Академический Документы
Профессиональный Документы
Культура Документы
&
MICROSOFT OFFICE
EXCEL
P. Ditl, J. Skrivánek
1
CONTENTS
INTRODUCTION 3
Decision-Making 3
Working Tools for Decision-Making 3
Complete System Characteristic 3
BASIC CONCEPTS 4
What Is Flowsheeting? 4
What Is a Balance? 4
What Is a Component? 5
What Is a Balanced System Boundary? 5
What Is a Limited Time of Balance? 5
What Is an Amount of Component? 6
What Is a Continuous Process? 7
What Is a Source Stream of Reaction? 7
Why Enthalpy Balance and not Heat Balance? 8
What is the Difference between Material Balance and Enthalpy Balance? 8
Enthalpy Balance 9
Formulation of the Problem Being Solved 9
How Many Equations Define the System Behaviour in Full? 9
Possibilities of Solving a Model 9
CONCLUSION 28
2
INTRODUCTION.
Decision-Making
Experience and practice have made us realise that mass and material balances represent effective
tools for decision-making. The concept of decision-making shall include the following spheres of
action:
• Sizing lines and individual apparatus in designing.
• Adjusting a line to the modified composition of materials.
• Adjusting a line to modified requirements for quality (composition) of a product.
• Diagnosing failures of operation of lines and locating causes of failure.
• Checking or substituting measured quantities by calculating those quantities and taking
advantage of this principle to ensure easier control or to carry out process or guarantee
measurements.
• Optimising operation of a line and searching for alternatives of operation using the method:
“What will happen if.....?”
• Training and teaching operating personnel.
This enumeration is certainly not complete, however, it gives us an idea of the content of the concept
of decision-making.
3
BASIC CONCEPTS
If we know the composition, temperature and pressure for a stream, we are able to determine:
• any intensive physical property of the stream – such as density, viscosity, or surface tension,
• whether the stream consists of one or more phases and what these phases consist of.
In general we can say that all intensive physical properties represent a function of composition,
temperature and pressure. With liquid and solid phases the effect of pressure on the value of intensive
properties is mostly negligible. As to ideal gases, the change of enthalpy with pressure is null. A more
noticeable dependence of enthalpy on pressure is encountered only with streams the position of which
is in the proximity of a two-phase range. That leads to the following conclusions:
• The composition of the stream must serve the purpose of mass balance.
• The temperature of the stream must serve the purpose of enthalpy balance.
• The pressure of the stream does not constitute the object of balance calculations. If we need
to know its value (for instance, in order to calculate in what phase the stream is – whether in a
gaseous or liquid phase), its value must be determined.
What Is Flowsheeting?
Flowsheeting consists of a flow sheet of the process being analysed and the complete system
characteristic. It includes neither dimensions and structural design of the apparatus nor the planning of
the piping system. Flowsheeting consists in the following steps:
• Drawing up a process flow sheet
• Defining components in individual streams
• Establishing balance equations
By working them out we obtain the missing information for complete system characteristic.
Flowsheeting is a working tool for decision-making.
What Is a Balance?
Any extensive property, that is a property, the numerical value of which changes with the size of the
system, can be balanced. This class includes mass, volume, internal energy, entropy, and so forth. On
the contrary, intensive properties are properties with their value being independent of the size of the
system, such as density, temperature, viscosity, specific heat, colour, hardness, and so forth.
Within the defined boundaries of the system being balanced and the limited time for which the
balancing is being performed, the following balance relation holds good for the extensive property
being balanced:
Input + Source = Output + Accumulation
• Input is the quantity of the extensive property being balanced that passes into the system
through the balanced system boundaries within the limited time for which the balance is being
performed.
• Source is the quantity of the extensive property being balanced that is generated within the
system boundaries in the course of the balanced period. Disappearance of the extensive
property is expressed as a source with a negative sign.
• Output is the quantity of the extensive property being balanced that gets out of the system
through the balanced system boundaries within the limited time, for which the balance is being
performed.
• Accumulation is the change in quantity of the extensive property being balanced within the
balanced system boundaries in the course of the balanced period.
The introduction of a source element enables us to balance all extensive properties, even those
properties to which the law of conservation does not apply (for instance, entropy, exergy, component
subject to a chemical reaction, and so forth). In order to apply a balance relation it is still necessary to
define in greater detail the concepts involved in the balance relation.
4
At the start of each balancing, three concepts must be defined clearly:
• Extensive property being balanced
• Balanced system boundaries
• Limited time for which the balance is being performed.
What Is a Component?
An extensive property being balanced will be hereinafter referred to as a component. Components can
be
• pure chemical compounds, such as methane, sulphuric acid, water, oxygen, to which a
specific molar mass can be attributed,
• polymers – chemically pure substances, whose molar mass is not clearly defined,
• substances representing a group of chemical compounds, such as fats, R2O3, silicates,
hydrocarbons C4+,
• substances that cannot be specified chemically, such as water-insoluble residue, substances
with density lower than water, substrate in bioreactors.
