: Metabolic network.

4 Balances in multiple systems

4.1 Analysis of degrees of freedom

4.1.1 Specification of a system

In multiple systems and/or processes, with many variables and equations, the cor-
rect specification of the problem to be solved is very important, that is, the correct
identification of the number of unknowns (Nx) and the definition of the number of
independent equations (Nec) that represent the same. This specification can lead to
three situations:
A. Nx > Nec Subspecified
B. Nx = Nec Specified
C. Nx < Nec Overspecified

The difference between the number of unknowns and the number of independent
equations constitutes the number of degrees of freedom of a system and/or process:
8 9 8 9
< number >
> = > < number of > =
GL = Nx − Nec = of − independent (4:1)
>
: ; >
> : >
;
unknowns equations

A subspecified problem (GL > 0) is essentially a design problem; therefore, it will be

necessary to determine a number of variables (equal to the number of degrees of
freedom) in a set of independent equations to which to assign values to solve the
equations. Depending on the set chosen, the different design methods for the pro-
cess units are defined.
A specified problem (GL = 0), all values are fixed only by the conditions speci-
fied in the problem statement, being able to obtain the solution (unique in most
cases) by solving the equations.
An overspecified problem (GL < 0) is sometimes caused by the redundancy of
correct information, but is usually the result of an error that has gone unnoticed. In
these cases, it is important to check the validity of each equation by extracting the
invalid equations. If all independent equations of an overspecified problem are vali-
dated, then the set that produces the most efficient or precise solution can be
chosen.

4.1.2 Calculation of the number of degrees of freedom

The number of unknowns for a control volume is given by the difference between
the number of variables and the number of data:

https://doi.org/10.1515/9783110624304-004
116 4 Balances in multiple systems

Nx = Nvariables − Ndata (4:2)

Among the most common variables in mass balances for steady-state systems, it is
worth highlighting:
i. the mass or molar flow rate for each component of the different streams, or the
concentration of each component plus the total flow rate;
ii. the degree of advancement or conversion of each of the chemical reactions;
iii. the recirculation and/or purge ratio.

In a process with “S” streams, “J” components and “I” independent chemical reac-
tions, the number of variables will be given by eq. (4.3):

Nvariables = NS · NJ + NI (4:3)

The most frequent independent equations to use are as follows:

i. Mass balances (with or without chemical reaction) of each of the components.
For a system of J components and U units, the units refer to the volumes of con-
trol on which to draw up the balances; therefore, the points of mixing and divi-
sion of streams are considered as units:

Nbalances = NJ · NU (4:4)

ii. Phase equilibrium relationships.

iii. Implicit relationships, for example, the concentration or quantity of a compo-
nent is zero in a given stream.
iv. Explicit relationships, such as a recovery fraction in a “separator.”

The number of independent equations will be given by the sum of the number of
balances and the other relationships or conditions of the system:

Nec = Nbalances + Nrelationships = NJ · NU + Nrelationships (4:5)

If eqs. (4.2), (4.3) and (4.5) are combined in eq. (4.1) to define the number of degrees
of freedom, the following general expression is obtained:

GL = Nx − Neq = ½NS · NJ + NI − Ndata  − NJ · NU + Nrelationships (4:6)

Example 4.1: Calculate the number of degrees of freedom of the steady-state process indicated in
Figure 4.1, as well as that of the R-101 reactor.

Solution:
Reactor R-101
The R-101 reactor is characterized by three process streams (two inputs and one output) where an inde-
pendent chemical reaction takes place; therefore, the number of variables will be given by eq. (4.3):

Nvariables = NS · NJ + NI = 3 · 3 + 1 = 10
 4.1 Analysis of degrees of freedom 117

(nA)4
T-101 4 (nB)4 = 0.97
(nC)4
R-101
= 0.9
A+B→C (nA)3
3 (nB)3
10 kmol B/h (nC)3
2
(nA)5
10 kmol A/h
5
= 0.85
1 (nB)5 = 0.88
(nC)5

Figure 4.1: Flow diagram of a stationary-state process consisting of two units: reactor and
distillation tower.

Corresponding to the molar flow rates of each of the streams and the degree of advancement of
the reaction: (nA)1, (nB)1, (nC)1, (nA)2, (nB)2, (nC)2, (nA)3, (nB)3, (nC)3, ζA.
Three data are provided: molar flow of A in stream 1 (nA)1, molar flow of B in stream 2 (nB)2 and
the degree of advancement of the reaction, ζA. Consequently, the number of unknowns:

Nx = Nvariables − Ndata = 10 − 3 = 7

The independent equations for reactor R-101 (single unit) correspond to the following:
– Balances: Nbalances = NJ · NU = 3 · 1 = 3
– Implicit relationships: the molar flow of B and C in stream 1 is zero and the molar flow of A and C
in stream 2 is zero.
– Independent equations: Nec = Nbalances + Nrelationships = 3 + 4 = 7.

Finally, the number of degrees of freedom of the reactor will be zero, that is, a specified system,
where when solving the balances, a unique solution will be obtained:

GL = Nx − Nec = 7 − 7 = 0
Overall process
Unknown:

Variables: ⇒ Nvariables = NS · NJ + NI = 5 · 3 + 1 = 16
– 5 streams
– 3 components (A, B, C)
– 1 chemical reaction

Data: ⇒ Ndata = 3
– 2 molar flow rates
– Degree of advancement of the reaction

Unknowns: ⇒ Nx = Nvariables − Ndata = 16 − 3 = 13

118 4 Balances in multiple systems

Independent equations:

Balances: ⇒ Nbalances = NJ · NU = 3 · 2 = 6
– 3 components
– 2 units (R-101 y T-101)

Implicit relationships: ⇒ Nimplicit relationships = 4

– Stream 1 [2]: molar flow rates of B and C are zero
– Stream 2 [2]: molar flow rates of A and C are zero

Explicit relationships: ⇒ Nexplicit relationships = 3

– Recovery fraction of C (in head), A and B (in bottom)

Independent equations: ⇒ Neq = Nbalances + Nrelationships = 6 + 7 = 13

Number of degrees of freedom:

Degrees of freedom ⇒ GL = Nx − Nec = 13 − 13 = 0

It is a perfectly specified problem that can proceed to the resolution of the system of independent
equations that will allow to obtain a unique solution.

4.2 Solution strategies

There are two calculation strategies for solving mass balances in multiple systems:
– Simultaneous solution method: The equations that represent the whole system and/
or process are defined, and then proceed to their simultaneous resolution. It is
also called an equation-based or equation-oriented method. Most of the examples
and problems proposed in Chapters 2 and 3 have been solved using this method.
– Sequential modular method: In this case, the independent equations (balances and
any other equation that defines process specifications or physical considerations)
of each control unit/volume that constitutes each of the modules into which the
system and/or process can be divided are solved sequentially. Most simulators use
this method because it is easier to apply in multiple systems, being able to detect
calculation errors more quickly. If there are no recirculation streams, the calcula-
tion goes from one unit to the next until all of them are covered. In systems with
recirculation streams, an iterative calculation will be required until an acceptable
convergence in the closing of the matter balance is obtained.

The closing of the mass balance (εM) is defined as the relationship between the ve-
locity of material flow at the inlet and outlet of a system:
 4.2 Solution strategies 119

 
P
mi
i
εM ð%Þ =  output · 100 (4:7)
P
mi
i input

The acceptable value of εM depends on the type and purpose of the mass balance.
For simulation/modeling calculations, the seal must be 100.0%, but with data mea-
sured in real processes, a seal between 90 and 110% may be acceptable. For chemi-
cal process design calculations, the closure of the mass balance is generally set
above 99.9%. The closure of the mass balance is an important issue in the applica-
tion of the sequential modular method.

Example 4.2: One of the removal alternatives for 17β-estradiol in urban wastewater is oxidation
catalyzed by the enzyme laccase in membrane reactors. One of the mechanisms described corre-
sponds to the formation of the C–C-dimer of estrogen:

OH
CH3

OH
CH3 OH
CH3
HO
OH
2

OH
17β-estradiol Dimeric compound
The design of a process is proposed (Figure 4.2) with a conversion per step in the reactor of 36%,
which is introduced in a nanofilter (F-101) that retains 12% of the 17-estradiol and 85% of the
dimer; the rest is recirculated at the entrance of the reactor. If the feed stream has a flow of
15 mmol/h of the estrogen, calculate the overall conversion and recirculation ratio. Apply both the
simultaneous solution method and the modular sequential method.

F-101

4
R-101
1 2

Figure 4.2: Flowchart of a process for the elimination of 17β-estradiol by laccase.

120 4 Balances in multiple systems

Solution:
A. Number of degrees of freedom
The necessary data for the calculation of the number of degrees of freedom are as follows:

Variables: Data:
– 5 streams – Molar flow rate of 17β-estradiol in the feed
– 2 components – Degree of advancement of the reaction
– 1 chemical reaction

Balances: Implicit relationships:

– 2 components – Flow of dimeric compound in stream 1 is zero
– 3 units (valve, R-101, F-101) Explicit relationships:
– Filter efficiency

Figure 4.3 shows the calculation of the number of degrees of freedom by applying eqs. (4.1)–(4.5).
Depending on the number of degrees of freedom, cell C85 automatically displays the type of prob-
lem from the point of view of the specification:

A B C D E F G H
52
53 Variables - unknown
54 Variables:
55 Nvariables = Ns·NJ +NI = 11
56
57 Streams (S) = 5
58 Components ( J) = 2
59 Chemical Reactions (I) = 1 - Flow of estrogen in the
60 Unknown stream 1
61 Data = 2
62 - Degree of conversion of the
63 Nx = Nvariables – Ndata = reaction
9
64
65
66 Independent equations
67 Balances: - Valve
68 Units (U) = 3 - R-101
69 - F-101
70 Nbalances = NJ · NU = 6
71 - The flow of the dimeric
compound in stream
72 Implicit relationships = 1 1 is
73 Explicit relationships = 2
74 Equations:
75 Neq = Nbalances + Nrelationships = - Filter efficiency
76
77 9
78
79 Degrees of freedom
80
81
82 GL = Nunknown – Neq = 0
83
84
85 Specified problem
86
87

Figure 4.3: Degrees of freedom in Example 4.2.

 4.2 Solution strategies 121

C85: = IF(E89 = 0; “Specified problem”; IF(E89 < 0; “Over-specified, check for errors”; “Degrees
of freedom”))
In this example, the problem is perfectly specified and therefore the solution to the problem can
be obtained by solving the equations independent of the process.

B. Simultaneous solution method

Step 1: Flowchart with identification and enumeration of streams
Reaction data: If we call A1≡C18H24O2 (17β-estradiol) and A2≡C36H46O4 (C–C dimer) the reaction
can be expressed as follows:
A2 − 2A1 = 0

Being C18H24O2 the limiting reactant and, therefore, k = 1 and a degree of conversion of 0.36.
Process data: Filter efficiencies, η1 = 0.12 and η2 = 0.85:

ðn1 Þ4 = η1 · ðn1 Þ3
ðn2 Þ4 = η2 · ðn2 Þ3

Step 2: Basis of calculations

The feed flow rate of C18H24O2 shall be considered as the calculation basis: (n1)1 = 15 mmol/h.

Step 3: Definition of control volumes and formulation of the mass balances

To calculate the molar flow of the components in each stream, the component balances with and
without chemical reaction will be applied:
– Mass balance without chemical reaction:
   
– Any component:
nj input =
nj output (4.8)

– Mass balance with chemical reaction:

 X
h 
– Limiting reactant ðkÞ: nk = nko 1 − ζ ki (4.9)
i=1

Xh  
αji
– Other reactants and products ð jÞ: nj = njo − nk0 i · ζ ki · (4.10)
i=1
αki

– Volume control to the mixing point of the feed and recirculation

Balance for CHO ðn1 Þ1 + ðn1 Þ5 = ðn1 Þ2

Balance for CHO ðn2 Þ1 + ðn2 Þ5 = ðn2 Þ2

– Control volume corresponding to reactor R-

Balance for CHO (limiting reactant) ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ

Balance for CHO α2

ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 ·
α1
122 4 Balances in multiple systems

– Control volume corresponding to filter F-

Balance for CHO and filter efficiency ðn1 Þ3 = ðn1 Þ4 + ðn1 Þ5 ⇒ ðn1 Þ5 = ð1 − η1 Þðn1 Þ3
ðn1 Þ4 = η1 · ðn1 Þ3

Balance for CHO and filter efficiency ðn2 Þ3 = ðn2 Þ4 + ðn2 Þ5 ⇒ ðn2 Þ5 = ð1 − η2 Þðn2 Þ3
ðn2 Þ4 = η2 · ðn2 Þ3

Step 4: Solving the system of equations

From the above equations, the system is defined by six linearly independent equations:

Equations Unknowns Coded equations

½1 ðn1 Þ1 + ðn1 Þ5 = ðn1 Þ2 x = (n) ½1 x1 − x5 = ðn1 Þ1

½2 ðn2 Þ1 + ðn2 Þ5 = ðn2 Þ2 x = (n) ½2 x2 − x6 = ðn2 Þ1
½3 ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ x = (n) ½3 ð1 − ζ 1 Þx1 − x3 = 0
x = (n)  
α2 α2
½4 ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 · x = (n) ½4 − ζ 1 · x1 + x2 − x4 = 0
α1 α1
½5 ðn1 Þ5 = ð1 − η1 Þðn1 Þ3 x = (n)
½5 ð1 − η1 Þx3 − x5 = 0
½6 ðn2 Þ5 = ð1 − η2 Þðn2 Þ3 ½6 ð1 − η2 Þx4 − x6 = 0

First, a copy of the “6 variables” sheet from the “Appendix D_Matrix Inversion” file (see Appendix D) to
the book where the solution to the problem is being elaborated. Both sheets are then “interconnected”
with the introduction of the coefficients of the linear equations as data or as a formula, as appropriate,
when related to the spreadsheet of the problem. When you finish entering the coefficients, you will
automatically obtain the calculation of the solution of the system of linear equations that we can, in
turn, transfer to the corresponding cells in the main spreadsheet of the problem (Figure 4.4).
Applying eq. (4.7) you can obtain the closing of balances for each of the units and the overall
process, where you get a closing of 99.7% for the overall process. With the molar flows of all streams
both the overall conversion and the recirculation ratio can be calculated:
– Global conversion of 82%: G54: = ((F51–I51)/F51)
– Recirculation ratio of 1.36: G55: = ((J51 + J52)/(F51 + F52))

C. Sequential modular method

Steps 1 and 2: Flowchart with identification of streams and choice of calculation basis
Both steps are common to the simultaneous solution method, since the difference lies in the strat-
egy for solving the equations independent of the process.

Steps 3 and 4: Formulation and resolution of the mass balances

The modular sequential method is based on the solution of the balances for each of the units (mod-
ules) consecutively.

Valve Reactor (R-) Filter (F-)

ðn1 Þ2 = ðn1 Þ1 + ðn1 Þ5 ðn1 Þ3 = ðn1 Þ2 · ð1 − ζ 1 Þ ðn1 Þ4 = η1 · ðn1 Þ3
ðn2 Þ2 = ðn2 Þ1 + ðn2 Þ5 α2 ðn2 Þ4 = η2 · ðn2 Þ3
ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ2 · ζ 1 ·
α1 ðn1 Þ5 = ðn1 Þ3 − ðn1 Þ4
ðn2 Þ5 = ðn2 Þ3 − ðn2 Þ4
 4.2 Solution strategies 123

B C D E F G H
42 Process data and specifications:
43 Reaction data: Filter efficiency:
44 Degree of conversion: 0.36
45 aj η1= 0.12
46 C18H24O2: k=1 –2 η2= 0.85
47 C36H46O4: j=2 1
48 Process mass balance: stream table
49 1 2 3 4 5
50 Compound: M (g/mol) mmol/h
51 C18H24O2: 272.0 15.0 34.341 21.978 2.637 19.341
52 C36H46O4: 542.0 0.0 1.091 7.272 6.181 1.091
53 Closing of balances:
54 Total: mg/h 4,080.0 9,931.9 9,919.5 4,067.6 5,851.9

55 Valve Reactor Filter Global

56 ςminput: 9,931.9 9,931.9 9,919.5 4,080.0 mg/h

57 ςmoutput: 9,931.9 9,919.5 9,919.5 4,067.6 mg/h

58 ɛM = 100.0 99.9 100.0 99.7 %
59 Process characteristics
60 Process parameters
(n1)1–(n1)4 (n)5
61 Global conversion: 0.82 XGlobal = r=
(n1)1 (n)1
62 Recirculation ratio: 1.36

Figure 4.4: Spreadsheet with mass balance data.

