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MICROSOFT OFFICE

EXCEL

P. Ditl, J. Skrivnek

CONTENTS

INTRODUCTION

Decision-Making

Working Tools for Decision-Making

Complete System Characteristic

3

3

3

3

BASIC CONCEPTS

What Is Flowsheeting?

What Is a Balance?

What Is a Component?

What Is a Balanced System Boundary?

What Is a Limited Time of Balance?

What Is an Amount of Component?

What Is a Continuous Process?

What Is a Source Stream of Reaction?

Why Enthalpy Balance and not Heat Balance?

What is the Difference between Material Balance and Enthalpy Balance?

Enthalpy Balance

Formulation of the Problem Being Solved

How Many Equations Define the System Behaviour in Full?

Possibilities of Solving a Model

4

4

4

5

5

5

6

7

7

8

8

9

9

9

9

Solving a System of Equations a Model

General Information

1. Process Basis and Data Available with Respect Thereto

2. Process Flow Sheet and Definition of Balance Blocks, Incidence Matrix

Flow Sheet

Incidence Matrix

3. List of Components in Streams and Their Definitions

4. Basis of Calculation and Conversion of Specified Flows and Compositions

Reference Stream Basis of Calculation

Conversion

5. Chemical Reactions, Determination of Number of Independent Chemical Reactions

Source Stream

Determination of Number of Independent Chemical Reactions

6. Specification Table and Matrix of Coefficients

Specification Table

Matrix of Coefficients

7. Formulation of Additional Relations

Types of Additional Relations

Enthalpy Balance

8. Conditions of System Solvability

9. Solving a System of Equations Using Methods of Linear Algebra, with the Advantage

of Using Excel

10. Table of Solutions Containing Complete System Characteristics

10

10

11

12

13

13

15

15

17

18

19

20

20

20

22

22

23

25

25

25

27

27

CONCLUSION

28

Enthalpy Data

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_reactor file)

28

29

EXCEL file

EXCEL files

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:

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.

Decision-making that involves any one process requires a quantitative model. This decision-making

shall mean either proposing a new process, or modifying a process, or controlling an existing process.

Such a model should give us an opportunity to study behaviour of the system if the initial conditions

change. In other words, the model should enable one to study changes of the system behaviour after

modifying initial conditions, that is to search for an answer to the question: What will happen if. Such

a model constitutes a prerequisite for an objective quantitative economic analysis of the system. It is

necessary to bear in mind at all times that the quantitative model should be exact. That means we

receive one and only solution for the selected values of the designating parameters. When using

empirical coefficients, such as efficiency, yield, or adjustable constants guaranteed by the provider of

the equipment, maximum attention must be paid in order to define these coefficients accurately. The

use of empirical coefficients is thus limited to cases where those coefficients include deviations from

the ideal behaviour, express efficiency of the process, or adjust the theory to the real behaviour of the

equipment. These adjustable parameters often constitute the subject of know-how. In any case,

however, exact mass and enthalpy balances constitute the basis of the model. Thereby a quantitative

model of a process establishes a reliable foundation of the systems economic model, which is the

final tool for the management in making decisions.

The law of conservation of mass and the law of conservation of energy can be used as an exact

model for processes accompanied by a chemical reaction and heat exchange. On the basis of this

model, mass and enthalpy balances can be drawn up for the process in question and subsequently

complete system characteristic can be acquired.

Material balances are used for obtaining a complete characteristic for all streams that are present in

the process flow chart. This information is essential both for a designer and for the operation control

itself. A complete characteristic contains the following details:

Where the stream comes from and where it goes that defines the direction of the stream, i.e.

its orientation.

-1

-1

Size of the stream, expressed as weight per time unit (kg.s ) or moles per time unit (kmol.s ).

What components the stream contains and their part, expressed as a weight or mole fraction

of the component in the stream in question. The method of expressing the composition of the

stream should be invariant to temperature and pressure.

Temperature and pressure for each stream are added to the above-mentioned in the case of

enthalpy balance.

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:

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.

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 50 up to 100, 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 particles 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.

A boundary of the system being balanced must be defined in order that a component can enter or get

out of the system only by crossing the systems boundaries. System boundaries do not have to be

identical with the apparatus housing. A system can also be an imaginary volume defined within the

apparatus. This method is very often used to define differential volume, it being the system with dx, dy

and dz dimensions in rectangular coordinates. Then the balance relation for the component leads to a

partial differential equation.

