UNIVERSITY OF THE ATLANTIC

SCHOOL OF ENGINEERING
CHEMICAL ENGINEERING PROGRAM

MATERIAL BALANCE MODULES

Prepared by:

Freddy Andrés Díaz Mendoza y Leda Pernett Bolaño

Barranquilla, February 2005

1
1 INTRODUCTION TO CALCULATIONS IN CHEMICAL ENGINEERING
At the end of this section, you should be able to:

Add, subtract, multiply and divide units associated with numbers.

2) Identify the associated units in the international system (SI) and the American system
engineering (SAI).

3) Convert a quantity expressed in a set of units to another system using the

corresponding conversion factors

4) Define and use the conversion factor gc.

5) Explain the concept of dimensional consistency and apply this concept to given the
units of certain terms of an equation, assign the units of the other terms.

1.1 DIMENSIONS AND UNITS

Una dimensión es una propiedad que puede medirse. Una cantidad medida tiene un valor numérico
and one unit:

2 feet} One dimension: Length

Valor Unit
Numerical

Dimensions: Length, mass, time, temperature, or they can also result from the
multiplication or division of other units:

Length/time = speed

Length3 = volume

Mass/Length3= density

The numerical values of two or more quantities can only be added or subtracted if the units are
the same ones:

3 cm - 1 cm = 2 cm 4m2-2 m3= ??

Numerical values and their corresponding units can be combined by multiplication or

division

5 km / 2 hours = 2.5 km/h

2
 3 cm × 4 cm = 12 cm2

6 grams
= A numerical value that has no units: dimensionless quantity
2 grams

Note that although you can divide or multiply units, if the dimension is the same, they must be
equal in order to carry it out, i.e. (abbreviation of id est, Latin phrase that translates to this is):

6m3 6m3
=
20 cm30.2 m3

1.2 SYSTEMS OF UNITS

A system of units has the following components:

• Basic units [=] Length, mass, time, and temperature.

• Derived units are the multiplication or division of basic units.

A list of the basic units in the International System (SI) and the American System
Engineering (SAI) is presented in the following table:

Dimension YES SAI

Length m ft

Era kg lbm

Time s s

Temperature K ºR

Volume m3 ft3

Strength N lbf

Pressure Pa psi

Energy J Btu

The SAI system has two difficulties: one, 1 ft = 12 inches (which means they are not multiples of 10), and
the other is that lbf≠lbmthat is to say, the units of two different dimensions can be confused, pound
mass with pound force.

One of the units derived in the International System is the unit of force:

3
 m
F= m! a [=] kg
s2
m
1N" 1 kg! 1
s2

1 N is equivalent to the force that is applied or communicated to 1 kg to achieve an acceleration of 1 m/s.2.

In the American Engineering System, the derived unit is known as [Link] is defined as
the product of one unit of mass (1 lbmby the acceleration of gravity measured at sea level
and a latitude of 45º, where g = 32.174 ft/s2.

m
1N ! 1 kg" 1
s2
ft
1 pound f! 1 lbm" 32.174
s2
m
1kgf! 1 kg" 9.806
s2
ft
1lb ! 1 slug" 1
s2

Unit conversion is unpleasant, but essential in any technical calculation. For

to convert an amount expressed in one unit in terms of another unit, the must be used
conversion factors.

Example: convert 6 ftà cm

12 in 2.54 cm
6 ft× × = 182.88 cm
1 foot 1 inch

We have expressed the conversion factor in the form of a quotient

400 in3 cm3

Exercise: convert !
1 day min

To convert a force from a defined unit (i.e., N) to a natural unit (kg m/s)2),
we use the corresponding conversion factor:

m
25 Nà kg
s2

4
The value of gc it can have different values depending on the system of units

System gc
1 kg m s2
YES 1N
32.174 lbmft s2
SAI 1 lbf
9.806 kg m s2
Metric 1 kgf
2
1 slug feet per second
British 1 lb

The value of gcit is a conversion factor and should not be confused with the value of acceleration of the
gravity, which is written as g.