In the case of recirculation streams, as in this case, the calculation must be iterative until the
desired convergence is reached (Figure 4.5). The initial value considered at the feed and recircula-
tion mixing point for the molar flow velocities of the recirculation streams (n1)5 and (n2)5 was zero.
After seven iterations the balance closes with 98.6% (cell J84), obtaining a global conversion of
83% and a recirculation ratio of 1.35.
The use of spreadsheet allows a simpler application of the modular sequential method, starting
from the application of the “circular reference” tool for iterative calculation. Thus, the equations can
be entered directly into the corresponding cells of the molar flow velocities (Figure 4.6a), so that
when writing the flow velocities of the filter recirculation stream (stream 5) the program will issue a
note about the existence of a circular reference. Enabling this calculation (see Appendix C) will show
the calculation that is obtained either after 100 iterations or that calculation that reaches a conver-
gence between the flow velocities of stream 5 such that the difference in values of the molar flow
velocity is less than 0.00001 (Figure 4.6b). The result is, in this case, identical to that obtained with
the simultaneous solution method: global conversion of 82% and recirculation ratio of 1.36.
 A B C D E F G H I J
124

64 Sequential calculation (iterations)

65
66 Iteration
67 Initial valor 1 2 3 4 5 6 7
68 Feed:
(n1)1 =
69 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00
(n2)1 = 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
70
71 Valve
(n1)2 = (n1)1 + (n1)5
72 15.00 23.45 28.21 30.89 32.39 33.24 33.72 33.99
(n ) = (n ) + (n2)5
2 2 2 1 0.00 0.41 0.69 0.87 0.96 1.02 1.05 1.07
73
74 Reactor (R-101):
(n1)3 = (n1)2 · (1 – ζ1)
75 9.60 15.01 18.05 19.77 20.73 21.28 21.58 21.76
4 Balances in multiple systems

α
(n2)3 = (n2)2 –(n1)2 · ζ1 · 2
α1 2.70 4.63 5.77 6.43 6.79 7.00 7.12 7.19
76
77 Filter (F-101):
(n1)4 = η1 · (n1)3
78 1.15 1.80 2.17 2.37 2.49 2.55 2.59 2.61

79 (n2)4 = η2 · (n2)3 2.30 3.93 4.91 5.46 5.78 5.95 6.05 6.11
(n1)5 = (n1)3 – (n1)4 8.45 13.21 15.89 17.39 18.24 18.72 18.99 19.14
80
(n2)5 = (n2)3 – (n2)4 0.41 0.69 0.87 0.96 1.02 1.05 1.07 1.08
81
82 ςminput(mg/h) 4,080.0 4,080.0 4,080.0 4,080.0 4,080.0 4,080.0 4,080.0 4,080.0

83 ςmoutput(mg/h): 1,557.2 2,620.9 3,247.9 3,605.2 3,807.1 3,920.9 3,985.0 4,021.1

84 ɛM (%) = 38.2 64.2 79.6 88.4 93.3 96.1 97.7 98.6
85

Figure 4.5: Iterative calculation when applying the sequential solution method to Example 4.2.
 B C D E F G H
42 Process data and specifications:
Reaction data: Filter efficiency:
(a)
43
44 0.36
45 αj η1= 0.12
46 C18H24O2: k=1 –2 η2= 0.85
47 C36H46O4: j=2 1
48 Process mass balance: S–
49 1 2 3 4 5
50 Compound M (g/mol) mmol/h
51 C18H24O2: 272 15 =D51+H51 =E51*(1–D44) =F51*H45 =F51–G51
52 C36H46O4: 542 0 =D52+H52 =E52–E51*D44*(D47/D46 =F52*H46 =F52–G52
53 Closing of balances:
54 Total: mg/h =D51*C51+D52*C52 =E51*C51+E52*C52 =E51*C51+F52*C52 =G51*C51+G52*C52 =H51*C51+H52*C52
55 Valve Reactor Filter Global
56 Σminput: =D54+H54 =E54 =F54 =D54 mg/h
57
58 Σmoutput: =E54 =E54 =G54+H54 =G54 mg/h
59 εM = =(D57/D56)*100 =(E57/E56)*100 =(F57/F56)*100 =(G57/G56)*100 %
60 Process characteristics
61 Process parameters
(n1)1– (n1)4 (n)5
62 Global conversion: =((D51–G51)/D51) XGlobal = r=
(n1)1 (n)1
63 Recirculation ratio: =((H51+H52)/(D51+D52))

Figure 4.6: (a) Cells with the formulas to apply the modular sequential method by circular reference in Example 4.2 and (b) result after enabling the
calculation with circular reference.
Press CTRL + ` (grave accent): Switch between displaying formulas and their results.
4.2 Solution strategies
125
126 4 Balances in multiple systems

B C D E F G H
42 Process data and specifications:
43 Reaction Data: Filter efficiency:
44 Degree of conversion: 0.36
45 αj η1= 0.12
46 C18H24O2: k=1 –2 η 2= 0.85
47 C36H46O4: j=2 1
48 Process mass balance: stream table
49 1 2 3 4 5
50 Compound M (g/mol) mmol/h
51 C18H24O2: 272.0 15.0 34.341 21.978 2.637 19.341
52 C36H46O4: 542.0 0.0 1.091 7.272 6.181 1.091
53 Closing of balances:
54 Total: mg/h 4,080.0 9,931.9 9,919.5 4,067.6 5,851.9
55 Valve Reactor Filter Global
56 Σminput: 9,931.9 9,931.9 9,919.5 4,080.0 mg/h
57 Σmoutput: 9,931.9 9,919.5 9,919.5 4,067.6 mg/h
58 εM = 100.0 99.9 100.0 99.7 %
59 Process characteristics
60 Process parameters
(n1)1−(n1)4 (n)5
61 Global conversion: 0.82 XGlobal= r=
(n1)1 (n)1
62 Recirculation ratio: 1.36

Figure 4.6 (continued )

4.3 Synthesis of methanol

Methanol (CH3OH) is the most significant representative of the group of organic

compounds of a carbon atom (group C1), which under normal conditions of pres-
sure and temperature is presented as a colorless, flammable and toxic liquid that is
used as antifreeze, solvent and fuel.
It is used as a raw material in the synthesis of other compounds of group C1
such as formaldehyde (a key element in the manufacture of adhesives) and of
group C2 such as acetic acid (whose esters, vinyl acetate or cellulose acetate are the
basis for the manufacture of nylon, cellophane and other polymers; Figure 4.7).
Methanol is produced primarily from synthesis gas from natural gas by catalytic
reaction of hydrogen with CO2 (Figure 4.8).
Natural gas desulfurized with 1.2% (% molar) N2 (stream 1) undergoes catalytic
reforming (cracking or methane rupture) in a multitubular furnace (H-101) where
the synthesis gas is obtained by reacting with H2O vapor at high temperatures:

CH4 + 2H2 O ! CO2 + 4H2 Main reaction

CH4 + H2 O ! CO + 3H2
 4.3 Synthesis of methanol 127

O
H3C Acetic acid
OH
O
Methyl H2C
methacrylate OCH3
CH3
O CH3
O CH3 Methyl tert-
H3 C
Formaldehyde butyl ether
H H CH3

H
N CH3
H

Methylamines

Figure 4.7: Different chemical compounds obtained from methanol, which in turn are the basis for
different polymers.

12 Purge

13 11

O2
9 V-103
V-101 4
10

5
CH3OH
R-101 R-102
7 8
CH4 1 3

H2O(v) 2
6 CO2
H-101
V-102

Figure 4.8: Simplified flowchart for methanol synthesis.

In order to favor a global conversion of methane, an excess of 12% is used in

the water vapor (stream 2), with a yield of 88% CO2 (H-101). A complete conversion
of CO to CO2 takes place by reaction with O2 in stoichiometric quantities (R-101):

2CO + O2 ! 2CO2
128 4 Balances in multiple systems

To the resulting synthesis gas a CO2 stream is added that feeds the methanol syn-
thesis reactor (R-102) along with the recirculation gas maintaining an H2/CO2 ratio
of 3/1 at the reactor inlet (stream 8):

CO2 + 3H2 ! CH3 OH + H2 O

The degree of advancement of the CO2 reaction is 52%. The output of the R-102 reac-
tor cools and condenses methanol and water, recirculating the noncondensable
gases, where a ratio of 3/1 H2/CO2 is maintained (stream 13). To avoid an increase in
the concentration of inert materials, a purge is carried out in the synthesis circuit
(contains 4% N2).
On the basis of these data, a simulation of the process will be carried out based
on the mass balances, which will make it possible to estimate the flow and composi-
tion of the expected raw methanol flow, as well as other operational characteristics of
the process, for example, the relationship between the flow of the recirculation and
purge flows.

4.3.1 Degrees of freedom

For the calculation of the number of degrees of freedom of the global process, it is
necessary to determine the unknowns in function of the number of variables and
process data, as well as the number of independent equations obtained by the sum
of the number of matter balances and the number of implicit and explicit relations
of the process:
– Variables:
– The molar flows of the eight components (CH4, H2O, CO2, H2, N2, CO, O2 and
CH3OH) in each of the 13 streams: (n1)1, (n2)1, (n3)1, (n4)1, [..], (n6)13, (n7)13
and (n8)13,
– The degrees of advancement of the four chemical reactions: ζ1, ζ2, ζ3 and ζ4
– Data:
– Flows:
– Concentration of N2 in the streams 1 and 12
– Excess H2O in the stream 2
– O2 stoichiometric in the stream 4
– Reactions:
– Global conversion of CH4 into H-101
– Conversion of CO in R-101
– Conversion of CO2 in R-102
– Independent equations:
– Balances:
 4.3 Synthesis of methanol 129

– Mass balances with or without chemical reaction in each of the process

units: H-101, R-101, R-102 and V-103. As noted earlier in this chapter, the
mixing and flow separation points are also control volumes where balan-
ces are made and, therefore, computed within the term “units”: Valve5/
6→7, Valve7/13→8 and Valve11→12/13
– Implicit relationships:
– Stream 1: the flow rate of H2O, CO2, H2, CO, O2 and CH3OH is zero
– Stream 2: the flow rate of CH4, CO2, H2, N2, CO, O2 and CH3OH is zero
– Stream 4: the flow rate of CH4, H2O, CO2, H2, N2, CO and CH3OH is zero
– Stream 6: the flow rate of CH4, H2O, H2, N2, CO, O2 and CH3OH is zero
– Streams 7 and 8: the flow rate of CH3OH is zero
– Streams 7, 8 and 9: the flow rate of H2/CO2 is 3/1
– Streams 7 and 12: the flow rate of N2 is the same
– Stream 10: the flow rate of CO2, H2, N2 is zero
– Streams 11, 12 and 13:
– The flow rate of H2O and CH3OH is zero
– The concentration of N2 in the three streams is the same
– Explicit relationships:
– Mole ratio of H2/CO2 in the streams 8 and 13
– CO2 performance in H-101

Figure 4.9 shows the calculation of the number of degrees of freedom by applying
eqs. (4.1)–(4.5). Depending on the number of degrees of freedom, cell B76 automati-
cally shows the type of problem from the point of view of the specification.
In this example, the problem has a degree of freedom, being the one corre-
sponding to the calculation base that is chosen for the solution of the problem.

4.3.2 Simulation based on mass balances: sequential modular method

To obtain the simulation (based on mass balances) of the process, proceed in the
same way as described in the preceding chapters for the solution of mass balances.
Step 1: Flowchart with identification and enumeration of streams
– Reaction data (Figure 4.10)
– If we call A1≡ CH4, A2≡ H2O, A3≡ CO2, A4≡ H2, A5≡ N2, A6≡ CO, A7≡ O2
and A8≡ CH3OH, the reactions can be expressed:

R1: 4A4 + A3 − 2A2 − A1 = 0

R2: A6 + 3A4 − A2 − A1 = 0
R3: − A7 − 2A6 + 2A3 = 0
R4: A8 − 3A4 − A3 + A2 = 0
130 4 Balances in multiple systems

A B C D E F G H I J K L
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77

Figure 4.9: Calculation of the number of degrees of freedom in methanol synthesis.

– R1 and R2: CH4 is the limiting reactant and therefore k = 1. The degree of
advancement of each of these two reactions is unknown, but the overall
conversion (i.e., the sum of the two) is 100%.
– R3: Since oxygen enters in stoichiometric quantities, any of the reactants
can be considered a limiting factor. CO shall be considered as the limiting
reactant, k = 6. The conversion is 100%.
– R4: The H2/CO2 input ratio in the R-102 reactor is 3/1 (stoichiometric condi-
tions). The limiting reactant will be CO2, that is, k = 3 for this reaction. The
conversion is 52% CO2.
– Process data and specifications:
– Concentration of N2 in streams 1 and 12:
– Stream 1: The concentration of N2 is 1.2% and, therefore, the molar frac-
tion of CH4
   
xCH4 1 = 1 − xN2 1 = 1 − 0.012 = 0.988

– Stream 12: (xN2) = 0.04.

– Excess H2O in the stream 2: 12%.
 A B C D E F G H I J K L M N O
Methanol synthesis
2 Sequential modular method
3
4 Legend:
5 Data Purge
12
6 Basis of calculations
7 Calculations
8 Solution 13 11
9
10
11
12 O2 R3: 2CO + O2→2CO2
13
9 V-103
14
15
16 V-101 4
17
18
10
19
20 R1: CH4+2H2O→CO2+4H2
21 5
22 R2: CH4+H2O → CO + 3H2 CH3OH
23
24 R-101
25
R-102
26
27 7 8
28
29
CH4 1 3 R4: CO2 + 3H2 → CH3OH + H2O
30
31
32 H4O(V) 2
33 6 CO2
34 H-101
35
36 V-102
37
38 Process data and specifications:
39 Stream 1: H-101: R-101: Stream 8: Steam 12: Stream 13:
40 100.0
41 0.988
42 0.012
43 Reaction R1: Reaction R2: Reaction R3: Reaction R4:
44
45
46
47
48
49
4.3 Synthesis of methanol

50

Figure 4.10: Data and specifications for the simulation of methanol synthesis.
131
132 4 Balances in multiple systems

– Stream 4 (inlet to R-101) containing O2 has such a flow that the ratio is stoi-
chiometric, that is, an excess of 0% (Cell H41).
– There are two additional data that refer to two explicit process relationships:
– The CO2 yield in reaction R1 is 88%.
– The molar ratio in H2/CO2 in streams 8 and 13 is 3/1.

Step 2: Basis of calculations

The natural gas supply flow (n)1 = 100 mol/h shall be considered as the calculation
basis. Cell B40 is shown in Figure 4.10.