The system being balanced does not have to be identical with the individual units of apparatus. Units

of apparatus can be combined for the purposes of balancing. Admittedly, this reduces the number of

input data, required for the performance of the balance calculation, but the possibility of acquiring

further information is thereby lost. For instance, if we link, for the purposes of balancing, an

evaporating apparatus and crystalliser, we lose the information about the properties of the

concentrated solution entering the crystalliser, which is an information necessary for the structural

design of the evaporating apparatus. An opposite approach is possible as well. For instance, instead

of balancing the whole distillation column individual levels can be balanced.

If we divide all elements of the balance relation by the limited time of balance, we will obtain the

components quantity per unit of time.

This quantity can be termed as stream. Then the balance relation for any one component can be

posted as follows:

Input Stream + Source per Unit of Time = Output Stream + Rate of Accumulation

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.

In order to substitute into the above-mentioned relation we need to know the stream of the component,

which is the quantity of the component per unit of time. However, we do not usually have the

opportunity to measure the component stream directly. In most cases we measure the overall stream

and its composition. The component stream can be calculated from these two pieces of information.

If the component is a differential particle size, the size of the stream of this component can be

calculated by multiplying the overall flow of particles by the relative frequency of occurrence of the

particles within the monitored interval. When reducing the interval of the particle size to zero we get a

differential and integral description known in literature as population balance.

The numerical value of the flow of the component is required to be invariant to temperature and

pressure. This requirement excludes the overall stream to be expressed as volume per unit of time.

There remains the possibility of expressing the flows of components as mass or amount (number of

pieces) kilograms of flour and number of eggs per unit of time.

Furthermore, it is required to have the opportunity to convert mass to amount (number of pieces) and

vice versa. For it is common practice to weigh small screws instead of counting our thousands of

pieces. The approach is accurate only if every piece has exactly the same mass as the other ones.

This requirement is satisfied strictly only with molecules. Molecules are too small to be counted out.

However, we know that one kmol of any substance contains the same number of molecules,

26

-1

corresponding to the Avogadros number, which is 6.0221367102 kmol . If we know the molar mass

-1

for a component (kgkmol ), we can convert the amount of substance (kmol) to mass (kg) and vice

versa. If a component cannot be attributed molar mass, its quantity can be expressed only as mass in

kg.

Consequently, we shall express the fraction of the component present in the stream only as a weight

-1

-1

fraction or a mole fraction, depending on whether the overall stream is expressed in kmols or kgs .

It is common practice in industry and business to encounter the definition of composition in volume per

cent. The following example will show us what ambiguousness this can lead to.

The content of alcohol in rum commonly available in the market is declared on the label as 38 volume

per cent. Lets assume this denotes a solution created by mixing 38 volume parts of ethanol with 62

volume parts of water. If we perform this operation at different temperatures, solutions with various

alcohol content are formed as the following table shows.

Sample Problem: Declared composition of rum

38

Composition of rum with 38 volume per cent in weight fractions at various temperatures

temperature

kg/m3

ethanol

water

m3/kg

ethanol

0

10

20

water

806.0

798.0

789.0

999.8

999.6

998.2

0.001241

0.001253

0.001267

0.001000

0.001000

0.001002

33.07

32.85

32.64

66.93

67.15

67.36

38.00

38.00

38.00

30

40

50

781.0

772.0

763.0

995.6

992.2

988.0

0.001280

0.001295

0.001311

0.001004

0.001008

0.001012

32.47

32.29

32.13

67.53

67.71

67.87

38.00

38.00

38.00

60

754.0

983.2

0.001326

0.001017

31.97

68.03

38.00

ethanol

water

ethanol

70

745.0

977.7

0.001342

0.001023

31.87

68.17

38.00

water

0C

999.8

0.001342

0.001000

31.35

68.65

38.00

temperature

ethanol

70C

745.0

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

kmols 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 kmolkmol in the first case or weight fraction of kgkg

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.

The accumulation of a component in the system is the change in quantity of the property being

balanced (hold-up). If a process is run continuously in a steady state, the change in hold-up and its

composition with time is null, and therefore the rate of accumulation is also null.