• Also, a component may be defined as a particle with a size of 50µ up to 100µ, or a particle
with other than white colour.
When defining a component it is necessary to define in a precise manner the method through which
the component is determined. Differences in methods used for determining a component can lead to
significant discrepancies. For instance, it is not enough to define a component as water content in a
solid phase, it being loose material. Water can be on the surface of particles; in the case of porous
particles it can be bound through adsorption to the inner surface of particles; it can be water of
crystallisation if the particles are of crystalline nature, and in the case of some substances it can be
chemically bound water. Based on the method of determining the water content, results can differ
even in the order of magnitude.
This applies also to a component defined as a particle size. If we determine the proportion of particles
of a specific dimension by measuring the particle’s largest dimension under the microscope, by
separating on sieves, or by measuring the distribution of the particles using the settling method, we
will arrive at different results.
5
Source of component per unit of time (rate of source) can be seen as an imaginary (fictive) stream that
enters into the system; however, it does not cross its boundaries at the same time. It can have both
positive – a component is formed – and negative - a component disappears - value.
Accumulation per unit of time can be designated as the rate of accumulation; it is the change in
quantity of the balanced component in the system with time. Therefore, the final form of the balance
relation reads as follows:
Input Stream of Component + Fictive Stream of Component = Output Stream of Component +
Accumulation Rate of Component.
6
70 745.0 977.7 0.001342 0.001023 31.87 68.17 38.00
The view of revenue offices on this case is not clear. The relative deviation of the highest and lowest
value is more than 5%. However, this implies for us that from now on we will use either the amount in
-1 -1
kmol·s or in kg s for expressing the size of the stream in balancing. This is in agreement with the
-1 -
expression of composition by mole fraction of kmol·Σkmol in the first case or weight fraction of kg·Σkg
1
in the second case.
The dimensions of flows selected in that manner agree with the SI system. Energy flows come out in
-1
enthalpy balances as kW, that is kJ s .
It is necessary to point out that there are also other possibilities of expressing the composition to make
it invariant to temperature and pressure – for instance, a relative mole fraction, molar concentration,
and the like. However, it is not difficult to convert these values to mole or weight fractions.
7
• enter the component’s stoichiometric coefficient into the component’s row, with a positive sign
if the component is a product of the reaction (second term on the right side of the
stoichiometric equation), or with a negative sign if the component is a reactant (first term on
the left side of the stoichiometric equation) in the case of material balance;
• multiply, in addition, the stoichiometric coefficient (with the appropriate sign) by the
component’s molar mass in the case of mass balance.
Sample Problem:
If we take the stoichiometric equation of formation of sodium hydrogen carbonate in manufacturing
soda
NaCl + NH3 +CO2 + H2O = NaHCO3 + NH4Cl
as an example, the column for the fictive stream will read as follows:
for molar balance: for mass balance:
components nr components mr
1 H2O -1 1 H2O -18.02
2 NaCl -1 2 NaCl -58.44
3 CO2 -1 3 CO2 -44.01
4 NH3 -1 4 NH3 -17.03
5 NaHCO3 1 5 NaHCO3 84.01
6 NH4Cl 1 6 NH4Cl 53.49
8
Individual parts of the balance equation are expressed in kW.
Removal of energy into the surroundings has a plus sign, while power supply has a negative sign. The
system in which the interchange of energy with the surroundings is zero, is called adiabatic.
Only one enthalpy balance holds good for the balanced block.
Enthalpy Balance
To draw up an enthalpy balance physical and chemical data of individual components must be
available. Various databases can serve as sources of data. Data from individual databases may not
be quite consistent and therefore it is practical to use only one database if possible and not to take
data for various components from different databases. A database adapted for Excel from the book by
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood - The Properties of gases and liquids (Mc Graw Hill
1982) is used for the purposes of teaching at the Czech Technical University.
The database of the National Bureau of Standards or the DECHEMA database can be recommended
for industrial applications. The respective Internet addresses are provided at the end.
9
software, however, it is an absolute illusion to expect that someone would be willing to sacrifice the
time needed in order to become familiar with the software.
However, there is software available with the following advantages:
• It is installed in every computer in an enterprise – one can assume that Microsoft Office is
installed in every PC.
• Almost everyone, who is able to use a computer, has a good command of it. And if the
manager is not willing to communicate with a computer, his secretary is bound to have a
good command of this programme.
• Operating records and source data are stored by means of this programme. Transmitting
source data into our model is therefore possible without even one number being retyped
using a keyboard.
• All and any economic and statistical analyses are performed by means of this programme.
Transferring data for these analyses is also performed through floppy disks, over the net and
through other channels, but not by typing the data on the keyboard.
• Tables and diagrams obtained using this programme can be, without the slightest difficulty,
transferred into the most widespread Word processor.
We are talking about Excel. Working with Excel may not be as elegant as working with special
programmes, but the above-mentioned advantages are significant to such an extent that for the time
being Excel cannot be replaced with any other tool – exception perhaps being Lotus II, but it is fully
compatible with Excel.