Step 3: Definition of the volume of control and formulation and resolution of the
mass balances
The modular sequential method is based on the solution of the balances for each of
the control units or volumes consecutively. The following equations shall be used
for this purpose:
– Mass balance without chemical reaction:
– Any component:
   
Σ nj input = Σ nj output (4:11)

– Mass balance with chemical reaction:

– Limiting reactant(k):
 X h 
nk = nko 1 − ζ ki (4:12)
i=1

– Other reactants and products(j):

Xh  
αji
nj = njo − nk0 i · ζ ki · (4:13)
i=1
αki

– Component in excess( j):

njo n
αj − ko=αk
%Aj = nko= · 100 (4:14)
αk

– Performance of a component( j):

njo − nj αk
Rj = · (4:15)
nko αj

Feed streams
From the total molar flow of stream 1 (calculation basis) and the composition of
each component the molar flow of each component can be calculated:
 4.3 Synthesis of methanol 133

ðn1 Þ1 = ðnÞ1 · ðx1 Þ1

ðn5 Þ1 = ðnÞ1 · ðx5 Þ1

They are introduced into cells C54 and C58 (Figure 4.11) to obtain values of 98.80
and 1.20 mol/h, respectively:
C54: = $B$40*B41
C58: = $B$40*B42

The molar flow rate for all other components in stream 1 is zero (implicit ratio). In
stream 2, the molar flow of H2O is obtained by clearing the value of (n2)2 from
eq. (4.14):
 
α21 % A21
ðn2 Þ2 = ð n1 Þ 1 1 +
α11 100

This equation is introduced in cell D55 that reflects a value of 221.31 mol/h. The
molar flow rate for the rest of the components in stream 2 is zero.
D55: = (C47/C46)*C54*(1 +(E41/100))

Furnace H-101
First, it will be necessary to calculate the degree of progress for each of the reac-
tions that occur in the furnace. For this purpose, from the CO2 yield (eq. (4.11)) the
molar flow of CO2 at the exit of the furnace can be calculated to then obtain the
degree of progress of the first reaction when considering the CO2 balance (eq. 4.10)
since only the first of the reactions is involved in its formation:
 
ðn3 Þ½1 − 2 − ðn3 Þ3 α11 α31
R3 = · ) ðn3 Þ3 = ðn3 Þ½1 − 2 − ðn1 Þ1 · R3 ·
ðn1 Þ1 α31 α11
α31 ðn3 Þ½1 − 2 − ðn3 Þ3 α11
ðn3 Þ3 = ðn3 Þ½1 − 2 − ðn1 Þ1 · ζ 1 · ) ζ1 = ·
α11 ðn1 Þ1 α31

Since the overall methane conversion is the sum of the conversions that are achieved
in the two reactions, the degree of advancement of the second reaction can be
obtained:

ζ CH4 = ζ 1 + ζ 2 ) ζ 2 = ζ CH4 − ζ 1

These equations are introduced in cells E56 (Figure 4.10), C44 and F44 (Figure 4.11),
respectively:
E56: = (C56 + D56)-(C54*(E42/100)*(C48/C46))
C44: = (((C56 + D56)–E56)/C54)*(C46/C48)
F44: = E40-C44
 A B C D E F G H I J K L M N O
134

51 Process mass balance: stream table

52 1 2 3 4 5 6 7 8 9 10 11 12 13
53 Compound: M (g/mol) mol/h
54 CH4: 16.0 98.80 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
55 H2O: 18.0 0.00 221.31 35.57 0.00 35.57 0.00 35.57 35.57 156.15 0.00 0.00 0.00 0.00
56 CO2: 44.0 0.00 0.00 86.94 0.00 98.80 28.98 127.78 231.89 111.31 0.00 111.31 7.20 104.11
57 H2: 2.0 0.00 0.00 383.34 0.00 383.34 0.00 383.34 695.66 333.92 0.00 333.92 21.60 312.32
58 N2: 28.0 1.20 0.00 1.20 0.00 1.20 0.00 1.20 18.55 18.55 0.00 18.55 1.20 17.35
59 CO: 28.0 0.00 0.00 11.86 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
60 O2: 32.0 0.00 0.00 0.00 5.93 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
61 CH3OH: 32.0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 120.58 120.58 0.00 0.00 0.00
62 Closing of balances
63 Total: kg/h 1.61 3.98 5.60 0.19 5.79 1.28 7.06 12.75 12.75 6.67 6.08 0.39 5.69
64 H-101 R-101 Valve5/6→7 Válvula7/13→8 R-102 V-103 Valve11→12/13 Global
65 ςminput: 5.60 5.79 7.06 12.75 12.75 12.75 6.08 7.06 kg/h
4 Balances in multiple systems

66 ςmoutput: 5.60 5.79 7.06 12.75 12.75 12.75 6.08 7.06 kg/h
67 ɛM = 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 %
68 Process characteristics
69 CH3OH(aq) composition Recirculation: Purge: Recirculation/purge ratio:
70 mol/h % molar kg/h % percent by weight mol/h mol/h (n)13
71 H2O: 156.15 56.43 2.81 42.14 CO2: 104.11 CO2: 7.20 = 14.46
(n)12
72 CH3OH: 120.58 43.57 3.86 57.86 H2: 312.32 H2: 21.60
73 Total: 276.73 100.00 6.67 100.00 N2: 17.35 N2: 1.20
74 Total: 433.77 Total: 30.00

Figure 4.11: Mass balances and process characteristics in the simulation of methanol synthesis.
 4.3 Synthesis of methanol 135

The remaining molar flows of stream 3 for each of the components involved
in the reaction are obtained by means of the corresponding balances with
chemical reaction (eq. (4.9) and (4.10)), bearing in mind that the limiting re-
actant is CH4:

Methane balance ) ðn1 Þ3 = ðn1 Þ3 · ð1 − ζ 1 − ζ 2 Þ

α21 α22
Water balance ) ðn2 Þ3 = ðn2 Þ2 − ðn1 Þ1 · ζ 1 · − ðn1 Þ1 · ζ 2 ·
α11 α12
α41 α42
Hydrogen balance ) ðn4 Þ3 = ðn4 Þ1 − ðn1 Þ1 · ζ 1 · − ðn1 Þ1 · ζ 2 ·
α11 α12
α62
Carbon monoxide balance ) ð n6 Þ 3 = ð n6 Þ 1 − ð n1 Þ 1 · ζ 2 ·
α12

The molar nitrogen flow at the outlet of H-101 will be the same as at the inlet as it is
an inert component (eq. (4.8)):
ðn5 Þ3 = ðn5 Þ1 + ðn5 Þ2

All these equations are entered into cells E54, E55, E57, E58, E59 and E60 (Figure 4.11).
Stream 3 is fully characterized because the molar flow of oxygen and methanol is zero:
E54: = C54*(1-C44–F44)
E55: = D55–C54*C44*(C47/C46)–C54*F44*(F47/F46)
E57: = C57–C54*C44*(C49/C46)–C54*F44*(F49/F46)
E58: = (C58 + D58)
E59: = C59–C54*F44*(F48/F46)

The closing of balances for this unit is obtained with eq. (4.7), previously calculat-
ing the mass flow in streams 1, 2 and 3. This mass flow is obtained by multiplying
the molar flow by the molecular weight of the components. As an example, the
equation for the stream 1 in cell C63 is described (units of kg/h), being obtained in
an analogous way for the rest of streams (Figure 4.12):

A B C D E F
62 Closing of balances
63 Total: kg/h 1.61 3.98 5.60 0.19
64 H-101 R-101 Valve5/6→7 Valve7/13→8
65 ςminput: 5.60 5.79 7.06 12.75
66 ςmoutput: 5.60 5.79 7.06 12.75
67 ɛM = 100.00 100.00 100.00 100.00

Figure 4.12: Closing balances for H-101.

C63: = (C54*$B$54 + C55*$B$55 + C56*$B$56 + C57*$B$57 + C58*$B$58 + C59*

$B$59 + C60*$B$60 + C61*$B$61)/1000
136 4 Balances in multiple systems

Therefore, the incoming, outgoing and closing balance mass flow for the H-101
unit are presented in cells C65, C66 and C67, respectively:
C65: = C63 + D63
C66: = E63
C67: = (C66/C65)*100

The mass balance is closed with a value of 100%.

Reactor R-101
The input streams to the reactor are number 3 (fully characterized) and number 4,
which corresponds to a flow of oxygen in stoichiometric conditions, that is, clearing
the value of (n7)4 in eq. (4.14) for an excess value of zero (in this way it will be possi-
ble to simulate various situations later regarding the flow of oxygen):
 
α73 % A73
ðn7 Þ2 = ðn6 Þ3 1 +
α63 100

This equation is written in cell F60. All other values for stream 4 are zero (implicit
ratio):
F60: = (I47/I46)*E59*(1 +(H41/100))

Analogously with eqs. (4.9) and (4.10) the molar flow at the reactor output (stream
5) can be obtained for the components involved in the reaction:
α33
Carbon dioxide balance ) ðn3 Þ5 = ðn3 Þ3 − ðn6 Þ3 · ζ 3 ·
α63
 
Carbon monoxide balance ) ðn6 Þ5 = ðn6 Þ3 · 1 − ζ 3
α73
Oxygen balance ) ðn7 Þ5 = ðn7 Þ4 − ðn6 Þ3 · ζ 3 ·
α63

For the inert ones in the reaction (CH4, H2O, H2, N2) the balance corresponds to the
eq. (4.8):
     
nj 5 = nj 3 + nj 4

Therefore, these equations are introduced in cells G54 to G60 (Figure 4.10). In
stream 5 the methanol value is zero, cell G61:
G54: = E54 + F54
G55: = E55 + F55
G56: = E56-E59*I44*(I48/I46)
G57: = E57 + F57
G58: = E58 + F58
G59: = E59*(1–I44)
G60: = F60-E59*I44*(I47/I46)
 4.3 Synthesis of methanol 137

Control volume corresponding to valve5/6→7

This control volume corresponds to the mixing point of stream 5 with stream 6
(CO2) such that a stream 7 is obtained, which must have a ratio 3/1 of H2/CO2 be-
cause at the input of the reactor (stream 8) this ratio must be obtained. For the rest
of the components, it is verified that the molar flow in stream 7 is identical to that
of stream 5 (eq. (4.8)):
   
nj 7 = nj 5

The value of CO2 in the streams 6 and 7 [(n3)7, (n3)7,] is obtained from the explicit
relationship of the molar flows of H2/CO2 and the balance of CO2 to the valve:

ðn4 Þ7 ðn4 Þ7
½r½4=37  = ½r½4=38  = ½r½4=313  ) ½r½4=37  = ) ðn3 Þ7 =
ðn3 Þ7 ½r½4=37 

ðn3 Þ6 = ðn3 Þ7 − ðn3 Þ5

The rest of the molar flows in stream 6 are zero (implicit relation). These equations
are introduced into the corresponding cells (Figure 4.10).

Control volume corresponding to valve7/13→8

This control volume corresponds to the mixing point with the recirculation stream
(stream 13) containing CO2, H2 and N2. Therefore, when applying eq. (4.8):
     
CO2 , H2 and N2 : )  nj 8 =  nj 7 + nj 13
Other components: ) nj 8 = nj 7

Reactor R-102
Equations (4.9) and (4.10) allow to obtain the molar flow at the output of the reactor
(stream 9) for the components involved in the reaction:
α24
Water vapor balance ) ðn2 Þ9 = ðn2 Þ8 − ðn3 Þ8 · ζ 4 ·
α34
 
Carbon dioxide balance ) ðn3 Þ9 = ðn3 Þ8 · 1 − ζ 4
α44
Hydrogen balance ) ðn4 Þ9 = ðn4 Þ8 − ðn3 Þ8 · ζ 4 ·
α34
α84
Methanol balance ) ðn8 Þ9 = ðn8 Þ8 − ðn3 Þ8 · ζ 4 ·
α34

For the inert ones in the reaction (in this case only N2 enters the unit) the balance is
given by the eq. (4.8):
ðn5 Þ9 = ðn5 Þ8
138 4 Balances in multiple systems

Condenser V-103
In the V-103 unit there is complete condensation of methanol and water (stream 10)
while the gases CO2, H2 and N2 come out through the stream 11. The balances
(eq. (4.8)) are as follows:
   
CH3 OH and H2 O: ) nj 10 =  nj 9
CO2 , H2 and N2 : ) nj 11 = nj 9

Purge stream (12)

The main purpose of the purge stream is to avoid the accumulation of N2 in the system,
so the molar flow in stream 7 must be the same as in stream 12 (implicit relation):
ðn5 Þ12 = ðn5 Þ7

Since the concentration of nitrogen in stream 12 is available (problem data) and the
molar ratio of H2/CO2 in the same stream (separating streams have the same compo-
sition), it is possible to calculate the flows of CO2 and H2 in stream 12:
ðn3 Þ12 · ½1 − ðx5 Þ12 
ðx5 Þ12 =
ðn5 Þ12 ðn3 Þ12 =  h i
ðn3 Þ12 + ðn4 Þ12 + ðn5 Þ12
ðx5 Þ12 · 1 + r½4=3
) 12
ðn4 Þ12
½r½4=312  = ½r½4=313  = ðn3 Þ12 ðn4 Þ12 = ðn3 Þ12 · ½r½4=312 

Control volume corresponding to valve11→12/13

Stream 11 is subdivided into stream 12 (purge) and 13 (recirculation), being the bal-
ances for CO2 and H2 (eq. (4.8)):
     
nj 13 = nj 11 − nj 12

By entering these equations in cells O56 and O57, the program will activate a “circu-
lar reference” message that must be enabled (see Appendix C) in order for the itera-
tive calculation to be performed.
To calculate the molar flow of nitrogen in stream 13 it must be taken into ac-
count that the composition of N2 in the same stream as in purge (dividing streams
have the same composition):

ðn5 Þ13 ðx5 Þ12 · ðn3 Þ13 + ðn4 Þ13

ðx5 Þ13 = ðx5 Þ12 = ) ðn5 Þ12 =
ðn3 Þ13 + ðn4 Þ13 + ðn5 Þ13 1 − ðx5 Þ13

Step 4: Process characteristics

All the streams have been characterized and, therefore, the main characteristics of
the process can be evaluated: composition of the product and relationship between
the recirculation and purge stream.
 4.4 Circular economy: obtaining sodium alginate from marine algae 139

Product composition: Relationship between recirculation and purge:

A E F K L M
69 CH3OH(aq) Composition 70
70 % percent by weight (n)13
H2O: 71 r 13 = = 14.46
71 42.14 [ 12 ] (n)12
72 CH3OH: 57.86 72
73 Total: 100.00
74

Questions/simulations:
i. Effect of the calculation basis: The calculation basis has no influence on the
composition or relationship of the recirculation/purge ratio, although it does
influence the molar flows. If, for example, the value of 250 mol/h is entered in
the B40, the result will not change.
ii. Scenario simulation: Simulation makes it possible to evaluate the situation of
the process in different scenarios by estimating the new characteristics of the
process. If the data were considered as described in Figure 4.13, the methanol
composition would increase to 58.92%.

A B C D E F J K L M N O
38 Process data and specifications:
39 Stream 1: H-101: Stream 8: Steam 12: Stream 13:
40 (n)1= 100.0 mol/h ζCH = 1.00
41 xCH : 0.990 ExcessH O= 10.00 % (nH /nCO )= 3.00 XN = 0.05 (nH /nCO )= 3.00
42 xN : 0.010 RCO = 90.00 %

Figure 4.13: Process data and specifications for the new evaluated scenario.

4.4 Circular economy: obtaining sodium alginate

from marine algae

Although the term circular economy was coined in the 1980s, it was not until the
2010s that it became widely used in all productive sectors. The circular economy is
the intersection of environmental and economic aspects. The linear system of our
economy (extraction, manufacture, use and disposal) has reached its limits. The
technical feasibility of a production process is not synonymous of sustainability.
The protection of existing resources must be ensured by taking into account the mini-
mization of both resource consumption and, consequently, waste production, as well
as the implementation of strategies for the recovery of waste. The production process
is proposed under the premise that waste is a resource that is not used properly.
Therefore, the circular economy proposes a new model of society that uses and opti-
mizes stocks and flows of materials, energy and waste and aims to be efficient in the
use of resources. It is based on a multi-R system (Figure 4.14): the waste of some
140 4 Balances in multiple systems

Circular economy
Extraction

Production

Recycle Retrieve

Consume

Repair Reuse

Figure 4.14: Multi-R system of the circular economy.

processes becomes a resource for others; the product must be designed to be decon-
structed and repair and reuse are other elements in this new productive paradigm.
The application of circular economy strategies has reconfigured both produc-
tion processes and defined new production or business models (Figure 4.15). One of
these is based on obtaining energy and resources from waste, recovering the value
of a product at the end of its life cycle for use in a new cycle and allowing waste to

Circular Resource Product life Sharing Servicizing

supplies recovery extension platforms

Figure 4.15: Business models arising from the perspective of the circular economy.
 4.4 Circular economy: obtaining sodium alginate from marine algae 141

be transformed into value through innovative valorization systems. The solutions

range from industrial symbiosis to integrated recycling in closed cycles or “Cradle
to Cradle” systems. This model is ideal for companies that produce large volumes of
waste or that can recover and reprocess waste in a profitable way.
Marine biotechnology (also called blue biotechnology) is an emerging sector for
which annual growth is estimated at 10%, with a global market value of around
2.4 billion euros (year 2015). In recent decades, it has been possible to obtain a wide
variety of high value-added products from marine organisms, with applications in
the pharmaceutical, cosmetic or agri-food sectors, among others.
One of the most interesting raw materials is algae, from which high added-
value products such as sodium alginate can be obtained. Pérez et al. (2014)16 evalu-
ated from an environmental perspective the use of Sargassum muticum (invasive
species in the Galician coast) as a source for a biorefinery process where sodium
alginate is one of the products obtained (Figure 4.16).