The accumulation of mass is usually applied in batch systems. If we choose a limited time of balance

exceeding the time of a batch process cycle by a long way, we can accept the assumption of a zero

rate of accumulation. If we choose no matter how long balance period, the system accumulation will

be given by the level of the system hold-up at the end of the balance period minus the system hold-up

at the start of the balance period. This can be the difference between the maximum and the minimum

hold-up at the most. If we choose the balance period to be just as long so that the maximum

accumulation possible is negligible compared with the input and output streams for the balance period,

we can regard also the periodical batch processes to be continuous and deem the rate of

accumulation to be zero.

Complete system characteristic does not say anything about the dimensions of individual pieces of

equipment, and therefore the relations we use for balancing do not contain any parameters of the

equipment. However, in order to calculate the rate of accumulation it is necessary to know the hold-up,

which constitutes a parameter of the equipment. Therefore, our concern will be focused on continuous

and periodical batch processes, where the accumulation rate can be ignored.

Just as in the case of accumulation, it is necessary to know the hold-up of the equipment in which the

chemical reaction takes place in order to calculate the source of a component directly. The rate of

generation of the component being balanced is the amount of component generated at the given place

in the unit of capacity of the system per unit of time. That means that an intensive property is involved.

Since the source in balances is an extensive property, we have to integrate the intensive property

through the capacity of the system being balanced. In the case of an ideal stirred tank, where

composition and temperature do not constitute functions of the place, we simply multiply the

mentioned intensive property by the capacity of the hold-up, which is, however, a parameter of the

equipment. In order to avoid this difficulty, we can substitute the source by a fictive stream of reaction.

For every independent reaction there will be one fictive stream, which will be denominated as nrk for

balances of amount of substance and as mrk for mass balances, where k is the serial number of

reaction in case that more independent reactions are taking place in the block being balanced.

Instead of posting mole and/or weight fractions into the fictive stream column in the specification table

for k, we

enter the components stoichiometric coefficient into the components 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

components 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:

components nr

components

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

mr

5 NaHCO3

5 NaHCO3

84.01

6 NH4Cl

6 NH4Cl

53.49

The change in energy of 1 kg of water upon being heated by 0.5C corresponds to the change in the

-1

mass flow rate of the same by 65 ms or raising by 213 m. Such changes in kinetic and potential

energy can be hardly encountered in a chemical plant, the exception thereof being power-producing

machinery (turbines). For the purposes of balancing we can therefore ignore potential and kinetic

energy of streams and substitute heat balance by enthalpy balance.

This has the same advantage as disregarding the accumulation rate. In order to calculate kinetic and

potential energy of a stream at the given place we need to know the diameter of the piping and its

height above the ground, which are parameters of equipment that do not belong into the system

characteristic. We do not need this information to calculate the enthalpy of a stream, and therefore we

replace the overall heat balance by enthalpy balance. The mistake that can be thereby caused is

negligible in the absolute majority of cases.

For a continuous process or a batch process occurring periodically, material balance of a component

has the following form:

Input Stream of Component + Fictive Stream of Component = Output Stream of Component +

Accumulation Rate of Component.

That applies to every component, which means that for a balanced system we have as many material

balances as there are components present in the system.

-1

-1

The system being balanced can interchange energy with the surroundings not only through the

material streams, but also through the exchange across the system boundaries heat exchangers, or

stirrers as the case may be, and so forth.

In that case, the enthalpy balance for a continuous process or a batch process occurring periodically

will have the following form:

Input Stream Enthalpy + Efficiency of Source = Output Stream Enthalpy + Interchange of Energy with

Surroundings

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.

In order to comply with the law of conservation of mass and enthalpy the following equations must

hold true for every block of the flow sheet:

material balance for every one component (in order words, the number of balance equations

agreeing with the number of different components present in the streams, which pass into or get

out of the given block we take into account both real and fictive streams);

summation equations for every one stream (in other words, the total of weight or mole fractions of

all components in the given stream must equal one);

other equations, if any, follow from the laws that determine the relations among the composition,

pressure, and temperature of individual streams. These are the laws of thermodynamics, chemical

and phase balance, or laws of kinetics of processes. These relations are almost always non-linear;

other equations issue from specifications given by technological regulations (such as yield,

selectivity) or in data provided by the producer of the equipment (such as efficiency of machines);

Enthalpy balance is non-linear, which is given by the fact that molar heats represent functions of

temperature.