1.3 DIMENSIONAL CONSISTENCY AND DIMENSIONLESS QUANTITIES

We had previously established that certain amounts could be added and subtracted only if the
units were the same. If the units are the same, their dimensions are also the same. This gives us
It states that for an equation to be valid, it must have dimensional consistency, or what is the same.
the same, it must be dimensionally homogeneous, i.e., all terms must have the same
units.

Exercise: A(ft) = 3t (seconds) + 4 What should be the units of 3 and 4?

There are certain parameters that have no units and are called dimensionless groups. Therefore
an example of a dimensionless group frequently used in fluid mechanics is the Reynolds number:

5
 m L
L! !
Re= L3 t = dimensionless
m
L! t

The exponents, for example x2 and the arguments of transcendental functions like sine(x), log(x),
exthey are dimensionless quantities, that is, they have no units.

Exercise: Yes! = 1.13 exp (1.2" 10-10P), where the density is in g/cm3y P in N/m2Which
-10
they must be the units of 1.13 and 1.2
! 10 ?

2 PROCESSES AND PROCESS VARIABLES

At the end of this section you should be able to:

• Explicar con sus propias palabras: a) qué es proceso, b) cuáles son las unidades de proceso más
important in the chemical processes industry, c) the meaning of the mole, d) the difference
between density and relative density.

• Convert moles to mass (and vice versa) and calculate the molecular weights of a substance from
of its molecular weight.

• Calculate the density of a substance from the values of its relative density (y
vice versa.

• Calculate the mass (or mass flow), the volume (or volumetric flow) or the moles (or molar flow)
of a species given a value of one of the variables and known its density and molecular weight.

• Convert the composition of a mixture expressed in mole fraction to mass fraction, and
vice versa.

• Determine the average molecular weight of a mixture based on its molar composition.
music.

• Convert the concentration of a material from one measure to another, including mass/volume,
moles/volume, ppm and molarity.

• Define what temperature is and how to convert a given temperature into any scale (K, ºC, ...
°F, °R), to another.

6
2.1 PROCESSES AND PROCESS UNITS1
A process is an operation or series of operations that causes physical, chemical, or
biochemicals in a material or mixture of materials. A process unit is a device in which
carries out one of the operations that is part of the process. A process with its parts is
shown in the following figure:

As part of their job, the chemical engineer does:

• Design individual process units

• Supervise the operation of a process

• Modify and optimize the design of a process.

But in order to carry out these tasks he must know the compositions and the conditions of the
output and input flows, known as process variables.

When only physical changes occur in the processing units, these are known as
unit operations. Examples: distillation, liquid-liquid extraction, filtration, drying,
leaching, absorption and adsorption. If the unit involves a chemical change, it is known as
reactor. Basically, there are three types of reactors: the batch or discontinuous reactor, the continuous reactor
complete mix and piston flow reactor. Other types of reactors include the catalytic reactor
fixed bed, the fluidized bed reactor and the membrane reactor.

1
Translation and adaptation taken from the Visual Encyclopedia of Chemical Engineering Equipment, developed by the
Professor Susan Montgomery from the University of Michigan. The encyclopedia comes on the Interactive compact disc.
Chemical Process Principles (ICPP), which comes with the text Elementary Principles of Chemical Processes by Richard
M. Felder and Ronald W. Rousseau (3rd Ed., John Wiley & Sons, 2000).

7
2.1.1 REACTORS

Batch reactor

The batch reactor is the simplest of the reactors used in the

chemical processing industry. In it, the reactants are introduced into the reactor, mixed, and allowed to
that react for a certain period of time, and then the final mixture, composed of the
products and unreacted reagents. A batch reactor diagram is shown in the
next figure (adapted from Elements of Chemical Reaction Engineering, by H. Scott Fogler,
Prentice Hall, 2nd Ed., 1992):

Batch reactors operate under non-stationary conditions, i.e., the composition varies.
over time, although at each moment it is uniform throughout the volume of the reactor. They are used
basically for liquid phase reactions, where long reaction times are required. A
reactor batch has the advantage of being usable for different products, it is easy to clean and
puede alcanzarse conversiones altas dejando reaccionar los reactivos el suficiente tiempo. Entre sus
disadvantages include the high cost of maintenance and labor during production, and
the downtime during loading, unloading, and cleaning.