Section 100: pretreatment 7

8
H2O
P-101 10
3
Freezer D-101
T-101

V-101 5
2
9
1
11
Biomass C-101 6
4

Section 200: alginate extraction

16 22
12
13
H2O 21 H2O 27
17 23

Na2CO3
CH2O 14 18 H2SO4 19 24 25

GR-201 GR-202 T-203

15 20
T-201 T-202
Section 300: alginate purification
C2H6O C2H6O C3H6O
28 29
26 31 34

38
30 33 36

S-301 32 T-301 35 T-302 37 D-301

Figure 4.16: Flow diagram for obtaining sodium alginate from the algae Sargassum muticum.

16 Pérez-López et al. (2014). Comparative environmental assessment of valorization strategies of

the invasive macroalgae Sargassum muticum. Bioresource Technology 161:137–148.
142 4 Balances in multiple systems

Biomass, once extracted from the sea, washed and transported to industrial fa-
cilities, contains (% by weight on a dry basis): 11.39% alginate, 20.61% extracts,
24.21% other components, 26.40% fines and 17.39% solid waste. The moisture con-
tent of the biomass is 85.5% (by weight). The algae are frozen for one week to facili-
tate the subsequent stages of alginate extraction and purification. The biomass is
washed (T-101) with water (ratio of 54 L kg dry biomass) and then dried (D-101) in
an air recirculation system under the following conditions:
– 97.8% water removal efficiency;
– humidity of fresh inlet air (stream 7): 0.002 kg H2O/kg dry air;
– humidity of the air inlet to the dryer (stream 8): 0.006 kg H2O/kg dry air;
– exhaust air humidity (stream 11): 0.016 kg H2O/kg dry air.

The dried algae are then ground (C-101) prior to the units of the extraction section,
which consists of the following stages:
i. Extraction with formaldehyde (T-201; ρ = 815 kg/m3) to eliminate the fraction
“other components” with an efficiency of 82.6% and a recovery of 92.8% of
CH2O. The extraction requires 565 mL of pure formaldehyde per kg of dry sea-
weed, for which a solution of 1% (volume) of CH2O is used.
ii. Washing with H2O (169.3 L/kg dry seaweed) and filtration (GR-201) that re-
moves the remains of the formaldehyde solution, together with 97.6% of the
washing water.
iii. Extraction with sulfuric acid (T-202; ρ = 1,800 kg/m3) to remove heavy metals.
A solution (0.2 N) is used in a ratio of 56.4 L/kg dry seaweed. 92.8% of the sul-
furic acid is recovered in stream 20.
iv. Washing with H2O (169.3 L/kg dry seaweed) and filtration (GR-202) that elimi-
nates the remains of sulfuric acid with a recovery of 100% of the washing water
in the stream 24.
v. This section ends with an extraction with a solution of Na2CO3 (56.4 L/kg dry sea-
weed) of a concentration of 1% that solubilizes the sodium alginate that is sepa-
rated by stream 26, while the rest of the compounds are separated by stream 27 to
feed other biorefinery processes. About 92.8% of Na2CO3 is recovered in stream 26.

The purification section has the following stages:

i. Precipitation (S-303) of sodium alginate (stream 30) and separation of the entire
Na2CO3 (stream 29), by the addition of 95% ethanol (stream 28) with a flow of
200 L/kg Na2CO3. In stream 29, 100% of the ethanol and 95% of the incoming
water are recovered.
ii. Washed with pure ethanol (T-301), 54.5 L/kg alginate, which separates all water
by the stream 32 and with a 95% recovery of ethanol. The rest of the ethanol
along with the sodium alginate is incorporated into stream 33.
 4.4 Circular economy: obtaining sodium alginate from marine algae 143

iii. Washed with acetone (T-302), 74.3 L/kg alginate, which eliminates impurities,
recovering 95% of the acetone in stream 35. Stream 36 contains alginate, etha-
nol and the rest of acetone.
iv. Finally, with a vacuum drying, ethanol and acetone are eliminated, obtaining
pure sodium alginate in stream 38.

Calculate the daily production of sodium alginate for a feed stream of 100 kg/h of
dry seaweed. In addition, determine the production yield (kg alginate/kg dry sea-
weed) and the air recirculation ratio in the D-101 dryer.

4.4.1 Simulation based on mass balances

To obtain the simulation (based on mass balances) of the process, proceed in the
same way as described in the preceding chapters for the solution of mass balances.

Step 1: Flowchart with identification and enumeration of streams

Figure 4.16 corresponds to the flowchart of alginate production, which allows identifi-
cation of the nomenclature and correlation of the starting data (Figure 4.17).

Step 2: Basis of calculations

The flow of dry algae is considered as the basis of calculation: 100 kg/h (cell B54 in
Figure 4.18).
 A B C D E F G H I J K L M N O P Q R S T U
44
144

45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
4 Balances in multiple systems

Figure 4.17: Data for the production of sodium alginate.

 4.4 Circular economy: obtaining sodium alginate from marine algae 145

V
U
T
S
R
Q
P
O
N
M
L
K
J
I
H
G
F
E
D

Figure 4.18: Stream table.

C
B
A
146 4 Balances in multiple systems

Step 3: Definition of the volume of control and formulation and resolution of the
mass balances.

A B C D E F G H I J
114 Feed: V-101: Freezer T-101: Washing tower
115
116 H2O
117 .
118 Freezer 3
119 2
1 T-101
120
121 .
= = V-101
122 5
123
124 2
125
126
127 4
128
129
130

K L M N O P Q R S T U V
114 D-101
115
116
117
118 P-101
119 D-101 Dry material:
120
121
122 H2O:
123
124
125 Total water balance
126
127
128
129
130
131 Balance on the EGR valve:
132
133
134
135
136
137
138
139
140
141 Balance on the stream divider:
142
143
144
145
146
147

A B C D E F G H I J
131 C-101 T-201
132 (mi)13 = (mi)12 Other components:
133 C-101
134 (mothers)15 = αT–201 .(mothers)12
135
136
137
138 Water:
139 CH2O
140 (mH O)13 = (mH O)12 + (mH O)14 . [1– (FRSolvent)]
141
(mi)6 = (mi)12 2 2 2

142
143 Solvent:
144
145 (VCH O)14 = (mdry algae)12 . φCH = 56,500.00 mL (mCH O)14 = (VCH O)14 . ρCH O
2 2O/kg 2 2 2
146 56.50 L
147
148 5,593.50 L (mH O)14 = (VH O)14 . ρH
2 2 2O
149
150
151 (mCH2O)15 = (FRSolvent) . (mCH2O)14
152
153 (mH O)15 = (FRSolvent) . (mH O)14
2 2
154
 4.4 Circular economy: obtaining sodium alginate from marine algae 147

A B C D E F
156 GR-101
157 (mH O)16 = φH O . (mdry algae)2
2 2
158
159 16
160 13
(mi)17 = (mi)13
161 17
162 (mothers)17 = (mothers)13 – (mothers)18
163
164 (mCH O)17 = (mCH O)13– (mCH O)18
2 2 2
165 18
166 (mH O)17 = (mH O)13+ (mH O)16 – (mH O)18
167 2 2 2 2
168
(mothers)16 = αGR–201 . (mothers)13
169
170 (mCH2O)18 = αGR–201 . (mCH2O)13
171
172 (mH O)18= (mH O)Solvent + (FR)GR–201 . (mCH O)16
2 2 2
173
174
175 (mCH O)18
2
176 ρCH O
(mH O)18 = 2 · (1 – xCH O) + (FR)GR–201 · (mH O)16
177 2 xCH2O 2 2
178

G H I J K L M N O
156 T-202
157 (mi)21 = (mi)17
158
159
160 (mH2SO4)19 = [M] .Vsolution .MMW
161 21
162 17
(m )
163 (VH O)19 = (Vsolutions)19 – H2SO4 19
164 2 ρH SO (mH ) = (mH SO )19 –(mH SO )20
2 4 2SO4 21 2 4 2 4
165
166 H2SO4 19 (mH O)21 = (mH O)17 + (mH O)19 – (mH O)20
167 2 2 2 2
168
169 (mH2SO4)20 = (FRSolvent) . (mH2SO )19 20
170 4
(mH2O)20 = (FRSolvent) . (mH2O)19 T-202
171
172
173
174

P Q R S T U V
156 GR-202
157
158 (mH2O)22 = φH2O .(mdry algae)2
159
160
161 22
162 H2O
21
163 23
(mi)23 = (mi)21
164
165
166
167 (mH2O)23 = (mH2O)21 + (mH2O)22 + (mH2O)24
24
168
169 GR-202
170
171
(mH2SO4)24 = αGR–201 . (mH2SO4)21
172
173
174 (mH2O)24 = αGR–201 . (mH2O)22
175
148 4 Balances in multiple systems

A B C D E F
179 T-203
180
181 (mi)27 = (mi)23
182 27
183 23
184 (malginate)27 = (malginate)23 – (malginate)26
185
186
187 25 26
188 (malginate)26 = αT–203 . (malginate)25
189 T-203
190 (mNa2CO3)26 = (FRSolvent) . (mNa2CO3)25
191
192 (mH2O)25 = φH2O .(mdry algae)2
193 (mH2O)26 = (FRSolvent) . (mH2O)25
194 (mNa2CO3)25 = VSolvent . (wNa2CO3)25
195
196
197
G H I J K L M N O
179 S-303
180
181
182
183
184
185
186 26
28 29
187
188
189
190 30
191
192
193 S-301
194
195
196

P Q R S T U V
179 T-301
180
181 (mC2H6O)31 = ρC2H6O . VC2H6O = ρC2H6O . [ φ. malginate)30]
182
183
184 C2H6O
185 31
186 (mC2H6O)33 = (mC2H6O)31 – (mC2H6O)32
187
188
189
30 33 (malginate)33 = (malginate)30
190
191 32 T-301
192
193 (mC2H6O)32 = (FRC2H6O) . (mC2H6O)31
194
195
196 (mH2O)32 = (mH2O)30
197
 4.4 Circular economy: obtaining sodium alginate from marine algae 149

A B C D E F
198 T-302
199
200 (mC H O) = ρC H O . VC H O = ρC H O . [ φ. malginate)33]
3 6 34 3 6 3 6 3 6
201
202 C3H6O
203 34
204
205 (mC3H6O)36 = (mC3H6O)33 – (mC3H6O)34
206
207 33 36
(malginate)36 = (malginate)33
208
209
210 35 T-302 (mC2H6O)36 = (mC3H6O)33
211
212 (m
C3H6O)35 = (FRC3H6O) . (mC3H6O)34
213
214

G H I J K L M
198 D-301
199
200
201
202
203 (malginate)38 = (malginate)36
38
204
205 36
206
207
37 D-301
208
209
210 (mC2H6O)37 = (mC2H6O)36
211
212 (mC3H6O)37 = (mC3H6O)36
213
214

The application of these balances allows to obtain the stream table (Figure 4.18).

Step 4: Process characteristics

All the streams have been characterized and, therefore, the main characteristics of
the process can be evaluated (Figure 4.19).

A B C D E F G H I J K L
107 Process characteristics
108 Alginate production: Yield: Air recirculation ratio
109 mDry Air
110 11.4 kg/h 0.114 kg alginate/kg dry algae 0.286
111 273.4 kg/d 11.4 % mDry Air = 28.6 %
112

Figure 4.19: Process characteristics.

B110: = T86
B111: = B110*24
F110: = B110/B54
F111: = F110*100
K110: = L82/J82
K111: = K110*100
150 4 Balances in multiple systems

4.5 Proposed case studies

4.5.1 Production of iodine (I2)

One of the conventional processes for obtaining iodine (I2) is through the reduction
of sodium iodide (NaI) contained in algae with manganese oxide (MnO2) in the pres-
ence of sulfuric acid (H2SO4) (Figure 4.20):

2NaI + MnO2 + 2H2 SO4 ! Na2 SO4 + I2 + 2H2 O + MnSO4

V-101
R-101 S-101
H2SO4 1

I2
7
H2O
V-102 6

Algae 2

4 H2O
MnSO4
V-103 5 MnO2
8
3 Na2SO4
MnO2
9 Inerts
NaI , H2SO4, MnO2

Figure 4.20: Simplified flow diagram for obtaining iodine from seaweeds.

Thus, a given flow of algae (6.5% NaI, 35% H2O and rest inert) is treated in stoi-
chiometric quantities with MnO2 and H2SO4 in a reactor with a conversion of 82%.
Part of the reactor output stream is recirculated and mixed with the fresh feed
(Figure 4.20). The rest of the reactor outflow is fed into a separation unit where it
is obtained:
i. Product: 55% I2 and 45% H2O.
ii. Waste stream with residual content of H2O, MnSO4, Na2SO4 and inert.
iii. Recirculation: 25% of MnO2.

All percentages are expressed as % by weight. Calculate:

a. Kilograms of I2 per ton of fresh feed seaweed.
b. Stream composition 8.

Solution: (a) 55.03 kg I2/t algae; (b) 32.54% H2O, 3.20% Na2SO4, 3.40% MnSO4,
60.86% inerts.
 4.5 Proposed case studies 151

4.5.2 Biomass gasification

Forest biomass is one of the major raw materials that must be valued in order to
seek or close processes based on the circular economy. Various pilot and industrial-
scale initiatives are being developed under the auspices of European research pro-
grams. One of the different strategies consists of coupling to a conventional wood
chip gasification process several reaction and separation units that make it possible
to valorize the gas phase and obtain an H2/CH4 mixture that can be used as an alter-
native fuel to natural gas (Figure 4.21).

40.8% H2
25.4% CO
22.9% CO2
6
10.9% CH4 CO
7
CO2
25°C
5

H-101

T-101
350 °C H2
1 atm R-101 8 0.2% CO
4
CH4
Chips
1 3 Tar

O2 2 H2O

Figure 4.21: Simplified flow diagram for obtaining a fuel mixture of H2/CH4 from biomass.

In the gasifier (H-101) a thermochemical process takes place in which biomass is

transformed into a combustible gas by the addition of oxygen (under limiting con-
ditions) and water vapor. The biomass used (6 Tm/d) contains 48.5% C, which is
transformed into H2 and CH4 according to the following reactions:

CðsÞ + H2 OðgÞ ! COðgÞ + H2ðgÞ

1
COðgÞ + O2 ðgÞ ! CO2ðgÞ
2
2COðgÞ + 2H2ðgÞ ! CH4 ðgÞ + CO2ðgÞ

The noncarbon fraction of biomass such as carbonate that does not react is con-
verted to tar (stream 4). The degree of conversion of the oxidation reaction from CO
to CO2 is 100%. The gas produced (stream 5) has a flow of 20 Nm3/h of wet gas with
a dry to wet gas fraction of 0.4, which is introduced into a fixed bed reactor with a
Fe/Cr catalyst where the water gas shift reaction takes place at 350 °C and 1 atm
152 4 Balances in multiple systems

pressure, which allows additional hydrogen to be obtained. This reaction is revers-

ible and exothermic:

COðgÞ + H2 OðgÞ ! H2 ðgÞ + CO2ðgÞ

Callaghan (2006)17 has defined the expression of the equilibrium constant as a func-
tion of temperature for a range of 600–2,000 K:

2, 180.6
log10 Keq = − 2.4198 + 0.0003855 · T +
T

Finally, the gases produced are introduced into an adsorption column (T-101)
where all the CO2 and a majority of the CO are separated to obtain a stream with a
high H2 and CH4 content that can be used as a substitute for natural gas.
Calculate:
a. Conversion of the carbonate fraction.
b. The vapor fraction, expressed as kg vapor/kg biomass, fed to the gasifier.
c. The CO recovery fraction in R-101.
d. The dry base concentration of H2 in the stream 8.

Solution: (a) 92.2%; (b) 2.28; (c) 87.0%; (d) 85.5%.

4.5.3 Alkylation: iso-octane synthesis

Alkylation is a catalytic process in which an isoparaffin (iso-butane) and an olefin

(butylene) are combined to produce a higher molecular weight compound (iso-oc-
tane) called alkylate:

iC4 H10 + C4 H8 ! iC8 H18

The fresh feed stream has a mass flow rate of 50,000 kg/h with a concentration of
25% iso-butane, 25% butylene and 50% n-butane (all expressed as molar percent-
age). The n-butane is an inert in this process. The fresh feed is combined with three
recirculation streams (Figure 4.22) prior to entry into the reactor. Virtually all of the
butylene fed into the reactor is consumed. The output stream from the reactor is
partially recirculated to the reactor, and the remaining flow is fed into a decanter
where the aqueous phase (sulfuric acid) and the organic phase are separated. The
aqueous phase is recirculated to the reactor, and the organic phase with the hydro-
carbons is fed to a distillation column. At the head of the column is separated iso-
octane and n-butane, and the background stream (only contains iso-butane) is re-
circulated to the reactor inlet.