10
Solving a System of Equations – a Model
In general, tasks are not noticeably complicated from the mathematical point of view. Solving a system
of equations, most of which are linear, is always involved.
It is important to solve the essential question of whether the system has been overdetermined, that is
whether also data that should be the result of the calculation are available for the system
characteristic, or whether the system has been determined insufficiently, that means that not enough
information is available to enable us to determine the complete system characteristic.
The method of how to proceed from process description to solvable mathematical model has certain
logic, which must be adhered to when computing with a calculator as well as when using programmes
such as PRO, MAX, or CHEMCAD. The mentioned programmes obtain the required information from
the user using various menus. Formation of and recording in what is known as a specification table is,
in fact, making a list of all equations that are available to us to solve the problem.
The methods for EXCEL have exactly the same logical structure as the mentioned programmes, with
the difference consisting in that we know exactly why we take respective steps. Although this method
is more laborious, we know the logic and subject-matter of the procedure, and therefore we are able to
eliminate any contingent mistake or error in the specification right at the beginning.
A system can be solved using a calculator only in the cases where it is possible to apply the solution
through iterative method by means of substitution.
11
The following part demonstrates in detail on sample problems the application of the general methods
discussed above. Stress is put on the uniform procedure, which must be unconditionally observed for
success of the solution to be guaranteed.
General Information
In describing the methods we will proceed by providing the reader with a standard text and with a
solution in EXCEL of the problem being described. This file has been provided with quite a detailed
description and numerous commentaries, so that the standard text can serve, after the initial working
through, only as reference. In addition, series of problems solved in EXCEL have been attached so
that the user can review the methods on other problems as well. This file contains problems ranging
from the most simple to the larger-scale ones. Commentaries on these problems do not constitute part
of the standard text anymore; the commentary, with which the EXCEL file has been provided, should
be sufficient for the user.
Let’s discuss the individual phases of the procedure in detail.
Description of Technology
A saturated solution of NaCl contains 35.6600 g NaCl/ 100g H2O.
It reacts with the yield of 100.0000 %
with a gas mixture consisting of 32.0000 volume % NH3
and 68,0000 volume % CO2.
Solid sodium bicarbonate (NaHCO3) and mother liquor
containing, on the top of NH4CL, also 7.5300 g NaHCO3/100g H2O
are formed in the reaction.
The plant processes 100.0000 tons NaCl / day.
This description, which corresponds to a typical textbook example, is quite insufficient from the point of
view of industrial application.
However, let’s pay attention to the most relevant characteristic of the process description, which are
the cells marked in colour. An essential rule applies to the methods:
The content of the cells can be changed (by entering a value using the keyboard) only in the fields
distinguished with colour.
Let’s take notice of the cell giving the content of carbon dioxide in the entrance gas. If the entrance
gas contains only two components and if the content of ammonia has been entered, the content of
carbon dioxide cannot be entered since the percentage of its content must correspond to 100 – the
percentage of ammonia.
It is very important to obey this rule. If it is disobeyed, the programme will not present a correct result
should any parameter be changed in a proper manner. It is very difficult to try to find, especially with
larger files, the cell into which a numerical value was entered by mistake instead of allowing the
operation with other cells. The greatest danger arises if there are more persons with access to the
programme. If another person different from the author uses the programme, the following precaution
must be taken:
To lock all cells apart from the ones marked with colour (i.e. into which data can be entered using
k eyboard).
12
In describing the technology it is necessary to have the opportunity to check the accuracy of such
description. All numerical entries must come from somewhere. The source must be obvious with every
numerical entry. It must be clear whether the figure in the cell has been taken from literature, operating
records, whether it is the required value, or an assumption or estimate.
Let’s see to what extent the above-mentioned description meets these requirements:
It has been stated that the saturated solution contains 35.66 g NaCl / 100 g H2O. However, it has been
mentioned neither from which monograph this information was taken nor for which temperature this
information holds true.
It reacts with the yield of 100%. It has not been stated whether this is required or assumed. Only one
component can actually disappear from the reacting system. If NaCl disappears completely, it means
that the relief gases will contain a negligible amount of NH3. In this case it is necessary to distinguish
precisely whether those 100 % constitute an assumption or requirement.
The composition of the gas mixture – the information that the entrance gas contains only carbon
dioxide and ammonia and that there is 38 volume per cent of ammonia – must come from some
source – Encyclopaedia by Kirk-Othmer, operating records from another soda processing plant,
assumption of a designer, estimate – but in any case this source must be provided.
As to solubility of NaHCO3, it must be clear for what temperature this solubility holds true, whether the
influence of NH4Cl being present is considered, or whether a saturated or supersaturated solution is
taken into account.
The amount of processed salt can be limited by the sales of the salt, transmission capacity of traffic
roads, permissible quantity of salts in a watercourse, investment means available, and so forth.