Continuous Stirred-Tank Reactor (CSTR)

Continuous Stirred Tank Reactors (CSTR)

Reactors are open systems (i.e., there is continuous input and output of materials to the system), that
they operate in steady state (i.e., the conditions in the reactor do not vary over time). Due to
the action of a stirrer, the mixture is completely homogeneous, and its properties are
relatively uniform throughout the entire volume of the reactor. Likewise, the conditions of the
The outlet current is the same as the mixture inside the reactor.

Complete mix reactors are used in the chemical process industry.

fundamentally in homogeneous reactions in the liquid phase and can be used in series or in
parallel. They normally have a jacket to exchange heat. The fermenters are
complete mix reactors that are used in biological processes, such as breweries,
antibiotics and water treatment. Among its advantages are: easy temperature control,
economic and easy to access inside. Among their disadvantages are that the conversions of

8
the reactants to products by reactor volume is small compared to other reactors
continuous. A complete mix reactor used as a fermenter is shown in the following
figure (adapted from: [Link], New Brunswick Scientific Co., Inc., New Jersey, USA):

Plug Flow Reactor (PFR)

The plug flow reactor (PFR) consists of

a tube through which the reagents flow. They generally operate in a steady state, and the reagents
they are continuously consumed as they flow through the reactor, causing a gradient of
concentration. Finally, the products (and unreacted reagents) leave the reactor
continuously.

The PFR can be a single tube or a bank of tubes. Its diameter varies from a few millimeters.
up to several meters. The selection of diameter depends on construction, pumping, and
of the heat transfer requirements.

Piston flow reactors are used in liquid or gas phase reactions. Among their
Advantages include: easy maintenance as they have no moving parts, high conversions due to
volume of the reactor, mechanically simple, the quality of the products does not vary, good for
to study rapid reactions and for large volume processes. Among its disadvantages are included
which are difficult to control, due to variations in their temperature and composition A reactor
piston or tubular flow is shown in the following figure:

9
Packed Bed Reactor (PBR)

The fixed bed reactors (PBR, for Reagents

Packed Bed
Reactor) consists of a tube or shell, Reagents
inside which there is a bed
catalyst fixed. This system of
reaction heterogeneous if use
mainly for phase reactions
soda. In the PBR the reactants
they enter the reactor, flow into the bed
catalytic, where they react to form
the products that come out of the reactor.
Catalyst
When designing a PBR, it must be taken into account solid
count the lifespan of the catalyst,
since it establishes how long he/she will work
the reactor before it is needed
regenerate the catalyst. The pills
of the catalyst are generally
granular, with diameters between 1 and 5
mm.

PBRs are easy to build, operate

and maintain, economic, are achieved
high conversions by weight of
catalyst, and effective for reactions
to work at pressures and temperatures Products
high. However, the processes of
heat transfer to or from it Products
reactor and temperature control are
difficult, causing the formation of Fixed bed catalytic reactor: a single tube and
temperature gradients; the catalyst multiple tubes. (Adapted from Heterogeneous
it is complicated to replace, and they tend to Catalysis, by Mark G. White, Prentice Hall, 1990 and
to form pipelines along the Elements of Chemical Reaction Engineering, by H.
reactor, just like side reactions. Scott Fogler, Prentice Hall, 2nd Ed., 1992.

2.1.2 SEPARATION UNITS

Distillation tower

Distillation columns are primarily used for liquid-liquid separations. The column of

10
The plate is the column used. Distillation is used when there are differences in volatility.
relative. The difference in concentration causes the more volatile component to transfer from the
steam flow to liquid flow. The steam that comes out of the condenser contains the component
more volatile, while the less volatile exits through the liquid line of the reboiler.

When the power supply current enters the column, at a point generally centered (see
figure), the steam that rises in the upper section of the feeder is washed with the liquid that
it descends absorbing the less volatile component and allowing for separation. At the top of
The column steam condenses in a condenser. The condensate flow splits into two.
currents: one that returns to the column, known as reflux, and another, the product current or
distilled. At the bottom, a reboiler separates the stream into a liquid stream, the residue, while
that a steam flow returns to the column.

Adaptation taken from Visual Encyclopedia of Chemical Engineering Equipment, Susan

Montgomery, University of Michigan.