This set of equations forms a mathematical model, for which methods of solving must be established.

A system is defined in full if the sum of balance equations, summation equations, equations for

physical laws, specification equations, and enthalpy balance is equal to the number of unknowns in

the equations.

The issue of simplicity of information transmission plays an important role with the model used. There

is specialised software available for these models, such as CHEMCAD, PRO, or MAX. In addition,

advantage can be taken of mathematical software, such as MATLAB, Mathematica, MATHCAD, and

so forth.

This software has two big disadvantages firstly, it is very expensive, and secondly, to become

proficient in the software requires great efforts and a lot of time. It is necessary to bear in mind that a

model set up by means of certain software will be used from a certain level of management upwards.

At this level it is possible to encounter the willingness to sacrifice the financial means to buy the

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.

The methods of solving have been drawn up to be generally valid and uniform for all types of balance

cases. Exactly the same procedure is used for all cases, ranging from the problem of what ratio to use

to mix two streams of water with different temperatures so that the resulting stream can have the

temperature required, to systems containing dozens of blocks and streams.

These uniform methods have facilitated the elaboration of an exact method of solving, which is

available to the engineering public at large and which consists of the following steps:

The following is required for any process we wish to balance:

1.

2.

3.

4.

5.

6.

7.

8.

9.

Process Flow Sheet and Definition of Balance Blocks, Incidence Matrix.

List of Components in Streams and Their Definitions.

Basis of Calculation and Conversion of Specified Flows and Compositions.

Chemical Reactions, Determination of Number of Independent Chemical Reactions.

Specification Table and Matrix of Coefficients.

Formulation of Additional Relations.

Conditions of System Solvability.

Solution of a System of Equations Using Methods of Linear Algebra, with the Advantage of

Using Excel.

10. Table of Solutions Containing Complete System Characteristic.

Comments:

Once the balance sheet has been drawn up and once it has been established which components are

present in individual streams, the rest of the balancing is, more or less, a matter of routine for there is

an exact procedure that leads step by step straight to the ultimate goal.

When strictly following the stated procedure the result may be incorrect only if the streams (both real

and fictive) and components have not been defined correctly. An operations engineer, who has a

perfect command of the process and knows the methods of measuring and analyses in detail, is the

most suitable person to set up the balance programme in Excel (or to take part in this task).

Putting together a list of components and defining these components is essential to satisfy the

summation equation. The requirements for perfect acquaintance with the process are focused in this

very issue.

10

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.

Lets discuss the individual phases of the procedure in detail.

It is demonstrated on the Solvay process. The following table contains a typical process description:

Description of Technology

A saturated solution of NaCl contains

with a gas mixture consisting of

100.0000 %

32.0000 volume % NH3

and 68,0000 volume % CO2.

containing, on the top of NH4CL, also

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, lets 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.

Lets 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.

Lets 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.

Flow Sheet

A flow sheet is the next step following the process description. This phase gives a lot of freedom to the

user. The nodes being balanced can be drawn as rectangles or as schematic drawings of the pieces

of apparatus, which they represent, streams connecting individual nodes can have any thickness,

equipment with one input stream and one output stream, with which the amount and composition of

the stream does not change, can be left out from the flow sheet. The examples of such equipment

include, for instance, an intermediate storage tank or a pump. Individual nodes (units of apparatus)

can be interconnected for the purposes of balancing into greater units-blocks and these can be

subsequently marked in various ways. However, it is necessary to observe certain rules:

The nodes being balanced are designated using alphanumerical signs visibly different from the

numbers assigned to the streams.

Standard types of nodes:

1.

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

4.

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.

K

R

5

6

D

2

2

8

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

Condenser column

Divider column

Blender column

Surroundings

with

with

with

with

with

R

K

D

S

O,

then the incidence matrix for the given flow sheet will read as follows:

stream

1

2

3

4

5

6

7

8

9

10

11

incmat

R

1

-1

-1

0

0

0

0

0

1

1

-1

K

0

0

1

-1

-1

0

0

0

0

0

0

D

0

0

0

0

1

-1

-1

0

0

0

0

S

0

0

0

0

0

0

1

1

-1

0

0

O

-1

1

0

1

0

1

0

-1

0

-1

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.