17 https://web.wpi.edu/Pubs/ETD/Available/etd-050406-023806/unrestricted/ccallaghan.pdf.
 4.5 Proposed case studies 153

n-C4H10
i-C8H18
10
T-101
R-101 i-C4H10
n-C4H10
i-C4H10 i-C8H18
C4H8 1
n-C4H10 8
H2SO4 7 V-101
2 3 4
i-C4H10
n-C4H10
i-C8H18
5

6
H2SO4

9
i-C4H10
11

Figure 4.22: Simplified flow diagram for isooctane synthesis.

Data
i. Stream 4 contains 190 moles of iso-butane per mole of butylene and 2 kg of sul-
furic acid (91% by weight) per kg of hydrocarbons.
ii. Stream 2 contains 4.5 moles of iso-butane per mole of butylene.

Solution: 217.4 kmol/h of i-C8H18 in stream 10 and 760.9 kmol/h of i-C4H10 in

stream 11.

4.5.4 Catalytic desalkylation of toluene for benzene production

Desalkylation is a chemical process by which the alkyl radical (methyl group, –CH3)
of a molecule is suppressed. This type of reaction is of great importance in the pet-
rochemical and pharmaceutical industries.
One of the industrial processes for the production of benzene consists of the
catalytic desalkylation of toluene in the gaseous phase with hydrogen (Figure 4.23):

C7 H8 + H2 ! C6 H6 + CH4

A step conversion of 24.5% of toluene is achieved in the reactor, but there is also a
secondary reaction, the generation of biphenyl (diphenyl, phenylbenzene or 1,1-bi-
phenyl) from benzene:

2C6 H6 ! C12 H10 + H2

Data
i. The reactor input (stream 2) has a molar ratio of H2/C7H8 of 5.
ii. The molar ratio of H2/CH4 in stream 10 is 1.
iii. C6H6/C7H8 efficiency is 97.5%.
154 4 Balances in multiple systems

9 H2

8 7 H2/CH4

4
T-101 6
10

V-101
3
5 C6H6
C7H8
1 2

T-102

R-101

11

13
C7H8

12 C12H10

Figure 4.23: Simplified flow diagram for obtaining benzene by catalytic desalkylation of toluene in
gaseous phase with hydrogen.

Calculate for a load of 2,500 mol/h of C7H8 at the input of the reactor (stream 2):
(a) The production of benzene and biphenyl.
(b) The recirculation/purge ratio for the line with H2 and CH4.
(c) The degree of conversion of the secondary reaction.

Solution: (a) 46.58 kg/h benzene and 1.18 kg/h biphenyl; (b) 20.41; (c) 2.5%.

4.5.5 Synthesis of sulfuric acid

The contact method for the production of sulfuric acid is based on the use of a cata-
lyst (platinum or vanadium pentaoxide) to convert SO2 into SO3, which is subse-
quently transformed into H2SO4. (Figure 4.24). In a furnace (H-101) SO2 is obtained
by combustion of pure S (1.25 Tm/h) reaching a conversion of 100%:

SðsÞ + O2 ! SO2

The combustion products are fed into a converter (R-101) where a part of the SO2 is
converted to SO3 at high rate due to the high temperature of the gas. Subsequently,
the gas is cooled and in a second converter (with an addition of air) allows a higher
conversion of SO2 to be achieved:
 4.5 Proposed case studies 155

H2SO4
98%
R-101 R-102 9

8
4 7

T-101
3 V-102
H-101 6
cw 11 H2O
E-101 cw
E-102

10
12 H2SO4
5 Air 95%
S 1 2 Air R-103
V-101

Figure 4.24: Synthesis of sulfuric acid by the contact method.

1
SO2 + O2 ! SO3
2
It is not convenient to directly hydrate SO3 to obtain sulfuric acid because the reac-
tion releases a lot of energy and is potentially dangerous. This SO3 is passed through
an absorption tower where it is combined with concentrated sulfuric acid to form py-
rosulfuric acid (oleum), which is then broken down by hydration into sulfuric acid:

HSO4 + SO3 ! H2 S2 O7
H2 S2 O7 + H2 O ! H2 SO4

The data of the installation are as follows:

– About 45% excess enriched air in the furnace (23% O2).
– The concentration (% by volume) of SO2 at the output of R-101 (stream 4) is
3.75%.
– Standard air in flow 5.
– About 90% conversion of SO2 to R-102.
– The concentration of SO3 at the output of R-102 (stream 7) is 8.75% (% by
volume).
– In the absorption column, the SO3 conversion is 100%. All SO2, O2 and N2 are
coming out of stream 9.
– About 5% in excess of H2SO4 in stream 8.

Solution: 95% sulfuric acid production is 336.6 kg/h (stream 12).

156 4 Balances in multiple systems

4.5.6 Second-generation bioethanol production

The term bioethanol refers to ethanol produced by fermentation of cellulosic, sugar

or starchy raw materials. The engines of most vehicles can directly use ethanol–gas-
oline blends in percentages of 5–10%. For mixtures with percentages from 10 to
85%, flexible fuel vehicles are required, which are equipped with a fuel sensor that
detects the proportion of ethanol and gasoline, adapting the injection and ignition
systems to the characteristics of the mixture.
There are different technologies for obtaining ethanol (C2H5OH) from lignocellu-
losic biomass (also known as second-generation bioethanol),18 the separate hydrolysis
fermentation technology being one of them (Figure 4.25). The hemp biomass (25%
moisture) undergoes acid hydrolysis in the processing unit (TK-101) to convert cellu-
lose into hexose and hemicellulose into pentose with the following yields (9.9% and
90%, respectively). The composition of the biomass is 37.14% cellulose –C6H10O5–,
32.38% hemicellulose –C5H8O4– and 30.48% lignin and the H2SO4 requirement (93%)

CO2 8 H2O
7
H2SO4
C5H10O5
4
6
3

1 R-101 12 T-101
9
2
Biomass 10
TK-101 5

Hemicellulase Must
F-101
(12%)
Cellulase 13
V-101
11
TK-102 C6H12O6
R-102
14
cw
E-202 19

E-203
T-201
15 V-201
21
C2H5OH
(50%) 20 C2H5OH
(94%)

Lignin 18 Vapor T-202

H2O
17 16
Residual E-201 22 H2O
sugars

Figure 4.25: Simplified flow diagram for the production of ethanol from lignocellulosic biomass.

18 González-García et al. (2010). Renewable and Sustainable Energy Reviews 14: 2077–2085
 4.5 Proposed case studies 157

is 20 kg/ton of dry biomass. (percentage by weight). Stream 2 is introduced in a solid–

liquid separator (F-101), to which a cocktail of hemicellulases (20 U/g biomass) is
added. This allows a conversion of 100% of hemicellulose to pentoses that are sepa-
rated (100% recovery) in a liquid stream (stream 3) with 75% of the input water. The
solid cake with cellulose and the rest of the components come out of the stream 10.
The pentoses (stream 3) are fermented (R-101) with a recombinant Zymomonas
mobilis bacterium to obtain ethanol with a conversion of 85%:

3C5 H10 O5 ! 5C2 H5 OH + 2CO2

Stream 4 carries all the CO2 produced and 1% of the ethanol generated, while
stream 5 carries the must stored in tank V-101 (where the concentration of ethanol
is 12%). Ethanol from streams 4 and 5 is recovered in Tower 101 by dragging with
water.
The cellulose of stream 10 is combined with cellulases (TK-102), which allows a
conversion of 90% into hexose. Hexoses are fermented (R-102) with a recombinant
Saccharomyces cerevisiae yeast (95% conversion):

C6 H12 O6 ! 2C2 H5 OH + 2CO2

As in the R-101 reactor, the gas stream contains all of the CO2 produced and 1% of
the ethanol generated. The must is poured into the V-101 tank.
The must (stream 14) is purified in a first distillation column (T-201) by steam
entrainment, which allows all the ethanol to be recovered at a concentration of
50%, which is fed to a dish distillation column where a concentration of 94% is
achieved. The flow rate used is 20%.
If the installation allows to feed 30 tons of dry biomass per hour, calculate:
i. Bioethanol production (kg/d).
ii. Biomass yield (kg ethanol/t dry biomass).
iii. The carbon footprint generated by the CO2 produced during fermentation (kg
CO2/kg bioethanol).

Note: Consider as density of ethanol and water 789 and 1,000 kg/m3, respectively.

Solution: (i) 5,356 kg/d; (ii) 7.44 kg/t; (iii) 0.95 kg/kg.

4.5.7 Synthesis of β-galactosidase

β-Galactosidase is an intestinal enzyme capable of hydrolyzing lactose in the mono-

saccharides that form it, glucose and galactose, which are easily absorbed into the
bloodstream. Lactose is found in milk and other dairy products, which play a key
role in the development and growth of the human being, providing elements such
as calcium, phosphorus or magnesium. However, many consumers are unable to
158 4 Balances in multiple systems

take advantage of this type of benefit due to intolerance or allergy to it, that is, they
are unable to digest this disaccharide due to a genetic deficiency of the enzyme
β-Galactosidase in the digestive tract. For this reason, products labeled “lactose-free”
are increasingly in demand, which means breaking down this disaccharide through
the action of β-galactosidase, which must be produced in industrial quantities.
Accordingly, aerobic fermentation is proposed in complete mix reactors oper-
ated in discontinuous (Figure 4.26) from cheese whey (50 g/L lactose – C12H22O11,
and 25% in excess) with recombinant Saccharomyces cerevisiae.19 As a source of ni-
trogen (TK-102) urea is used (CH4N2O: 2.5 g/L) complemented by various salts:
2.5 g/L de (NH4)2SO4, 5/L de KH2PO4 and 0.4 g/L de MgSO4·7H2O.

R-101

Whey 5

1 3
TK-101
2

MX-101 4

12 V-201
TK-102 6

11
8
9

MF-201 HG-201 UF-202

7 10

13 14
T-201

Figure 4.26: Simplified flowchart for the production of β-Galactosidase from whey cheese.

At the end of the fermentation reaction, the amount of biomass would be obtained
from the following stoichiometric ratio:

C12 H12 O11 + 1.2512NH3 + 5.4311O2 ! 6.2561CH1, 8 O0, 5 N0, 2 + 5.7439CO2 + 7.2463H2 O

The conversion is 100% with respect to ammonium and an excess of 500% air is
used. In order to extract the intracellular enzyme β-galactosidase from the biomass
and other reaction residues, the product has to be separated and purified through
various techniques. First, a hollow fiber microfiltration unit (MF-201) allows for the

19 Feijoo et al. (2017). Journal of Cleaner Production 165:204–212.

 4.5 Proposed case studies 159

reduction of broth volume and the elimination of extracellular impurities, as well

as reaching a concentration of 30 g/L of biomass in the broth. Homogenization then
takes place, where host cells are broken down and intracellular products are re-
leased. This cell rupture occurs due to the combination of large pressure drops and
high turbulence flows with strong shear forces. As a result, biomass is broken down
into amino acids (21%), β-galactosidase (4%), proteins (40%) and cellular waste
(35%, all representing percentages by weight). The biomass fraction that can be
broken is 85% (by weight). An ultrafiltration stage (UF-202) is then required to re-
move all remaining waste and biomass, which achieves a β-galactosidase recovery
fraction of 97.25% and a (stream 10) concentration of 2.1 g/L. This is followed by an
ultrafiltration stage (UF-202) to remove all remaining waste and biomass, which
achieves a β-galactosidase recovery fraction of 97.25% and a (stream 10) concentra-
tion of 2.1 g/L. Finally, the -galactosidase is purified in an ion-exchange column (T-
201), where the solution passes in two cycles through a fixed bed column contain-
ing diethylaminoethyl cellulose resins, a positively charged resin to which β-galac-
tosidase binds due to electrostatic forces. Once bonding occurs, the product is
eluted with a sodium chloride solution (2 m3/kg purified β-galactosidase and a con-
centration of 6.0 g/L). The column is then subjected to stages of equilibrium, wash-
ing and regeneration, while the eluted product is obtained (with a composition of
52.0 kg/m3 of β-galactosidase). The recovery fraction in the column is 98%.
Calculate the volume of the cheese whey stream (stream 1), volume of the stream
containing the nitrogen source (stream 2) and volume of air (stream 4) to obtain 30 kg
of the enzyme β-galactosidase.

Solution: V1 = 51.4 m3; V2: 62.1 m3 and V4 = 20.9 m3.

4.5.8 Biogas conditioning for a cogeneration system

One of the principles of circular economy is the conversion of waste into raw mate-
rial for the production of products and/or energy. One of the most widely used tech-
nologies today for the treatment of wastewater or waste consists of anaerobic
digestion that allows biogas to be obtained (mainly a mixture of methane and car-
bon dioxide). This biogas must be conditioned, that is, maximize the concentration
of methane for subsequent use as fuel in a cogeneration unit (Figure 4.27).
Thus, 158.5 kmol/h containing 72.5% CH4 and 27.5% CO2 (percentages by vol-
ume) is fed to a system of two absorption columns between which there is a recircu-
lation of methanol as an extractive separating agent (consider that for the purposes
of the process it is nonvolatile; therefore, it is not found in any of the gas streams of
the process units). In the absorption column T-102 a molar nitrogen flow (stream 6)
of 2.5 times, the biogas flow is fed. In the cogeneration unit (H-101), complete com-
bustion to CO2 and H2O is produced with 25% excess air.
160 4 Balances in multiple systems

2
98.7% CH4
N2
5
CO2

4 8
T-101 T-102

Biogas 1 CH3OH N2
2 7 Air
0.78% CO2
72.5% CH4
H-101
27.5% CO2

Figure 4.27: Flow diagram for biogas conditioning and subsequent methane cogeneration.

In addition to the value inherent in the benefit of obtaining energy obtained

in the unit, it is necessary to assess the reduction in global warming potential,
since the characterization factors defined by the IPPC20 for methane and carbon
dioxide are 25 CO2eq/kgCH4 and 1 kg CO2eq/kgCO2. The two emission scenarios are:
(a) stream 1 or (b) streams 5 and 8.
Calculate:
i. Recirculation flow rate (stream 4).
ii. Flow rate of the stream 3 and mole fraction of CO2.
iii. Fractional CO2 extraction expressed as absorbed moles/moles in the feed.
iv. Variation of CO2eq in the two emission scenarios.
v. For emission scenario (b), what would be the annual emission cost if the CO2
market price had a value of 5.00 €/Tm?

Solution: (i) 595.1 kmol/h; 637.1 kmol/h and 7.3% CO2; (iii) 96.5%; (iv) 40,910 kg
CO2eq; (v) 305,398 €/year.

20 Acronym for the Intergovernmental Panel on Climate Change: http://www.ipcc.ch/.

Nomenclature
A Notation in the algebraic formulation of a reagent and/or product
a Activity
c Concentration (kg/m3)
Ea Energy of activation
fiα Fugacity of component i in phase α
F Degrees of freedom
g Generation rate in molar units (mol/m3 s)
G Generation rate in mass units (kg/m3 s)
Go Standard Gibbs free energy
GL Number of degrees of freedom
K Kinetic coefficient
K Equilibrium constant
Ka/b Acidity or basicity constant
KPS Solubility product
Ki Equilibrium concentration ratio in the vapor and liquid phase
KHi Henry’s constant of the chemical species i
L Moles of liquid in equilibrium
m Mass flow rate (kg/s)
ma Mass of dry air (kg)
mv Mass of water vapor (kg)
M Mass (kg)
n Molar flow rate (mol/s)
N System mass in molar units
Nec Number of independent equations
NI Number of streams
NJ Number of components
NK Number of units
NS Number of independent chemical reactions
Nx Number of unknown variables
p Partial pressure (N/m2)
Pisat Saturation pressure of component i (N/m2)
P Pressure (N/m2)
q Volumetric flow rate (m3/s)
R Ideal gas constant
Rj Product yield/performance Aj
Sj Product selectivity Aj
T Temperature (K)
t Time (s)
V Volume (m3), or vapor moles
v Rate (m/s)
<v> Average/mean rate (m/s)
wi mass fraction (kg Ai/kg total mass)
x Mole fraction (mole Ai/total mol)
X Molar conversion
y Mole fraction of the vapor phase

https://doi.org/10.1515/9783110624304-005
162 Nomenclature

Subscripts

i Reaction: 1,2 . . . S
j Species or compound: 1,2 . . . w
k Limiting reagent

Greek letters

α Stoichiometric coefficient
αik Relative volatility of two chemical species i and k
αa/b Degree of ionization or dissociation of an acid or base
ρ Density (kg/m3)
ϕiV Fugacity coefficient of component i in the vapor phase
η Yield, performance or efficiency
γiL Fugacity coefficient of component i in the liquid phase
ξk Intensive conversion (mol/m3)
ζk Degree of conversion with respect to the limiting reagent
εM Closing the material balance
ϖ Specific humidity (kg H2O/kg dry air)
ϖr Relative specific humidity
Δ Difference between input and output flows; it also denotes increments
Glossary
Accumulation Corresponds to the amount of property within the system after a time t, so it can
be both positive and negative.