This determination of the origin of the data is not an end in itself. For purposes of optimising it is
necessary to know which parameters can be changed and to what extent. It is possible to change the
proportion of ammonia in the entrance gas to quite a considerable extent, but it is not possible to
change the solubility more than as adequate to the permissible temperature range.
2. Divider – output streams are of the same composition and of the same phase – at least two
streams exiting
13
3. Separator - output streams are of various composition and possibly of different phase as well
Streams are indicated by numbers. In compliance with the practice established in designing the
following indications are recommended:
2
2
Streams must be provided with arrows so that it can be unequivocally determined where the stream
proceeds from and where it passes into – orientation of the stream.
Streams cannot be connected or disconnected in any point. Such points must be drawn in the flow
sheet as the nodes being balanced (blenders or dividers).
In other respects, all and any tools can be used in order to draw flow sheets, be it a set of rectangles
connected by streams, represented by connected arrows perpendicular to one another, or more
elegant flow sheets taking advantages of the possibilities offered by AUTOCAD.
The following drawing can serve as an object example of a flow sheet. It was drawn up using EXCEL.
One can see the differentiation of the direction of streams and application of the “Divider” balance
nodes where the streams split and the “Blender” balance nodes where the streams join.
1 3
4
K
R 5
6
D
2
2
8
S
9
With flow sheets that consist of more balance nodes, an incidence matrix must be set up.
14
Incidence Matrix
An incidence matrix provides information about what streams enter into the pieces of apparatus and
what streams exit from the pieces of apparatus.
The number of columns of an incidence matrix exceeds the number of nodes being balanced by one.
This one extra balance node is the surroundings. The surroundings is formally regarded as a node
being balanced. The number of rows agrees with the number of streams.
For every stream in its respective row we enter -1 into the cell in the column corresponding to the
node from which the stream exits and +1 in the column corresponding to the node into which the
stream passes. We post zeros into the remaining cells in the row.
If we mark the
Reactor column with R
Condenser column with K
Divider column with D
Blender column with S
Surroundings with O,
then the incidence matrix for the given flow sheet will read as follows:
incmat
stream R K D S O
1 1 0 0 0 -1
2 -1 0 0 0 1
3 -1 1 0 0 0
4 0 -1 0 0 1
5 0 -1 1 0 0
6 0 0 -1 0 1
7 0 0 -1 1 0
8 0 0 0 1 -1
9 1 0 0 -1 0
10 1 0 0 0 -1
11 -1 0 0 0 1
The incmat i;k element of the incidence matrix is the value for stream i in block k.
We set up a matrix by first filling all cells with zeros. Then we proceed stream by stream – i.e. row by
row – and we mark in each row from which node the stream exits (we enter –1 into the respective cell)
and into which node the stream passes (we enter 1 into the respective cell).
Thereafter we perform a check by establishing in each column the number of streams passing into the
node – the number of cells containing 1 – and the number of streams exiting from the node – the
number of cells containing -1. This check must be performed carefully because an error may have
fatal consequences.
The incidence matrix will facilitate our further work when setting up a matrix of coefficients.
15
List of Components:
Column 1 contains the component’s serial number.
Column 2 contains the component’s name.
Column 3 contains, in the case of a defined chemical compound, the component’s molar mass.
The total of masses of all components in a sample of the stream must be equal to the total mass of the
sample.
Abidance by these definitions is necessary for successful balancing.
Every component is defined using the method through which its amount in the sample of the stream
has been determined. This seemingly simple operation is the most common source of errors. In
comparison with time we will need to look for an error, checking every step three times will actually be
a great saving. Remember to take components one after the other and refer to the list of streams to
see through which stream the component passes into the system and through which stream it exits
the system. It isn’t a waste of time.
Some components present in the system cannot be balanced. To decide which components will be
balanced and which won’t is the most difficult task in balancing.
Molar masses are to be taken from a database. These values are recommended not to be retyped
from the database, but to be copied using a box. Thereby we protect ourselves against error, which
could be made by retyping. In retyping we transfer rounded values and thus deprive ourselves of part
of the information.
The following examples demonstrate what such a list may look like:
The first example corresponds to the bicarbonate column, the flow sheet of which is shown on p. 12.
The second example is from the balance sheet of a desulphurisation plant. To facilitate
comprehension we provide a flow sheet as well. Notice that one component is defined as gasses from
which soluble salts are generated in the solution after absorption. That should serve as a proof of the
statement mentioned above that to define components is not a simple and primitive task. The
definition of the composition of streams and the definition of components is, indeed, the most difficult
5 process water A
B 8 gypsum
6 limestone slurry S
O F
9 recycle
R I
7 flying ashes
B L
7 flying ashes 10 bleed
E T
11 fictiv
R E
R
12 fictiv
16
part of the whole work as far as requirements for invention and knowledge of engineers are
concerned.