In creating a list of streams and list of components we proceed in the following manner:

List of Streams:

Column 1 contains the numbers of the streams.

Column 2 contains the working title of the stream - brine, feed, distillate, total solids, and so forth.

Column 3 contains the list of components present in the stream.

15

List of Components:

Column 1 contains the components serial number.

Column 2 contains the components name.

Column 3 contains, in the case of a defined chemical compound, the components 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 isnt a waste of time.

Some components present in the system cannot be balanced. To decide which components will be

balanced and which wont 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.

List of Streams:

1 salt brine

NaCl, H2O

List of

Components:

1

H2O

molar mass

kg / kmol

18.02

2 relief gases

CO2, NH3

NaCl

58.44

3 entrance gas

NH3, CO2

CO2

44.01

4 suspension

NH3

17.03

5 product

NaHCO3

NaHCO3

84.01

6 mother liquor

NH4Cl

53.49

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

1 flue gas in

3 oxidation air

4 process slurry

5 process water

6 limestone slurry

7 flying ashes

7 flying ashes

11 fictiv

A

B

S

O

R

B

E

R

8 gypsum

9 recycle

12 fictiv

16

F

I

L

T

E

R

10 bleed

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.

4. Basis of Calculation

Compositions

and

Conversion

of

Specified

Flows

and

Molar balance (kmol) is practicable only if molar mass can be attributed to all components being

balanced.

Mass balances are expedient for using the same expression of quantity as economic and production

records. We are interested to know the tons of sulphuric acid manufactured and the price for one

kilogram of soda. The amount of kilo-moles processed and the price for one kilo-mole are figures that

have no informative value in the world of economy. Economy requires kilograms, not kilo-moles.

Molar balances are expedient in the case where streams are gases. The composition of gases is

given in volume per cent, which represents mole per cent at the same time. This is the product of the

law of Avogadro which says that the number of molecules in an identical volume of any gas is, at the

given temperature and pressure, the same. Measurements of gas flow rate are performed by

measuring the volume flow rate, with temperature and pressure being measured at the same time, so

3

the state-of-the-art flow meters indicate the flow in Nm (standard cubic meters, which represents the

volume at the temperature of 273.15 K and pressure of 101.325 kPa). On the assumption of ideal

behaviour of the gas, volume can be converted to kmol using the equation of state for ideal gas:

PV = nRT

and vice versa even if we do not know the exact composition of the gas. However, to calculate mass

(kg) we must know the exact composition of the gas.

All relations provi ded to us by physical chemistry for calculating intensive properties, phase and

chemical balances, as well as relations for kinetics of mass transfer and for kinetics of chemical

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

weight fraction

of ethanol

0,40

0,20

0,00

0

As a non-binding rule we can recommend molar balances (kmol), if possible, with processes with

mostly gaseous streams and with chemical reactions in gaseous phase or, as the case may be, with

processes in which separation processes, such as absorption and distillation, take place.

When taking decisions it is necessary to bear in mind that the flow and composition of gaseous

3

streams is given in Nm and mole fractions, as distinct from kilograms and weight fractions with all the

other streams.

Balancing is practicable only if the magnitude of at least one stream is known in the system. If that is

not the case, we have to select one stream as a reference stream and attribute a numerical value to it.

It is completely arbitrary which stream we select as a reference stream and what numerical value we

attribute to it. It is sometimes expedient to attribute the value of 1 to the magnitude of the stream and

to select such a stream to be the reference stream to make the resulting balance directly indicate the

quantity of product made from one kilogram of material or how many kilograms of the respective

material are required to produce one kilogram of product. If the magnitude of at least one stream has

been specified, a reference stream does not need to be selected. The selection of a reference stream

will be illustrated in the sample problems.

The decision to balance amount of substance, or mass, also indicates the standard onto which the

data specified in the process description must be converted.

First of all, it is necessary to decide on how we shall denote the mass flow rate and the amount of

substance.

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 kmols 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

kmols

Mole fraction

x

-1

Mass flow rate

m

recommended dimension

kgs

Weight fraction

w

This notation is not binding; any other notation of fundamental properties can be used as long

as it is defined properly.

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

Normal temperature

Normal pressure

Gas constant R

273.15 K

101.325 kPa

-1 -1

8.31451 kJkmol 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.

3.

4.

5.

6.

The components present in the stream are entered into the first column.