Acid Any substance that tends to give up protons (hydrogen ions) (definition according to
the Brönsted–Lorry theory21).

Base Any substance that tends to accept protons (hydrogen ions) (definition according to the
Brönsted–Lorry theory).

Basis of calculation Unit (global quantity of a flow or of one of its components) on which all
unknowns in a balance of matter and/or energy are referred.

Catalyst Substance that modify the rate of a chemical reaction without being consumed during it.

Circular Economy It is a new production and consumption model based on the optimal use of
raw materials and energy, based on a multi-R system: redesign, rethinking, reduction,
retrieve, reuse, repair and recycling.

Combustion A chemical process in which substances mix with oxygen in the air to produce heat.

Conversion Number of moles that have reacted of that component for each mole of reactant
present in the initial mixture.

Degrees of freedom Degree of freedom of a system is the difference between the number of
unknowns and the number of independent equations.

Derivation or bypass A stream that avoids the physical and/or chemical transformation of a unit
to be reintegrated later into the system.

Furnace A structure or an apparatus in which heat may be generated.

Input/output This corresponds to the flow of property (mass and/or energy) that crosses the
limits of the system in a given time.

Limiting reactant It is the reactant found in the lowest stoichiometric proportion.

Linear equation It is any equation that can be written in the form: ax+b=0, where a and b are real
numbers and x is a variable. A system of linear equations is a collection of two or more linear
equations.

Mass fraction Ratio of mass of a component to the total mass of a mixture.

Mole fraction Ratio of moles of a component to the total moles of a mixture.

Most air Mixture of dry air and water vapor in which dry air is treated as if it were a pure
component.

21 Johannes Nicolaus Bronsted: Danish chemist and physicist (1879–1947); Thomas Martin Lowry:
English physicist and chemist (1874–1936).

https://doi.org/10.1515/9783110624304-006
164 Glossary

Nonlinear equation Equation in which one or more independent variables are multiplied by other
variables and/or are arguments in algebraic functions. A system of nonlinear equations is a
system of two or more equations in two or more variables containing at least one equation that is
not linear.

Packed bed column It is a chemical unit consisting of an hollow tube, pipe or other vessel that
is filled with a packing material.

Phase A homogeneous region of matter. A gas or gas mixture, a liquid or liquid solution and
a crystalline solid are examples of phases. Several phases may coexist, but they must be in
equilibrium in order to apply the rule of phases.

Pressure It is the action of a force that acts perpendicularly to a surface. It is called absolute (used
in most thermodynamic relationships) when measured against a perfect vacuum. The gauge
pressure is the difference between absolute pressure and atmospheric pressure.

Process flow diagram It is a diagram widely used in chemical engineering to indicate the flow
of chemical plant processes and equipment.

Property Any magnitude used to describe a system. They are classified in: (i) intensive, those that
do not depend on the mass of the system (temperature, pressure, density, etc.) and
(ii) extensive, those that depend on the mass of the system (volume, amount of movement, etc.).

Purge Output stream of a recirculation or unit in order to avoid unwanted accumulations.

Recirculation A discharge stream from a unit that is reintroduced back into the system.

Saturated air Mixture of dry air and saturated water vapor. The amount of water vapor in humid
air varies from zero in dry air to a maximum, depending on pressure and temperature, when
the mixture is saturated.

Solubility The maximum amount that can be dissolved from a solute in a given amount of solvent
or dissolution at a given temperature. Usually expressed in g/L or mol/L.

Stoichiometry Quantitative relation between substances consumed and generated in

chemical reaction.

Stream table Tabular quantitative summary of a mass balance on an open system.

Tray column Chemical equipment used to carry out basic operations (e.g., distillation and
absorption) in which it is necessary to transfer mass between a liquid phase and a vapor or gas-
eous phase To facilitate the transfer of matter, a series of plates (or tray) are arranged along the
column to facilitate contact between the two phases.

Valve A device that regulates flow by opening, closing or partially blocking a pipe or process unit.

Vapor pressure It is the pressure exerted by a pure component in the equilibrium at any
temperature, when the liquid and vapor phases coexist.

Yield Fraction of reactant converted to a product.

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Appendices
Appendix A Systems of units: Excel CONVERT
function

A.1 Absolute systems: international system of units

A magnitude is any quality relating to a natural process or a body that can be mea-
sured, either by direct or by indirect methods, and therefore expressed as a numerical
value. When we measure a certain magnitude, we need to express its measurement
with a unit, that is, a value next to the known pattern with which we have compared
the magnitude. Length, mass, volume, the quantity of a substance, voltage, and so
on are magnitudes. Units allow to express a magnitude quantitatively, for example,
grams for mass or centimeters for length.
Since the physical properties of bodies are related by the laws of physics, the
definition of a system of magnitudes and units requires a number of basic or funda-
mental magnitudes, deducing the remaining, called derived magnitudes, by means
of these laws.
Although the choice of the basic magnitudes is arbitrary, in the usual systems
there are always two: length, L, and time, t. To express the quantity of mass, a third
basic magnitude is required: mass, M, or weight, that is, the force of attraction that
the Earth exerts on a system, F. Based on the use of M and/or F, the systems of mag-
nitudes can be as follows:
– Absolute systems: They consider mass as a basic magnitude. The International
System, SI, belongs to this type of systems and kg is the unit for mass. Prior
to the SI, the absolute centimeter–gram–second system considered these
basic mechanical units for distance, mass and time. Similarly, the British sys-
tem considered foot–pound–second as the ternary of units. Table A.1 lists the
main characteristic units.
– Technical systems: They use force as a basic magnitude and, therefore, mass is
a derived magnitude.
– Engineering systems: They use mass and force as basic magnitudes.

A.1.1 Temperature

The concept of temperature originates in the perception of our senses, from the notion
of “heat” or “cold” that a body transmits. For its quantification, temperature scales are
used that are defined by numerical values assigned to the triple point of water (state of
equilibrium between steam, ice and liquid water). Thermodynamic or absolute temper-
ature scales are also used, where the assignment of temperature values does not de-
pend on the properties of a particular substance or type of substance (Figure A.1).

https://doi.org/10.1515/9783110624304-008
172 Appendix A Systems of units: Excel CONVERT function

Table A.1: Absolute unit systems.

Magnitude Centimeter–gram–second (CGS) British (FPS) International (SI)

Basic

Length, L centimeter (cm) foot (ft) meter (m)

Mass, M gram (g) pound (lb) kilogram (kg)
Time, t second (s) second (s) second (s)
Temperature, T degree Celsius (°C) degree Fahrenheit (°F) Kelvin (K)

Derived

Force, M·L·t− dyne (dyn) poundal Newton (N)

Pressure, M·L−·t− bar (Ba) poundal/ft Pascal (Pa)
Energy, M·L·t− erg (erg) poundal ft Joule (J)
Viscosity, M·L−·t− poise (P) lb/ft s kg/m s

Absolute scales Common scales

K °R °C °F

H2O
373.1 671.67 100.00 212.0
Vapor point

Triple point 273.16 491.69 0.01 32.02

Ice point
273.15 491.67 0.00 32.00

0.00 0.00 – –459.67

Absolute zero

Figure A.1: Comparison between the different temperature scales: Kelvin scale,22 Rankine scale,23
Celsius scale,24 Fahrenheit scale25.

22 William Thomson (1824–1907): British physicist, mathematician and inventor. He proposed

that a new scale be used to measure the temperature of bodies that would begin to count at the so-
called absolute zero, a temperature limit below which it is impossible to go below. In 1892 they
decided to name him Lord, being Thomson himself the one who proposed to be granted it as Lord
Kelvin, in honor to the small river on whose shore is settled the University of Glasgow where he
developed his professional career as professor and scientist.
23 William John Macquorn Rankine (1820–1872): Scottish engineer who stood out for his work
on the thermodynamics of steam engines.
24 Anders Celsius (1701–1744): Swedish astronomer.
25 Daniel Gabriel Fahrenheit (1686–1736): German physicist who invented various meteorologi-
cal instruments, such as an aerometer (measures air density), the alcohol thermometer and the
mercury thermometer.
 A.1 Absolute systems: international system of units 173

Equations (A.1), (A.2), (A.3) and (A.4) show the conversions between the different
scales:
T ðKÞ = T ð CÞ + 273.15 (A:1)

T ð RÞ = 1.8 · T ðKÞ (A:2)

T ð RÞ = T ð FÞ + 459.67 (A:3)

T ð FÞ = 1.8 · T ð CÞ + 32.0 (A:4)

A.1.2 International system

The General Conference on Weights and Measures defined the International System
of Units (SI) in 1960 with the aim of establishing a standard and homogeneous sys-
tem throughout the world (Table A.2).

Table A.2: SI basic units.

Magnitude Unit SI base unit

Length meter m
Mass kilogram kg
Time, duration second s
Electric current Ampere A
Thermodynamic temperature Kelvin K
Amount of substance mole mol
Luminous intensity candela cd

Decimal multiples and submultiples of SI units are formed by prefixes designating

the numerical decimal factors by which the unit is multiplied and which are listed
in the “factor” column (Table A.3).

Table A.3: SI multiples and submultiples.

Factor Prefix Symbol Factor Prefix Symbol

 −
 deca da  deci d
 hecto h − centi c
 kilo k − milli m
 mega M − micro µ
 giga G − nano n
 tera T − pico p
 peta P − femto f
 exa E − atto a
 zetta Z − zepto z
 yotta Y − yocto y
174 Appendix A Systems of units: Excel CONVERT function

A.2 Engineering systems

These systems are characterized by considering mass and force as basic magnitudes
(Table A.4).

Table A.4: Basic magnitudes for engineering systems.

Magnitude Metric system British system

Length, L meter (m) feet (ft)

Mass, M kilogram-mass (kg or kgm) pound-mass (lb or lbm)
Force, F kilogram-force (kgf) pound-force (lbf)
Time, t second (s) second (s)
Temperature, T degree Celsius (°C) degree Fahrenheit (°F)

When considering M and F as basic quantities it is necessary to explicitly introduce

the constant of proportionality into Newton’s second law, as indicated in eq. (A.5):
1
F= m·a (A:5)
gc

where gc is a fundamental physical constant that expresses the proportionality be-

tween the force and the product of mass by acceleration. From this point of view,
the pound-force is the force with which 1 pound-mass is attracted to the Earth at a
location where the acceleration of gravity is the standard value, 32.1740 ft/s2.
Therefore, eq. (A.5) would be expressed as

ð1lbÞ · 32.1740 ft
s2
1lbf = (A:6)
gc

From eq. (A.6), the definition of gc can be obtained:

lb · ft
gc = 32.1740 (A:7)
lbf · s2

Equivalently in the engineering metric system, kg and kgf, the value of gc can be
calculated:

kg · m
gc = 9.81 (A:8)
kgf · s2

A.3 Conversion factors

Table A.5 lists the conversion factors between different units for some magnitudes.
 A.4 Excel CONVERT function 175

Table A.5: Equivalences between units.

Length

meter (m) inches (in.) foot (ft) mille – U.S.- (mi)

 . . .·−

.·−  .·− .·−
.   .·−
,. .· . 

Mass

pound (lb) kilogram (kg)

 .
. 

Pressure

mmHg bar atm Pa (N/m)

 .·− .·− .·

.  . .·
 .  .·
.·− .·− .·− 

Energy, heat or work

Joules (J) calorie (cal) British thermal

unit (Btu)

 . .·−
.  .·−
.· . 

Power

Horse power (HP) kW Btu/s Watt (W = J/s)

 . . .·

.  . .·
. .  .·
.·− .·− .·− 

A.4 Excel CONVERT function

The CONVERT function interprets or converts data from one measuring system to
another:
=CONVERT (number, from_unit, to_unit)
– Number: the numeric value to convert.
– From_unit: the starting units for number.
– To unit: the ending units for the result.
176 Appendix A Systems of units: Excel CONVERT function

Table A.6 lists the nomenclature used by the CONVERT function for some of the
most commonly used units. The Excel help function allows you to obtain a detailed
description of them.

Table A.6: Nomenclature of the units in the CONVERT function.

Unit Change of unit Unit Change of unit

Mass Force

Gram “g” Newton “N”

Pound-mass “lbm” pound-force “lbf”

Length Pressure

Metro “m” Pascal “Pa”

Inch “in” Atmosphere “atm”

Time Energy

Day “day” July “J”

Time “hr” Erg “erg”
Second “s” Calorie (. J) “c”

Temperature Btu “BTU”

Degree Celsius “C” Power

Degree Fahrenheit “F” Horse-Power “HP”

Kelvin “K” Watt “W”
Appendix B Graphic symbols for process flow
diagrams

B.1 Process flow diagrams

The process flow diagram represents the operating mode, configuration and opera-
tion of a process plant or a section of plant. The representation must be clear, com-
prehensive, accurate and complete. There are several types of flow diagrams:
– Block diagram:26 This is the simplest form of representation and contains the
basic information with the stages and units of the process.
– Process diagram:27 It represents a process or a process plant by means of graphic
symbols linked by lines.
– Piping and instrumentation diagram:28 Based on the process diagram, it repre-
sents the technical realization of a process with the help of graphic symbols for
the equipment and the piping together with the graphic symbols representing
the measurement and control functions of the process.

Each part or unit shown in the process diagram (Figure B.1) must be identified with
a code number and a name. The identification number consists of a combination of
letters and digits with a general format XX-YZZ A/B, where

4
3
T-101
E–102

1
V–102
2 6
V-101
5
E–101
P–102A/B

9
E–103
P-101A/B
7
E–104
8

Figure B.1: Process flow diagram for a distillation unit with reflux and output recirculation.

26 Blocks flux diagram

27 Process flux diagram – PFD
28 Pipping and instrumentation diagram – P&I D
178 Appendix B Graphic symbols for process flow diagrams

– XX: it identifies the equipment (Table B.1);

– Y: it indicates the sector number of the plant where it is;
– ZZ: it is the number designated to each item for each class of equipment;
– A/B: it identifies units in parallel or in backup (generally, they are not dupli-
cated in the process diagram).

Table B.1: Letter code used in the

flowchart.

Symbol English

C Compressor/turbine
E Heat exchanger
H Fired heater
P Pump
R Reactor
T Tower
TK Storage tank
V Vessel

The piping and instrumentation diagram show the engineering details of the
equipment, instrumentation, piping, valves and fittings, as well as their arrange-
ment. Table B.2 lists the letter code for the different symbols used in the piping
and instrumentation diagram. Figure B.2 also shows the basic piping and instru-
mentation diagram for a distillation column.

Table B.2: Most common symbols used in the piping and instrumentation diagram.

Location of instrumentation

Instrument located in the plant.