List of Streams:
absorber components
1 flue gas in O2, N2, SO2, CO2, H2O, sgg 1 O2
2 flue gas out O2, N2, SO2, CO2, H2O 2 N2
3 oxidation air O2, N2, H2O 3 SO2
4 process slurry gypsum, CaCO3, H2O, solute, solids 4 CO2
5 process water H2O 5 H2O
6 limestone slurry CaCO3, H2O, solids 6 CaCO3
7 flying ashes solids 7 gypsum
8 gypsum product gypsum, CaCO3, H2O, solids 8 solids
9 recycle H2O, solute 9 solute
10 bleed H2O, solute 10 sgg
11 fictive gypsum, CO2, CaCO3, H2O, SO2, O2
12 fictive solute solute, CO2, H2O, sgg, CaCO3
The definition of some components follows
Definition of Components: gypsum CaSO4.2H2O
solids material not soluble in diluted sulphuric acid
solute dissolved material
sgg solute generating gases -sum of NOx and Cl2
In the case of the PRO 2, CHEMCAD, and MAX programmes as well as in the case of the methods for
EXCEL, the preparation of a flow sheet, list of streams and list of components makes the biggest
requirements on the skills of an engineer using these tools. Maximum attention must be paid to these
steps, and it is necessary to advise in strong terms against any haste and superficiality. Creativity and
knowledge must be shown in these very points.
In the following procedure we are already bound by strict rules and we have no chance to apply an
individual approach.
17
reactions are expressed by mole fractions. Therefore, it is more expedient to carry out all calculations
as molar balances and to convert just the final results to mass.
At the same time, it is necessary to bear in mind that amount of substance may be converted to mass
at any time while converting mass to amount of substance is possible only if molar mass can be
attributed to all components.
The relationship between a mole fraction and a weight fraction is non-linear, as shown in the graph for
a two-component mixture of ethanol – water.
1,20
1,00
0,80
0,60
0,40
weight fraction
0,20
of ethanol
0,00
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Notation:
• Amount of substance is usually designated in the same way as in the equation of state for
ideal gas PV=nRT, i.e. as n. Then the flow should be a dotted n, but EXCEL cannot do that,
-1
and therefore we shall indicate the flow in kmol·s as n as well.
• Mass is usually designated as m. Since the same rules apply here as with the flow of amount
of substance, we have no other option than to designate the mass flow rate as m.
• The letter x has been introduced in physical chemistry to denote a mole fraction. We shall
adhere to this established practice.
• In order to denote a weight fraction we shall choose a letter from the end of the alphabet as
well. However, y could be confused with the symbol introduced for a mole fraction in vapour
phase and z clashes with the symbol for compressibility factor. These two properties will be
18
present in our calculations, and therefore it is necessary to look for another sign to denote the
weight fraction. The nearest letter from the end of the alphabet is w.
• Designations of fundamental properties:
*1
Flow of amount of substance n recommended dimension kmol·s
Mole fraction x
-1
Mass flow rate m recommended dimension kg·s
Weight fraction w
• This notation is not binding; any other notation of fundamental properties can be used as long
as it is defined properly.
However, the indexing is binding.
• Every flow designation has an index that is identical with the number of the respective stream.
• Every designation of composition has two indexes:
• The first index designates the stream
• The second index designates the component.
Thus the mole fraction of the component 2 in the stream 3 is x3;2 – x3;2 can be used as notation in
order to increase the speed of posting in EXCEL. Similarly, one can post n3 instead of n3.
Conversion
3 -1 -1
To convert flows from Nm ·s to kmol·s one needs to know:
Normal temperature 273.15 °K
Normal pressure 101.325 kPa
-1 -1
Gas constant R 8.31451 kJ·kmol ·K
Then we can substitute values in the equation of state for ideal gas:
PV = nRT.
If the flow (production) is given in tons per year, this figure is not converted to the total number of
hours, but to the annual working capacity, which is 8,000 working hours per year as for continuous
chemical operations. This is the value recommended in case a more accurate figure cannot be
obtained.
In converting the composition in mole fractions to weight fractions we proceed as follows:
1.
2. The components present in the stream are entered into the first column.
3. The component’s quantity – mole fractions, mole per cent, any numbers designating the ratios
in the numbers of moles of the components - is entered into the second column.
4. Molar mass of the components is entered into the third column.
5. Scalar product of the second and third column is entered into the fourth column.
6. The fifth column is created by dividing the individual parts of the fourth column by the sum of
the fourth column. We get the weight fractions of individual components as a result.
This procedure can be tested on the following table:
[kmol] [kg/kmol] [kg] [kg/kg altogether]
NH3 32 17.03 544.96 0.154046 w3;4
CO2 68 44.01 2992.68 0.845954 w3;3
[kmol altogether] [kg altogether]
100 3537.64
In converting weight fractions to mole fractions we follow the same procedure, only the fourth column
is created by dividing the second column by the third column.
We will demonstrate the procedure in calculating the composition of saturated solution of salt in mole
fractions. The solubility of salt is specified as 35.66 g NaCl / 100g H2O.