The components 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.

Molar mass of the components is entered into the third column.

Scalar product of the second and third column is entered into the fourth column.

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.

NH3

CO2

[kmol] [kg/kmol]

32

17.03

68

44.01

[kmol altogether]

100

[kg]

[kg/kg altogether]

544.96

0.154046

w3;4

2992.68 0.845954

w3;3

[kg altogether]

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.

NaCl

H2O

[kg]

36,66

100

[kg ]

136,66

kmol

[kmol/kmol ]

0,6273

0,1016

5,5494

0,8984

[kmol ]

19 6,1767

kg/kmol

58,44

18,02

Important warning If properties taken from the cells marked in colour are present in the calculation

formulas for converting (for example, molar mass), we have to introduce the value of this property into

the formula by reference to the respective cell and not by retyping the value of such a property.

Reactions

Source Stream

The next phase is to determine which nodes function as chemical reactors, and to resolve how many

independent reactions take place therein. For the bicarbonate column, which is part of the Solvay

process, the flow sheet and description of the reaction will be as follows:

Flow Sheet Bicarbonate Column

2

1

3

4

5

filt

Reaction:

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 kgs 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.

The number of source streams present in the balance agrees with the number of independent

reactions taking place in the system. However, there is one problem, namely the word independent.

With more complicated reaction we are able to estimate, based on the fundamental knowledge of

chemistry, which chemical reactions could take place in a system. Almost all real processes do not

take place as a single reaction, but as a complex of reversible, parallel and consecutive elementary

reactions. However, we still need to establish which reactions are independent. This task is identical

with the task of determining the rank of a matrix of coefficients. Lets take the manufacture of nitric

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. Linern 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 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.

generation of zeros below the diagonal in the first column

-2

0

0

0

0

0

0

2

4

2

-4

-2

0

-2

-1

-1

-1

0

0

-1

0

0

2

1

-2

-1

0

-1

0

-4

-3

2

1

-2

1

0

0

1

2

1

2

1

We proceed in an analogous manner in generating zeros below the diagonal in the second column

and in the third column:

generation of zeros below the diagonal in the second column

-2

2

-1

0

0

0

0

4

-1

2

-4

0

0

0

1

0

2

-2

0

0

-1

0

-2

2

0

0

-1

0

-2

2

0

0

-1

0

-2

2

0

0

-1

0

-2

2

21

-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.

Specification Table

A specification table is a method of entering input data to make it capable of being used in

setting up a matrix of coefficients of a linear system of balance equations.

If we have converted all available data to the chosen basis of calculation, we arrange the

available values of the system characteristic into a specification table.

The specification table will have as many columns as there are streams present in the system,

plus one column for every independent reaction that takes place in the system.

The first row is reserved for magnitudes of streams. On the top of that, the specification table

will have as many rows for each block as there are components present in the block.

Individual fields in the columns of streams contain a weight or mole fraction of the component

corresponding to the respective row.

If we dont know the value that corresponds to the respective field, we will enter an

alphanumeric sign indicating this property. If we dont know the mass flow rate of the stream 5,

we will enter m5 into the respective field. If we dont know the mole fraction of the component

3 in the stream 4, we will write x4;3 into the respective field.

If we know the value required, we shall introduce it into the respective field by reference to the

cell in the Conversion paragraph never by retyping!

If we know that there is only one component in the stream, we will enter 1 into the respective

field, if we know that there is no component present in the stream, we will enter 0 into the

respective field.

We post stoichiometric coefficients of components of the corresponding reaction into the

columns for chemical reactions. Stoichiometric coefficients for reactants (components entering

into the reactions, or components on the left-hand side of the stoichiometric equation) are

attributed a negative sign. Stoichiometric coefficients of components, constituting products of

reactions (components on the right-hand side of the stoichiometric equation) will have a

positive sign.

That holds good in case we balance amount of substance. If we balance mass, we have to

multiply the individual stoichiometric coefficients by molar masses of the respective

components.

The number of unknowns agrees with the number of different alphanumeric signs in individual

cells. Beware of duplications!

For every block being balanced the number of balance equations available to us agrees with

the number of components present in the streams passing into or out of the blocks.

Attention: the overall balance of a node or a block is given by the sum of the component

balances, and therefore it is a dependent equation.