Instrument located on the front panel of the control room

Instrument located on the back of the control room panel

 B.1 Process flow diagrams 179

Table B.2 (continued )

Letter code – XYY

First letter (X) Second or third letter (Y)

C Conductivity Control
F Flow rate
I Indicate
L Level Light or low
P Pressure or vacuum Point
R Radioactivity Record
T Temperature Transmit

Type of line or connection

Pneumatic Electrical

Supply to instrument or Internal system link (program or data link)

process connection

PIC

E-101
Cooling water
FIC

T-101 V-101 LIC

YC

Distillate

P-101A/B
LIC

Steam

E-102 Condensate YC

Tails

Figure B.2: Piping and instrumentation diagram defining the basic control on a reflux distillation
column.
180 Appendix B Graphic symbols for process flow diagrams

B.2 Graphical symbols

Heat Transmission Equipment

Heater/Furnace Fired Heater/Furnace

Reboiler Heat Exchanger Cooling Tower

Heat Exchangers (basic symbols) Double pipe heat exchanger

Shell and tube heat exchanger

Plate & frame heat exchanger Evaporator (basic symbol)

Fluid Transport Equipment

Pump Centrifugal pump Centrifugal Fan

Compressor/Turbine/Pump
 B.2 Graphical symbols 181

Material Transfer Equipment

Packed column/Tower Tray column/Tower

Flash drum Reactor or absorber

Vessels

Storage tank Storage sphere

Gas Tank or Gasometer Storage drum/vessel

Separators

Cyclone Electrostatic precipitator or bag filter

Filter Clarifier/Thickener
182 Appendix B Graphic symbols for process flow diagrams

Valves

In-line valve Diaphragm control valve

3-way plug valve 4-way valve

Hand operated valve Ball valve

Needle valve Butterfly valve

Intermittent blowdown Plug valve

B.3 ISO standards

International Standard Organization – www.iso.ch

ISO 10628:1997. Flow diagrams for process plants – General Rules
ISO 14617-2:2002. Graphical symbols for diagrams – Part 2: Symbols having gen-
eral application
ISO 14617-3:2002. Graphical symbols for diagrams – Part 3: Connections and re-
lated devices
ISO 14617-4:2002. Graphical symbols for diagrams – Part 4: Actuators and re-
lated devices.
ISO 14617-5:2002. Graphical symbols for diagrams – Part 5: Measurement and
control devices
ISO 14617-6:2002. Graphical symbols for diagrams – Part 6: Measurement and
control functions
ISO 14617-7:2002. Graphical symbols for diagrams – Part 7: Basic mechanical
components
ISO 14617-8:2002. Graphical symbols for diagrams – Part 8: Valves and
dampers
ISO 14617-9:2002. Graphical symbols for diagrams – Part 9: Pumps, compres-
sors and fans
ISO 14617-10:2002. Graphical symbols for diagrams – Part 10: Fluid power
converters
ISO 14617-11:2002. Graphical symbols for diagrams – Part 11: Devices for heat
transfer and heat engines
Appendix C Solving nonlinear equations

C.1 Newton–Raphson method

For a single equation (y variable), f(x)=0, Newton29–Raphson’s30 method is one of the
most widely used formulas. The method is based on the expansion of the function in
a Taylor series around a reference point (an initial estimate for the solution) x0:

df ðx0 Þ
f ðxÞ ’ f ðx0 Þ + ðx − x0 Þ (C:1)
dx

If f(x) is equal to zero, the resulting equation can be solved for (x–x0):

f ðx0 Þ
ðx − x0 Þ = −
df ðx0 Þ=dx

f ðx0 Þ
x = x0 − (C:2)
df ðx0 Þ=dx

For an iteration k, xk will be obtained analogous to that expressed in eq. (C.2) from
the previous value xk–1 (Figure C.1):

f ðxk − 1 Þ
xk = xk − 1 − (C:3)
df ðxk − 1 Þ=dx

The application of Newton–Raphson involves the following:

– Knowing the derivative of the function either analytically or numerically:

df ðxk − 1 Þ f ðxk − 1 + ΔxÞ − f ðxk − 1 Þ

= (C:4)
dx Δx

– The initial value of the iteration must be close enough to the solution to ensure
convergence. Excel is an excellent tool to obtain a good initial value by graphi-
cally representing the function.

29 Isaac Newton (1642–1727): One of the greatest scientists of all time, together with Gottfried
Leibniz, is the creator of differential and integral calculus. He is the author of the “Philosophiae
naturalis principia mathematica,” in which he described the law of universal gravitation and estab-
lished the basis of classical mechanics. Among his other scientific discoveries are works on the na-
ture of light and optics.
30 Joseph Raphson (1648–1715): English mathematician, contemporary of Isaac Newton. His work
“Analysis aequationum universalis” contains a discussion of Newton’s method for approximating
the roots of an equation.
184 Appendix C Solving nonlinear equations

f (x)
f (x0)

f (x)

x0 x1 x2 x

Figure C.1: Graphical representation of the Newton–Raphson method.

One of the challenges faced by numerical methods is to determine estimates of

error in the absence of knowledge of true values. For example, in Newton–Raphson’s
method an approximation is made considering the previous approximation. This pro-
cess is carried out several times, or in an iterative way, to calculate in a successive
way, waiting each time for better approximations. In such cases, the error is often
calculated as the difference between the previous approximation and the current
one. Therefore, the relative percentage error is given as follows:

current approximation − previous approximation

εa = 100% (C:5)
current approximation

If a percentage tolerance is set, εs, the calculations are repeated until the result ob-
tained is within the acceptable level set previously:

jεa j < εs (C:6)

These errors should also be related to the number of significant figures in the ap-
proximation (eq. (C.7)). Thus, if the criterion defined in eq. (B.6) is met, the result is
certain to be correct in at least n significant figures:
 
εs = 0.5 · 102 − n % (C:7)

In the file “Newton–Raphson Method” the spreadsheets showing the application of

the different solution strategies using Excel are attached.

Example C.1: Resolution of a nonlinear equation by applying Newton–Raphson method

a) Solving the equation: 1.12x 5 − 30.78x 3 = 55.98
 2 
x
Solving the equation: elnðx + 0, 3Þ = ln
2
b) + 5.18
3

a) Analytical calculation of the derivative

Step 1:ߒCalculate the derivative of the function
 C.1 Newton–Raphson method 185

df ð x Þ
= 5.60x 4 − 92.34x 2
dx
Step 2:ߒExcel representation to obtain an initial iteration value close to the true root (Figure C.2).

A B C D E F G H
21 Step 2. Excel representation to obtain an initial iteration value close to the true root
22
23 x f(x) 1.0E+03
24 –5.00 2.92E+02
8.0E+02
25 –4.00 7.67E+02
26 –3.00 5.03E+02 6.0E+02
27 –2.00 1.54E+02 4.0E+02
28 –1.00 –2.63E+01
2.0E+02
29 0.00 –5.60E+01
30 1.00 –8.56E+01 0.0E+00
–6.0 –4.0 –2.0 0.0 2.0 4.0 6.0
31 2.00 –2.66E+02 –2.0E+02
32 3.00 –6.15E+02
–4.0E+02
33 4.00 –8.79E+02
34 5.00 –4.03E+02 –6.0E+02
35 –8.0E+02
36
–1.0E+03
37

Figure C.2: Graphical representation of the target function.

As can be seen from the graph, an x = −2 value would be a good starting point for the iteration.

Step 3: Using the Newton–Raphson formula (Figure C.3).

C42: -2.0 (initial iteration value)
D42: =1.12*C42^5-30.78*C42^3-55.98 (function)
E42: =5.60*C42^4-92.34*C42^2 (derivative)
F42: =C42-(D42/E42) (value of xk)
G42: =1.12*F42^5-30.78*F42^3-55.98 (function value in xk)
H42: =(ABS((F42-C42)/F42)*100 (relative percentage error)
C43: =F42

The other cells are obtained with the "copy" and "paste" commands.
The data for the first 25 iterations are presented in the spreadsheet.

Step 4: Calculation of the solution based on the relative percentage error, │εa│<εs.
Depending on the number of significant figures desired in the solution, the relative percentage
error tolerated can be calculated, εs (Figure C.4). To determine which point in the iteration meets
the desired error, the Excel IF function can be used:
=IF(logical_test;[value_if_true];[value_if_false])
In this case a search is made on the results obtained after iteration 5, 10, 15, 20 and 25 (Figure C.2)
by means of an interconnection of successive SI functions:
D75: =IF(H46<D71;F46;(IF(H51<D71;F51;(IF(H56<D71;F56;(IF(H61<D71;F61;(IF(H66<D71;F66;” keep
iterating”)))))))))
186 Appendix C Solving nonlinear equations

A B C D E F G H

41 Iteration (k) xK–1 f(xK–1) df(xK–1) /dx xK f(xk) εa(%)

42 1 –2.00000 1.54E+02 –2.80E+02 –1.44803 3.03E+01 3.81E+01

43 2 –1.44803 3.03E+01 –1.69E+02 –1.26847 3.16E+00 1.42E+01
44 3 –1.26847 3.16E+00 –1.34E+02 –1.24488 5.23E–02 1.90E+00
45 4 –1.24488 5.23E–02 –1.30E+02 –1.24447 1.52E–05 3.24E–02
46 5 –1.24447 1.52E–05 –1.30E+02 –1.24447 1.29E–12 9.43E–06
47
7 6 –1.24447 1.29E–12 –1.30E+02 –1.24447 0.00E+00 8.03E–13
48 7 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
49 8 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
50 9 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
51 10 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
52 11 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
53 12 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
54 13 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
55 14 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
56 15 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
57 16 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
58 17 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
59 18 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
60 19 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
61 20 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
62 21 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
63 22 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
64 23 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
65 24 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00
66 25 –1.24447 0.00E+00 –1.30E+02 –1.24447 0.00E+00 0.00E+00

Figure C.3: Newton–Raphson calculation.

A B C D
69
70 Significant figures 6
71 εs(%) 5.00E–05
72
73
74
Solution: –1.24447
75
76 ff(
(x)
f(x) 1.29E–12

Figure C.4: Solution according to the percentage tolerance set.

If the condition is not finally met, the message would be “keep iterating,” as greater convergence
to the real solution would be needed. It is also noted that by substituting the solution obtained the
result is close to zero. This test ensures certainty about the solution, since in some cases small
values can be obtained from εa as a result of slow or oscillatory convergence.
 C.2 Using the Excel circular reference application for iterative calculation 187

b) Numerical calculation of the derivative

Step 1: Define the value of Δx for the derivative calculation.

Step 2: Excel representation to obtain an initial iteration value close to the true root (Figure C.5).
As you can see from the graph, a value of x = 2 would be a good starting value to start the iteration.

Step 3: Using the Newton–Raphson formula (Figure C.6).

C41: 2,0 (initial iteration value)
D41: =((EXP(LN(C41^2+0.3)))/LN((C41^2/3)+5.18))-1 (function)
E41: =C41+$C$18 (value of xk−1+Δx). The command $ implies that the cell $C$18 has been entered
as an absolute reference, that is, the cell has been locked in a formula so that it will not
change when copied.
F41: =((EXP(LN(E41^2+0.3)))/LN((E41^2/3)+5.18))-1 (function value for xk−1+Δx)
G41: = (F41-D41)/$C$18 (numerical value of the derivative)
H41: =C41-(D41/G41) (value of xk)
I41: =((EXP(LN(H41^2+0.3)))/LN((H41^2/3)+5.18))-1 (function value for xk)
J41: =(ABS((H41-C41)/H41))*100 (relative percentage error)
C42: =H41

The other cells are obtained with the “copy” and “paste” commands. The data for the first 25 iter-
ations are presented in the spreadsheet.

Step 4: Calculation of the solution based on the relative percentage error, │εa│<εs.
Similar to the procedure followed in the previous section for the analytical calculation of the deriva-
tive, the SI function is used to define the solution based on the relative percentage error tolerated
(Figure C.7):
D74: =IF(J45<D70;H45;(IF(J50<D70;H50;(IF(J55<D70;H55;(IF(J60<D70;H60;(IF(J65<D70;H65;”keep
iterating”)))))))))

Note: This equation has two roots (Figure C.5) to obtain the second root just change the initial
value of the iteration to -2.0 in cell C41.

C.2 Using the Excel circular reference application for iterative

calculation

When a formula refers to its own cell, directly or indirectly, it is called a circular refer-
ence. In the case of iterative calculations this application simplifies the spreadsheet.
Thus, for step 3 of Example C.1 (Newton–Raphson method), the circular refer-
ence to force iterative calculation would mean that in cell C41 it would be con-
nected to H41 (Figure C.8):
C41: =H41 (value of xk−1)
D41: =((EXP(LN(C41^2+0.3)))/LN((C41^2/3)+5.18))-1 (function value for xk−1)
E41: =C41+$C$18 (value of xk−1+Δx).
F41: =((EXP(LN(E41^2+0.3)))/LN((E41^2/3)+5.18))-1 (function value for xk−1+Δx)
G41: = (F41-D41)/$C$18 (numerical value of the derivative)
H41: =C41-(D41/G41) (value of xk)
 A B C D E F G H
188

16 Step 1: Define the value of Δx for the derivative calculation

17
18 Δx = 1.00E–05
19
20 Step 2. Excel representation to obtain an initial iteration value close to the true root
21
22 x f(x) 1.0E+01
23 –5.00 8.72E+00
24 –4.00 5.93E+00 8.0E+00
25 –3.00 3.43E+00
26 –2.00 1.29E+00
6.0E+00
27 –1.00 –2.39E–01
28 0.00 –8.18E–01
4.0E+00
Appendix C Solving nonlinear equations

29 1.00 –2.39E–01
30 2.00 1.29E+00
31 3.00 3.43E+00 2.0E+00
32 4.00 5.93E+00
33 5.00 8.72E+00 0.0E+00
34 –6.0 –4.0 –2.0 0.0 2.0 4.0 6.0
35
–2.0E+00
36
37

Figure C.5: Graphical representation of the target function.

 A B C D E F G H I J

40 Iteration (k) xK–1 f(xK–1) xk–1+Δx f(xK–1+Δx) df(xK–1)/dx xK f(xk) εa(%)

41 1 2.00000 1.29E+00 2.00001 1.29E+00 1.88E+00 1.31276 1.56E–01 5.24E+01
42 2 1.31276 1.56E–01 1.31277 1.56E–01 1.40E+00 1.20117 5.31E–03 9.29E+00
43 3 1.20117 5.31E–03 1.20118 5.33E–03 1.30E+00 1.19709 7.37E–06 3.41E–01
44 4 1.19709 7.37E–06 1.19710 2.04E–05 1.30E+00 1.19708 3.93E–11 4.74E–04
45 5 1.19708 3.93E–11 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 2.53E–09
46 6 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
47 7 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
48 8 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
49 9 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
50 10 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
51 11 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
52 12 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
53 13 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
54 14 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
55 15 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
56 16 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
57 17 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
58 18 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
59 19 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
60 20 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
61 21 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
62 22 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
63 23 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
64 24 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00
C.2 Using the Excel circular reference application for iterative calculation

65 25 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00

66

Figure C.6: Newton–Raphson calculation.

189
190 Appendix C Solving nonlinear equations

A B C D E
68
69 Significant figures 5
70 εs(%) 5.00E–04
71
72
73
Solution = 1.19708
74
f(x) 0.00E+00
75
76
77

Figure C.7: Solution according to the percentage tolerance set.

C D E F G H I J
39
40 xK–1 f(xK–1) xK–1+Δ x f(xK–1+Δ x) df(xK–1)/dx xK f(xK) εa(%)
41 1.19708 0.00E+00 1.19709 1.30E–05 1.30E+00 1.19708 0.00E+00 0.00E+00

Figure C.8: Circular reference warning for Newton-Raphson calculation.

I41: =((EXP(LN(H41^2+0.3)))/LN((H41^2/3)+5.18))-1 (function value for xk)

J41: =(ABS((H41-C41)/H41))*100 (relative percentage error)

Microsoft Office Excel would display a warning message about the existence of a
circular reference.
To operate the circular reference:
1. Click on the Microsoft Office button, Excel Options and then on the Formulas
menu.
2. In the Calculation options section, select the Enable iterative calculation check
box. If you do not change the default value of the iteration, Excel will stop cal-
culations after 100 iterations or after all values in the circular reference change
less than 0.001 between iterations, whichever comes first.

C.3 Successive iterations method using Excel “Goal Seek”

application
A spreadsheet such as Excel can be used to locate the root through successive itera-
tions or trial and error. You can vary the value of x in a given cell until the cell of f(x)
approaches zero. Excel has two tools “Find Target” and “Solver” to systematically ad-
just the initial values. Find Target is used expressly to bring the equation to a value
(in this case, zero) by varying a single parameter.
 C.4 Iteration method by “Solver” 191

Example C.2: Solving a nonlinear equation using the “Find Target” application:

0.88x 3 + 3.38x 2 − 0.58x = 3.65

Step 1: Representation in Excel to obtain a value of the initial iteration interval close to the true
root.