4
5
filt
Reaction: 6
NaCl + H2O + CO2 + NH3 = NaHCO3 + NH4Cl
For every independent reaction we have one stream, which is given by the product of the reaction rate
and the reaction volume, and we shall call it the source stream. The formation or disappearance of
-1 -1
individual components in the reactor through the reaction in kg·s or in kmol s is given by the product
of the source stream and the respective stoichiometric coefficient (plus signs for products of reaction,
negative signs for reactants). In the event of more independent reactions the calculated properties
must be added up.
20
acid by absorption of gases of nitrogen into water as an example. The following reactions may take
place in the system.
2· NO + O2 = 2· NO2
NO + NO2 + H2O = 2· HNO2
3· HNO2 = HNO3 + 2 NO + H2O
3· NO2 + H2O = 2· HNO3 + NO
2· NO2 + H2O = HNO2 + HNO3
2· HNO2 + O2 = 2· HNO3
HNO2 + NO2 = HNO3 + NO
We can set up a matrix of coefficients from the stoichiometric coefficients, which are used for
multiplying the formulas of compounds in the individual stoichiometric equations:
NO NO2 O2 H2O HNO2 HNO3
-2 2 -1 0 0 0
-1 -1 0 -1 2 0
2 0 0 1 -3 1
1 -3 0 -1 0 2
0 -2 0 -1 1 1
0 0 -1 0 -2 2
1 -1 0 0 -1 1
We modify this matrix using the method of Gaussian elimination to make the cells below the diagonal
show zero. The Gaussian method of elimination is described for instance by J. Holenda in Linear
Algebra (Holenda J. Lineární algebra. Prague: Czech Technical University 1978).
With matrixes one is allowed to replace any row (column) with a linear combination of the initial row
(column) with any other rows (columns) of the matrix. Therefore, if we want to generate zeros below
the diagonal in the first column, we proceed as follows:
• row 1 – this remains the same,
• row 2 – we multiply the second row by –2 and add it up with the first row,
• row 3 – we add the third row up with the first row,
• row 4 – we multiply the fourth row by 2 and add it up with the first row,
• row 5 and row 6 remain unchanged,
• row 7 – we add the row 7 up with the row 2.
We get the following matrix
generation of zeros below the diagonal in the first column
-2 2 -1 0 0 0
0 4 -1 2 -4 0
0 2 -1 1 -3 1
0 -4 0 -2 2 2
0 -2 0 -1 1 1
0 0 -1 0 -2 2
0 -2 0 -1 1 1
We proceed in an analogous manner in generating zeros below the diagonal in the second column
and in the third column:
21
generation of zeros below the diagonal in the third column
-2 2 -1 0 0 0
0 4 -1 2 -4 0
0 0 1 0 2 -2
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
The elimination for the remaining columns does not take place since they already show zeros below
the diagonal. Our matrix has the rank 3, and consequently only three of the seven mentioned
stoichiometric equations are independent.
We can take the liberty to refrain from determining the rank of a matrix only if we are absolutely sure.
An error made by incorrect determination of the number of independent equations is very difficult to
find.
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Specification Table
stream 1 2 3 4 5 6 reaction
-1
kg·s 4,315 1,001157 m3 m4 m5 m6 mr
block component
column 1 H2O 0.732 0 0 w4;1 0 0 -18.02
2 NaCl 0.268 0.00 0 0.02 0 0 -58.44
3 CO2 0 w2;3 0.846 0 0 0 -44.01
4 NH3 0 w2;4 0.154 0 0 0 -17.03
5 NaHCO3 0 0 0 w4;5 0 0 84.01
6 NH4Cl 0 0 0 w4;6 0 0 53.49
filter 1 H2O 0 0 0 w4;1 0 w6;1 0
2 NaCl 0 0 0 0,02 0 w6;2 0
5 NaHCO3 0 0 0 w4;5 1 w6;5 0
6 NH4Cl 0 0.00 0 w4;6 0 w6;6 0
Matrix of Coefficients
A specification table can be transformed into a matrix of coefficients and a right-hand-side vector of
the system of linear algebraic equations in the following manner:
• We open a new clean sheet and transfer the reference to the top left corner of the
specification table into a suitable field (left margin). Only that one cell, not the whole matrix!
• We place the cursor onto the bottom right edge of the cell (+ will appear) and drag it onto the
whole column and then the whole matrix. Thereafter we copy the whole specification table.
Having been copied and slightly adjusted, the specification table on the Sheet 2 looks as follows:
1 2 3 4 5 6 reaction
-1
stream kg·s 4.315 1.0012 m3 m4 m5 m6 mr
1 H2O 0.732 0 0 w4;1 0 0 -18.02
2 NaCl 0.268 0 0 0.02 0 0 -58.44
3 CO2 0 w2;3 0.846 0 0 0 -44.01
4 NH3 0 w2;4 0.154 0 0 0 -17.03
5 NaHCO3 0 0 0 w4;5 0 0 84.01
6 NH4Cl 0 0 0 w4;6 0 0 53.49
1 H2O 0 0 0 w4;1 0 w6;1 0
2 NaCl 0 0 0 0,02 0 w6;2 0
5 NaHCO3 0 0 0 w4;5 1 w6;5 0
6 NH4Cl 0 0 0 w4;6 0 w6;6 0
• First of all, we create a right-hand-side vector. We place it at the end as the last column,
designate it, for instance, as “vps” and post zeros into all cells of this column.