Moreover, the sum of weight (or mole) fractions in every stream must equal one.

For illustration see the sample specification table provided for the case of bicarbonate column.

22

Specification Table

stream

1

-1

block

kgs

component

reaction

4,315

1,001157 m3

m4

m5

m6

mr

0.732

0.268

0

0.00

0

0

w4;1

0.02

0

0

0

0

-18.02

-58.44

3 CO2

w2;3

0.846

-44.01

4 NH3

w2;4

0.154

-17.03

5 NaHCO3

w4;5

84.01

6 NH4Cl

w4;6

53.49

1 H2O

2 NaCl

0

0

0

0

0

0

w4;1

0,02

0

0

w6;1

w6;2

0

0

5 NaHCO3

w4;5

w6;5

6 NH4Cl

0.00

w4;6

w6;6

column 1 H2O

2 NaCl

filter

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

stream kgs 4.315

2

1.0012

3

m3

4

m4

5

m5

6

m6

reaction

mr

1 H2O

2 NaCl

0.732

0.268

0

0

0

0

w4;1

0.02

0

0

0

0

-18.02

-58.44

3 CO2

w2;3

0.846

-44.01

4 NH3

w2;4

0.154

-17.03

5 NaHCO3

w4;5

84.01

6 NH4Cl

w4;6

53.49

1 H2O

2 NaCl

0

0

0

0

0

0

w4;1

0,02

0

0

w6;1

w6;2

0

0

5 NaHCO3

w4;5

w6;5

6 NH4Cl

w4;6

w6;6

-1

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

m6

vps

0.73

-1

-18

0.,27

-0.02

-58.4 0

-1

0.85

-44

-1

0.15

-17

-1

84

-1

53.5

-1

0.02

-1

-1

-1

-1

4.31

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

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.

m1

m2

mw2;3 mw2;4 m3

m4

m6

vps

0.73

-1

-18

0.27

-0.02

-58.4 0

-1

0.85

-44

-1

0.15

-17

-1

84

-1

53.5

-1

0.02

-1

-1

-1

-1

24

4.31

-1

-0.98

-1

Types of Additional Relations

In addition to balance relations and summation equations there are usually also other relations that

must be satisfied. They are called additional relations. In most cases they are defined in the

description of technology. They can include physical and chemical data (phase and chemical

balances), or adjustable parameters of the process and equipment specified by manufacturers and

technology support (efficiencies, specific consumption, conversions of chemical reactions). These

relations can be both linear and non-linear (most relations of equilibrium). Heat balance with nonisothermal processes can also be included in additional relations. Enthalpy balance can serve as an

additional relation as long as it does not contain new unknowns. In that case we actually deal with

enthalpy balance and molar balance at the same time. In most cases, molar and enthalpy balances

can be solved independent of each other, with enthalpy balance being based on molar balance.

In our case, the additional relation is the concentration ratio of sodium hydrogen carbonate and water

in mother liquor. The description of technology suggests that this relation will have the following form:

mw6;5 = 0,0753 mw6;1

We create another (this time final) end row for this additional relation and it shall read as follows:

m1

m2

mw2;3 mw2;4 m3

m4

m6

vps

0.075

-1

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 NewtonRaphson 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:

i=1

j=1

k=1

25

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

h i; j

i=1

j=1

Mj

incmati;l mi w i; j

+ nrk hrk = Q

k =1

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 298.15K. 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:

h j = CpA j Ti +

CpB j

Ti 2 +

CpC j

Ti 3 +

CpD j

4

Ti 4 H 0 j

where

H 0 j = CpA j 298,15 +

CpB j

2

298,15 2 +

CpC j

3

298,15 3 +

CpD j

4

298,15 4

By condensing the component. The database provides evaporation heat Hvap (condensation

heat with the opposite sign) for boiling temperature. It can be converted onto any other

temperature using the following equation:

h vap = Hvap

1 T C

TB

1

TC

0 , 374

This calculation is approximate. For a more accurate calculation access must be found to a

database containing data for Cp in a liquid phase.

In order to include heat of admixture, heat of dilution, melting heat and heat of crystallization,

one must refer to specialised databases.

Heat of reaction hr can be calculated from standard heats of formation Hform and stoichiometric

coefficients ? k;j that have a negative sign for reactants and a positive sign for products of reaction. For

one reaction:

C

hr = j Hform j

j =1

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

and the internet address of the National Bureau of Standards database

www.ddbts.de

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.