Step 2: Application of the “Goal Seek” option. First you must create a cell that has the value of the
function to be solved and then make the value dependent on another cell (Figure C.9).
The Goal Seek option exists by default in the different versions of Excel, although the configuration
in the menu may be different.

A B C D
30 Step 2: Goal seek
31
32 xK f(xK)
33 –3.71815 –4.54E–05
34

Figure C.9: Value of x and f(x).

In the subsequent dialog box one can specify the cell to adjust (i.e., the value of the function) D33,
with the default value for a value when another cell (x-value) is changed, C33.

Step 3: Multiple roots: To obtain the different solutions of the function, it is enough to vary the
initial value of the iteration with values close to the true root (Figure C.10) and to apply for each
case the option seek objective.

A B C D
35 Step 3: Multiple roots
36
37 xK f (xK)
38 –3.71815 –4.54E–05
39 –1.11919 –7.70E–04
40 0.99663 3.21E–04

Figure C.10: Initial iteration and result values after applying the “Goal Seek” option.

C.4 Iteration method by “Solver”

Solver is an excellent option for solving nonlinear equations system as a systematic

adjustment of the initial values in successive iterations. To load the Solver applica-
tion (it is not by default in Excel):
192 Appendix C Solving nonlinear equations

1. Click on Excel Options.

2. Click on Add-ins, select Solver and then click on go.
3. In the Available Add-ins box, check the box for Solver and then click on OK.

Example C.3: Solving a system of nonlinear equations using the “Solver” application:

f1 ð x Þ = x1 x2 − 3x2 x3 + x4 − 5.84

f2 ð x Þ = x2 + x3 − x1 x4 + 14

f3 ð x Þ = 2x1 − x2 − x3 − x3 x4 − 42.52

f4 ð x Þ = x1 + x2 − 0.5x1 x3 − x4 + 12

Step 1: Preparation of the spreadsheet. Figure C.11 shows the sheet for a system of four nonlinear
equations, where zero has been entered as the initial value of the iteration. Cell C16 corresponds
to the sum of squares of the function values. If it is met for all functions it should also be zero, so
it will be the target function.

A B C D E
1 Solving nonlinear systems
2 Solver application
3
4
f1(x) = x1x2 –3x2x3 + x4 – 5,84
5
f2(x) = x2 + x3 – x1x4 +14
6
f3(x) = 2x1 – x2 – x3 + x3x4 –42,52
7
8 f4(x) = x1 + x2 – 0,5x1x3 – x4 + 12
9

10 xk fi(x)
11 1 21.763 –4.33E–05
12 2 0.401 –4.28E–05
13 3 3.066 1.59E–04
14 4 0.803 1.36E–04
15
16 4.75E–08 Sum of squares
17 Objective function

Figure C.11: Spreadsheet for Solver application for a system of 4 non-linear equations.
Step 2: Application of Solver. On the Data, click Solver. In the subsequent dialog box, specify the
cell you want to set, C16, to 0 for a range of cells B11:B14. The solution obtained by Solver is shown
in Figure C.12.
 C.4 Iteration method by “Solver” 193

A B C D E
1 Solving nonlinear systems
2 Solver application
3
4 f1(x) = x1x2 –3x2x3 + x4 – 5.84
5 f2(x) = x2 + x3 – x1x4 +14
6
f3(x) = 2x1 – x2 – x3 + x3x4 –42.52
7
f4(x) = x1 + x2 – 0,5x1x3 – x4 + 12
8
9

10 xk fi(x)
11 1 21.763 –4.33E–05
12 2 0.401 –4.28E–05
13 3 3.066 1.59E–04
14 4 0.803 1.36E–04
15
16 4.75E–08 Sum of squares
Objective function
17

Figure C.12: Solution obtained by Solver.

Appendix D Solving a system of linear equations

D.1 Matrix inversion method

For a system of linear equation,

E1 : a11 x1 + a12 x2 +    + a1n xn = b1

E2 : a21 x1 + a22 x2 +    + a2n xn = b2
.. .. .. ..
. . . .
En : an1 x1 + an2 x2 +    + ann xn = bn

Simultaneous equations can be represented in matrix notation as follows:

AX = B (D:1)
2 3 2 3 2 3
a11 a12    a1n x1 b1
6 7 6 7 6 7
6 a21 a22    a2n 7 6 x2 7 6 b2 7
6 7 6 7 6 7
A=6 . . 7
.. 7 , X = 6 7
.. 7 , B = 6 . 7
6 .. .. . 5 6 6 .. 7
4 4 . 5 4 5
an1 an2    ann xn bn

where A is the matrix of coefficients, X the matrix of unknowns and B the matrix of
constants.
If A is a nonsingular square matrix of order n x n (the determinant of A is not
zero), then there exists a unique matrix A−1 such that

A − 1A = I (D:2)

The matrix A−1 is said to be the inverse of matrix A. Multiplying both sides of eq.
(D.1) by A−1 yields:

X = A − 1B (D:3)

The solution matrix is obtained by multiplying the matrix of constants by the in-
verse matrix of the coefficients.
The related functions in Excel are as follows:
– {=MDETERM(array)}: it allows to calculate the determinant of a matrix.
– {=MINVERSE(array)}: it calculates the inverse matrix of a matrix with the same
number of rows and columns.
– {=MMULT(array;array)}: it calculates the matrix product of two matrices.
 D.1 Matrix inversion method 195

When operating with matrix functions, the calculation of each term is obtained by
specifying it as a “matrix formula,” since the “copy” and “paste” commands do not
apply in these cases. In the file “Appendix D_Matrix Inversion” you will find the prede-
fined spreadsheets for systems of linear equations with 2, 3, 4, 5 and 6 variables.

Example D.1: Solving a system of five linear equations by matrix inversion

E1 : − x1 + x2 + x3 = 1
E2 : 190, 1 · x2 + 0, 1 · x3 = 100
E3 : 17, 02 · x2 + x3 = 10
E4 : x1 − x3 + x4 − x5 = 0
E5 : 0, 1 · x3 − 3, 5 · x4 + 4, 35 · x4 = 0

Step 1: Matrix of coefficients and matrix of constants (Figure D.1)

A B C D E F G H I J
16
17 –1.00 1.00 1.00 0.00 0.00 1.00
18 0.00 190.10 0.10 0.00 0.00 100.00
19 A = 0.00 17.02 1.00 0.00 0.00 B= 10.00
20 1.00 0.00 –1.00 1.00 –1.00 0.00
21 0.00 0.00 0.10 –3.50 4.35 0.00
22

Figure D.1: Matrix of coefficients and matrix of constants.

Step 2: Calculation of the determinant of A. As the determinant {I27=MDETERM(C25:G29)} is not

zero, the inverse matrix of A can be calculated and therefore this method can be applied to solve
the system of linear equations

Step 3: Inverse matrix

To obtain the inverse matrix of each of the terms, it is necessary to specify it as a matrix formula.
In the cell C35, enter the function you want to apply, {=MINVERSE(C17:G21)}, then select the range
C35:G39, press the F2 key and then CTRL+SHIFT+ENTER (Figure D.2).

A B C D E F G H I
34
35 –1.000 –0.085 1.009 0.000 0.000
36 0.000 0.005 –0.001 0.000 0.000
37 A–1 = 0.000 –0.090 1.009 0.000 0.000
38 5.118 –0.017 –0.016 5.118 1.176
39 4.118 –0.011 –0.117 4.118 1.176
40

Figure D.2: Inverse matrix calculation.

196 Appendix D Solving a system of linear equations

Step 4: The solution is obtained by the matrix multiplication of A−1 and B

To obtain the solution, the matrix product of the inverse matrix and the matrix of constants is made.
In the cell E47, enter the function to be applied, {=MMULT(array; array)}, then select the range E47:
E51, press the F2 key and then CTRL+SHIFT+ENTER (Figure D.3).

A B C D E
46
47 x1 0.582
48 x2 0.525
49 X= x3 = 1.056
50 x4 2.304
51 x5 1.830
52 Figure D.3: Calculation of the solution.

D.2 Gauss–Seidel method

For a system of linear equation,

E1 : a11 x1 + a12 x2 +    + a1n xn = b1

E2 : a21 x1 + a22 x2 +    + a2n xn = b2
.. .. .. ..
. . . .
En : an1 x1 + an2 x2 +    + ann xn = bn

If the elements of the diagonal (aii) are not zero, a classic eighteenth-century itera-
tive method can be used, such as that of Gauss31–Seidel32, which for the k iteration
the solution would be given as follows:
−1 
iP  n 
P 
ðkÞ ðk − 1Þ
− aij xj − aij xj + bi
ðkÞ j=1 j=i+1
xi = (D:4)
aii

One of the challenges of numerical methods is the calculation of error in the absence
of knowledge of true values. For example, in the Gauss–Seidel method, an approxi-
mation is made considering the previous approximation. This process is carried out
several times, or in an iterative way, to calculate in a successive way, waiting each
time for better approximations. In such cases, the error is often calculated as the

31 Johann Carl Friedrich Gauss (1777–1855): German mathematician, astronomer and physicist
considered “the prince of mathematics.”
32 Philipp Ludwig von Seidel (1821–1896): German astronomer and mathematician.
 D.2 Gauss–Seidel method 197

difference between the previous approximation and the current one. Therefore, the
relative percentage error is given by

current approximation − previous approximation

εa = 100% (D:5)
current approximation

If a percentage tolerance is set, εs, the calculations are repeated until the result ob-
tained is within the acceptable level set previously:

jεa j < εs (D:6)

These errors should also be related to the number of significant figures in the ap-
proximation. Thus, if the criterion defined in D.7 is met, it will be certain that the
result is correct in at least n significant figures:
 
εs = 0.5 · 102 − n % (D:7)

In the file “Appendix D_Gauss-Seidel” you will find the predefined spreadsheets for
systems of linear equations with 3, 4, 5 and 6 variables.

Example D.2: Solving a system of four linear equations using the iterative Gaussian–Seidel
method (Figure D.4):

E1 : 10x1 − x2 + 2x3 = 6
E2 : − x1 + 11x2 − x3 + 3x4 = 25
E3 : 2x1 − x2 + 10x3 − x4 = − 11
E4 : 3x2 − x3 + 8x4 = 15
First you enter the coefficients of the unknowns in Excel.

A B C D E F G H I J K
1 Solving linear system by iteration
2 Gauss–seidel method
3
4 j=1 j=2 j=3 j=4 b
5 i=1 10.00 x1+ –1.00 x2+ 2.00 x3+ 0.00 x4 = 6.00
6 i=2 –1.00 x1+ 11.00 x2+ –1.00 x3+ 3.00 x4 = 25.00
7 i=3 2.00 x1+ –1.00 x2+ 10.00 x3+ –1.00 x4 = –11.00
8 i=4 0.00 x1+ 3.00 x2+ –1.00 x3+ 8.00 x4 = 15.00
9

Figure D.4: Systems of linear equations with 4 variables.

Equation (D.4) displayed for a four-variable system leads us to the equations that must be imple-
mented in Excel (Figure D.5). In addition, the zero value in each of the variables has been consid-
ered as the initial value.
B13: =((−1)*($D$5*C12+$F$5*D12+$H$5*E12)+$K$5)/$B$5 (equation of the variable x1) The com-
mand $ implies that the cell $D$5 has been entered as an absolute reference, that is, the cell
has been locked in a formula so that it does not change when you copy and paste.
 198

A B C D E F G H I J K L
10
x1(k) x2(k) x3(k) x4(k)
11 Iteration (K) EQUATIONS
12 1 0.0000 0.0000 0.0000 0.0000
13 2 0.6000 2.3273 –0.9873 0.8789
–(a12x2(k–1) + a13x3(k–1) + a14x4(k–1)) + b1
14 3 1.0302 2.0369 –1.0145 0.9843 x1(k) =
15 4 1.0066 2.0036 –1.0025 0.9984 a11
16 5 1.0009 2.0003 –1.0003 0.9998
1.0001 2.0000 –1.0000 1.0000 –(a21 x1(k)) – (a23x3(k–1) + a24x4(k–1)) + b2
17 6
1.0000 x2(k) =
18 7 2.0000 –1.0000 1.0000 a22
19 8 1.0000 2.0000 –1.0000 1.0000
20 9 1.0000 2.0000 –1.0000 1.0000
–(a31 x1(k)) – (a32x2(k)) – (a34x4(k–1)) + b3
21 10 1.0000 2.0000 –1.0000 1.0000 x3(k) =
22 11 1.0000 2.0000 –1.0000 1.0000 a33
23 12 1.0000 2.0000 –1.0000 1.0000
24 13 1.0000 2.0000 –1.0000 1.0000 –(a41 x1(k) + a42x2(k) + a43x3(k)) + b4
25 14 1.0000 2.0000 –1.0000 1.0000 x4(k) =
a44
26 15 1.0000 2.0000 –1.0000 1.0000
27 16 1.0000 2.0000 –1.0000 1.0000
Appendix D Solving a system of linear equations

28 17 1.0000 2.0000 –1.0000 1.0000

29 18 1.0000 2.0000 –1.0000 1.0000
30 19 1.0000 2.0000 –1.0000 1.0000
31 20 1.0000 2.0000 –1.0000 1.0000
32 21 1.0000 2.0000 –1.0000 1.0000
33 22 1.0000 2.0000 –1.0000 1.0000
34 23 1.0000 2.0000 –1.0000 1.0000
35 24 1.0000 2.0000 –1.0000 1.0000
36 25 1.0000 2.0000 –1.0000 1.0000

Figure D.5: Application of the Gauss–Seidel method for a four-variable system.

 D.2 Gauss–Seidel method 199

C13: =((−1)*($B$6*B13)+((-1)*($F$6*D12+$H$6*E12))+$K$6)/$D$6 (equation of the variable x2).

D13:=((−1)*($B$7*B13+$D$7*C13)+((-1)*(+$H$7*E12))+$K$7)/$F$7 (equation of the variable x3).
E13: =((−1)*($B$8*B13+$D$8*C13+$F$8*D13)+$K$8)/$H$8 (equation of the variable x4).

Then you “copy” and “paste” these cells into as many rows as you want. The result for the first 25
iterations is shown on the sheet.
Depending on the number of significant figures desired in the solution, the relative percentage
error tolerated can be calculated, εs (D.7), and compared with the error obtained in the iterations:
P17: =(ABS((B16-B15)/B16))*100 (relative percentage error obtained in iteration five for variable x1)
To determine which number of the iteration fulfils the desired error, the IF function (=IF(logi-
c_test; [true_yes_value]; [false_yes_value]) of Excel can be used, through a successive interconnec-
tion of it:
=IF(P17<P14;B16;SI(P20<P14;B21;SI(P23<P14;B26;SI(P26<P14;B31;SI(P29<P14;B36;”please keep
iterating”))))) (condition for variable x1)
If the condition is not finally verified, the message that would be displayed would be “please
keep iterating,” as greater convergence to the true solution would be needed.
Index
β-Galactosidase 157 Macroscopic balance 3
Mass balances 2
Accumulation 3, 7 Mass flow rate 5
Acid–base reactions 110 Metabolic Engineering 95
Acidity constant 83 Metabolic network 96
Activity 71 Microscopic balance 3
Moisture content 27
Bioethanol production 156 Molar conversion 57
Boundary conditions 2 Multiple reactions 109
Bypass 24
Nonstationary state 31
Circular economy 139
Component balance 6 Overall balance 10, 14
Conservation laws 1
Control volume 2 Principles of conservation 1
Psychrometric diagrams 27
Degrees of freedom 10 Purge 16
Desalkylation of toluene 153
Dew point 27 Reaction rate 91
Dry bulb temperature 27 Recirculation/recycle 16
Relative humidity 27
Extent of dissociation 84
Selectivity 68
Feed/recirculation ratio 23 Sequential modular method 118
Fenton catalysis 94 Simultaneous solution method 118
Flowchart 12 Solubility product 111
Flow rate 1 Specific humidity 27
Fugacity 71 Specific volume 28
Spray temperature 28
Gauss–Siedel iterative method 23 Stoichiometric coefficients 52
General balance 1 Stoichiometry 51
Generation 3 Stream divider 25
Stream table 3
Heuristic rules 8 Synthesis of methanol 126
Humidity charts 27 System boundaries 9

Input/Output 3 Wet bulb or saturation temperature 28

Intensive conversion 57
Ionization constant 84

https://doi.org/10.1515/9783110624304-009