• Then we transfer the numerical values from the row of streams into the right-hand-side vector.
We proceed in the following manner:
• We create a new end row and post zeros into all fields.
• We post 1 in the last row of the column wherefrom we want to transfer the numerical value of
the stream.
• We drag and drop the numerical value (using an arrow) in the last row of the column of the
right-hand-side vector.
• We enter the alphanumeric designation of the stream for the respective column into the
cleared cell in the row of streams.
• We repeat this procedure for every stream for which we know the numerical value. In our case
we start with m1 and go over to m2.
23
The alphanumeric designation for concentration of components in streams is removed from the table
in the following manner:
• Behind the column with the alphanumerical designation of the composition of the stream we
insert as many new columns as there are unknown concentrations present in the stream.
• We fill the new columns with zeros.
• We enter into the row of streams that the values in the column indicate the product of flow and
composition. Therefore, we will have five columns for stream 6 – m6, mw6;1, mw6;2, mw6;5,
and mw6;6.
• We replace the alphanumeric designation of the content of the component in the stream by
zero and enter 1 into the respective column in the same row.
After these steps have been taken, the matrix reads as follows:
m1 m2 mw2;3 mw2;4 m3 m4 mw4;1 mw4;5 mw4;6 m5 m6 mw6;1 mw6;2 mw6;5 mw6;6 mr vps
0.73 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 -18 0
0.,27 0 0 0 0 -0.02 0 0 0 0 0 0 0 0 0 -58.4 0
0 0 -1 0 0.85 0 0 0 0 0 0 0 0 0 0 -44 0
0 0 0 -1 0.15 0 0 0 0 0 0 0 0 0 0 -17 0
0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 84 0
0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 53.5 0
0 0 0 0 0 0 1 0 0 0 0 -1 0 0 0 0 0
0 0 0 0 0 0.02 0 0 0 0 0 0 -1 0 0 0 0
0 0 0 0 0 0 0 1 0 -1 0 0 0 -1 0 0 0
0 0 0 0 0 0 0 0 1 0 0 0 0 0 -1 0 0
1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4.31
0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
Thereby we have created a matrix of coefficients for balance equations. Apart from balances of
components in individual nodes it must hold true that the sum of weight or mole fractions in every
stream equals 1.
This relation will be referred to as the “summation relation” and we will incorporate it into the matrix of
coefficients using the following procedure:
• We create a new end row and insert zeros into all fields.
• We choose one stream in which there are some unknown concentrations. We select the
blocks from which this stream exits or into which this stream enters. We enter the value of 1 –
the sum of absolute values of the content of the cells in the selected block - into the last row in
the column of this stream. If a known value is present in the stream – for instance in stream 4,
a value a will appear in the end row, for which the following holds true:
§ 0< a ≤ 1
• If all concentrations in the stream are unknown, then a = 1.
• We enter 1 into the end row in the columns for the flow-concentration product.
• We repeat this procedure for all streams, in which there were some unknown concentrations.
Thereafter the table of coefficients reads as follows:
m1 m2 mw2;3 mw2;4 m3 m4 mw4;1 mw4;5 mw4;6 m5 m6 mw6;1 mw6;2 mw6;5 mw6;6 mr vps
0.73 0 0 0 0 0 -1 0 0 0 0 0 0 0 0 -18 0
0.27 0 0 0 0 -0.02 0 0 0 0 0 0 0 0 0 -58.4 0
0 0 -1 0 0.85 0 0 0 0 0 0 0 0 0 0 -44 0
0 0 0 -1 0.15 0 0 0 0 0 0 0 0 0 0 -17 0
0 0 0 0 0 0 0 -1 0 0 0 0 0 0 0 84 0
0 0 0 0 0 0 0 0 -1 0 0 0 0 0 0 53.5 0
0 0 0 0 0 0 1 0 0 0 0 -1 0 0 0 0 0
0 0 0 0 0 0.02 0 0 0 0 0 0 -1 0 0 0 0
0 0 0 0 0 0 0 1 0 -1 0 0 0 -1 0 0 0
0 0 0 0 0 0 0 0 1 0 0 0 0 0 -1 0 0
24
1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4.31
0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
0 -1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 -0.98 1 1 1 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 -1 1 1 1 1 0 0
Full comprehension of the recommended procedure will best be ensured by the complete Excel file
with commentaries clarifying the particular steps in greater detail. This file is entitled problem_soda.