Using Excel we are able to solve the following problems:

1.

2.

3.

4.

5.

We have as many equations as unknowns, and the system is linear.

We have as many equations as unknowns, and one equation is non-linear.

We have as many equations as unknowns, and more equations are non-linear.

We have one equation less than unknowns, and the system is linear.

If our problem does not fit into any one of these categories, the problem must be redefined, i.e. other

additional relations must be found, some blocks in the block diagram must be consolidated, some of

the components must be disregarded, and so forth.

Advantage of Using Excel

Problem 1

When solving Problem 1 we proceed as follows:

We multiply the transposed matrix of coefficients by the matrix of coefficients to get a square

matrix of the most expectation values of the matrix coefficients in the sense of the method of

minimum squares. The formula has the following form: PRODUCT OF MATRIXES

(TRANSPOSITION(A1:D18);A1:D18), where A1 is the cell in the top left corner of the matrix

of coefficients and D18 is the cell in the bottom left corner.

We multiply the transposed matrix of coefficients by the right-hand-side vector to get a

corrected vector with the same dimension as the square matrix.

We multiply the inversion of the square matrix by the corrected vector to get the vector of

solutions.

Problem 2

We solve this problem by multiplying the inversion of the square matrix of coefficients by the righthand-side vector.

The formula has the following form: PRODUCT OF MATRIXES(INVERSION(A1:H8);I1:I8), where A1

is the cell in the top left corner of the matrix of coefficients and H8 is the cell in the bottom right corner.

Column I1:I8 would correspond to the right-hand-side vector.

Problem 3.

In solving Problem 3 we proceed as follows:

As a consequence of the incorrectness of the value fixed in this manner the non-linear

additional relation is not satisfied.

We keep modifying the fixed value until the non-linear relation is satisfied with the accuracy

required.

This procedure can be performed manually, however, using the Solver function is more

efficient. The procedure is described in detail in the problem_redukce file.

Problem 4

27

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. Kubcek Numerical Algorithms of Solutions to

Chemical Engineering Problems (Kubcek, M.: Numerick algoritmy reen chemicko-inenrskch

loh. 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.

A table of solutions provides complete characteristic for each stream; that is the flow of components,

overall flow, temperature and pressure. The columns represent individual streams and the rows are

used for entering the mentioned parameters (see, for instance, the problem_soda file).

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.

28

Address for consultation, training and advisory services: see the main Web page.

List of Selected Projects Solved by the Authors:

Project 1: Desulphurisation Unit of the Mitsubishi Company

Project 2: Co-generation Plant of the koda Company

Project 3: Catalytic Reactor - Draslovka Koln

Project 4: Co-generation Plant with the Utilisation of a Heat Pump - Brun &Sorensen - Denmark

Project 5: Manufacture of Cole-seed Oil - Sindat Engineering

Project 6: Refining of Crude Spirit - Alcohol Distillery

Project 7: Low-pressure Manufacture of Nitric Acid - Sindat Engineering

Project 8: Manufacture of Pure Salts OSRAM Bruntl

Project 9: Enthalpy Balance of a Bakery Factory - Pragosoja Strncice

Project 10: Enthalpy Balance of a Boiler for Steam Production - Detmarovice Power Plant - Mitsubishi

Co.

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)

29

38

Composition of rum with 38 volume per cent in weight fractions at various temperatures

kg/m3

m3/kg

temperature

0

10

ethanol

806.0

798.0

water

999.8

999.6

ethanol

0.001241

0.001253

water

0.001000

0.001000

ethanol

33.07

32.85

water

66.93

67.15

ethanol

38.00

38.00

20

30

40

789.0

781.0

772.0

998.2

995.6

992.2

0.001267

0.001280

0.001295

0.001002

0.001004

0.001008

32.64

32.47

32.29

67.36

67.53

67.71

38.00

38.00

38.00

50

60

70

763.0

754.0

745.0

988.0

983.2

977.7

0.001311

0.001326

0.001342

0.001012

0.001017

0.001023

32.13

31.97

31.87

67.87

68.03

68.17

38.00

38.00

38.00

0.001342

0.001000

31.35

68.65

38.00

ethanol

water

temperature

70C

745.0

0C

999.8

30

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