The linear additional relation as the one stated above is rather an exception than a rule. Additional
relations arising from phase or chemical balances or from enthalpy balances are non-linear. A problem
of a non-linear additional relation is dealt with in the problem_redukce file. The Excel file has been
provided with abundant commentaries that should be sufficient in order to make one understand the
applied procedure. One non-linear relation can be managed using the Solver function. If there are
more non-linear additional relations, the problem must be dealt with numerically using the Newton-
Raphson method. Excel suggests an elegant method of obtaining the value of Jacobian, which is
essential for the application of this method. The problem is solved in the problem_reactor file. The
commentaries provided in this file should be sufficient to make one understand the procedure.
Enthalpy Balance
The number of balance equations of components for each block agrees with the number of
components present in the given block.
We have one enthalpy balance for each block.
For the amount of matter and block l it will read as follows:
S C N
25
• Index i indicates streams and index j indicates components.
• S is the total number of streams; C is the total number of components.
• hi;j is the molar enthalpy of component j at the temperature and pressure of stream i.
• nrk is the source stream of the k-th reaction and hrk is the reaction enthalpy of this reaction.
• N is the total number of independent reactions.
• Q is the energy exchanged with the surroundings.
• All parts are expressed in kW.
Enthalpy balance for mass balance will have the following form:
S C h i; j N
∑incmati;l ⋅ mi ⋅ ∑ w i; j ⋅ Mj
+ ∑ nrk ⋅ hrk = Q
i=1 j=1 k =1
• Mj is the molar mass of component j.
Consequently, molar enthalpy of a component at the given temperature and pressure is the
fundamental property for enthalpy balance. It is a relative property; its value is related to a specific
state for which we choose the enthalpy of a component to be zero. These conditions shall be referred
to as standard state conditions.
In our calculations this component will behave like ideal gas at the temperature of 298.15°K. Pressure
does not need to be defined because with ideal gas enthalpy does not constitute a function of
pressure.
A component can be transferred from the standard state conditions into the final state using the
following steps:
• By heating component j from the standard state temperature up onto the final temperature Ti
(°K). The change in enthalpy is given by the following relation:
26
Our EnthalpyData database defines Hform by stating that a component in a gaseous state is formed
from elements.
We provide, for information, the internet address of the DECHEMA database www.ddbts.de
and the internet address of the National Bureau of Standards database webbook.nist.gov
An illustration of the application of the methods of calculating enthalpy balances in EXCEL can be
found in the problem_styrene file. In this case, the problem is solved on the basis of both molar
balance and mass balance.
27
This Problem is solved using the Newton- Raphson method.
The procedure can be clarified by studying the problem_reactor file. The sheet entitled Directions
provides a detailed method of applying this method in the environment of EXCEL. The description of
the method can be found for instance in the book by M. Kubícek Numerical Algorithms of Solutions to
Chemical Engineering Problems (Kubícek, M.: Numerické algoritmy rešení chemicko-inženýrských
úloh. Prague: SNTL 1983).
Problem 5
In this case we cannot obtain a solution, but functionality. We choose one of the unknowns to be an
independent variable, and then we can attribute some numerical value to it. Now the system is
solvable. We can study how other variables (unknowns) change subject to the value of the
independent variable selected, whereby we can obtain valuable information.
CONCLUSION
The proposed methods of balancing using EXCEL enable one:
• To create balance models of lines, nodes and equipment, with the aim to answer the question:
“What will happen if ….“
• To serve as a guideline for interventions in the operation of the line, especially if parameters
change unexpectedly.
• To acquire balance sheet values to elaborate a „basic design“.
• To determine the minimum number of measured quantities needed for the purposes of
determining the complete system characteristic.
• To evaluate and check industrial experiments and operating data.
• To balance raw materials, products, and wastes for the purposes of economy and ecology of
an enterprise.
• To make the training of the operating personnel easier.
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Address for consultation, training and advisory services: see the main Web page.
Problems Solved:
Problem 1: Solvay (Ammonia Soda) Process (problem_soda file)
Problem 2: Manufacture of Reduced Iron (problem_redukce file)
Problem 3: Manufacture of Styrene from Ethylbenzene (problem_styren file)
Problem 4: Catalytic Oxidation of SO2 to SO3 (problem_reaktor file)
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Declared composition of rum 38 volume per cent of ethanol
Composition of rum with 38 volume per cent in weight fractions at various temperatures
kg/m3 m3/kg weight per cent volume per cent
temperature ethanol water ethanol water ethanol water ethanol
0 806.0 999.8 0.001241 0.001000 33.07 66.93 38.00
10 798.0 999.6 0.001253 0.001000 32.85 67.15 38.00
20 789.0 998.2 0.001267 0.001002 32.64 67.36 38.00
30 781.0 995.6 0.001280 0.001004 32.47 67.53 38.00
40 772.0 992.2 0.001295 0.001008 32.29 67.71 38.00
50 763.0 988.0 0.001311 0.001012 32.13 67.87 38.00
60 754.0 983.2 0.001326 0.001017 31.97 68.03 38.00
70 745.0 977.7 0.001342 0.001023 31.87 68.17 38.00
30