Absorption towers

In absorption columns, a gas mixture comes into contact with a liquid, so that
one or more of the gas components dissolve in the liquid, resulting in a solution of these

11
in the liquid. The dehydration of natural gas with glycol is a typical example. In the column of
absorption involves passing the wet natural gas, which comes into contact with diethylene glycol. The
water is highly soluble in glycol, which generates a liquid flow with the absorbed water,
while the dehydrated natural gas current exits from above, as shown in the figure.

The liquid-liquid extraction towers are similar to absorption towers, but the difference is
that both phases are liquid. It is usually used when the components cannot be separated.
because their relative volatilities are similar.

Absorption tower. (Taken from Introduction to the Natural Gas Industry, Notes by Mauricio)
Field, Colombian Oil Company ECOPETROL, 2000.

Adsorption tower

Adsorption is a separation process in which a certain component of a fluid (the adsorbate) is

transfers or accumulates on the surface of a solid called adsorbent. Generally, the particles
the adsorbent is placed in a fixed bed, while the fluid is continuously passed through
through the bed, until the solid saturates and there is no more separation. The flow is changed to a
second bed, while the first bed regenerates.

There are two types of adsorption. The first, physisorption, is a physical phenomenon that occurs at
temperatures below 200ºC, where the material is adsorbed due to the physical interactions between
the adsorbate and the adsorbent, such as hydrogen bonds and van der Waals forces. In the second
In this case, chemisorption occurs at temperatures above 200ºC, and it occurs due to the formation of
a chemical compound. The adsorbent material can be natural or synthetic, typically granular and
extremely porous, with large internal surface areas. An adsorption system is
shown in the following figure (Adaptation taken from Unit Operations of Chemical Engineering, W.
L. McCabe, J.C. Smith, and P. Harriot, 5thEd., McGraw Hill, 1993.

12
 Nutrition

Open valve

Closed valve

Clean gas

Vapor Noble gas

A widely used adsorbent is silica gel, which is commonly found in small packets.
small bags as a drying agent accompanying medicinal, food, and electronic articles.

There are other separation processes both chemical and physical, such as separators,
crystallizers, dryers, ion exchange columns, humidifiers membranes
evaporators, cyclones, centrifuges, etc. When solids are present, these can be removed by
filtration or sedimentation.

2.2 PROCESS VARIABLES

2.2.1 THE MILL

A gram-mole (g-mol) or simply mole in the international system of measurements (SI) is the amount
of that species whose mass is numerically equal to its molecular weight and equal to 6.023! 1023
particles.

Other specifications of the mole are defined similarly:

1 lbmol of C12H22O11 = 342 lb of C12H22O11

1 kmol of C12H22O11 = 342 kg of C12H22O11

13
1 ton mole of C12H22O11 = 342 tons of C12H22O11

1 molecule of C12H22O11 = 342 ounces of C12H22O11

In short, if the molecular weight of a substance is M (let's remember that the molecular weight of
A substance is the sum of the individual atomic weights that make up the molecule; and the weight
The atomic mass of an element is the mass in grams of an atom on a scale that assigns carbon 12.
a molecular mass equal to 12), then:

1 gmol of a substance (or simply mole) = mg of the substance

1 lbmol of a substance = M lb of the substance

1 kgmol of a substance = M kg of the substance

1 ton mole of a substance = M ton of the substance

Just as we use conversion factors for different units of mass, we can

use it for the molar units.

How many particles are there in 270 grams of water?

1 gmol of water 23
270 g! = 15 gmol of water = 15! 6.023! 10 molecules of water
18 g

How many lbmol?

1 lbmol
15 gmol of water! 0.033 lbmol of water
453.6 g/mol

How many lbmol of H?

2 lbmol of H
0.033 lbmol of water! 0.066 lbmol of H
1 lbmol of water

2.2.2 DENSITY

Density is the mass per unit of volume of the substance.

m m g kg lbm
!" {=} 3 [ =] 3 ,3 3 ,
V L cmm ft
g 1.6 g it is equivalent to saying that: 1 cm3from the
If the density of a substance is! = 1.6 "
cm 3
1 cm3
the substance has a mass of 1.6 grams or that 1.6 grams of the substance occupies a volume of 1
cm3and should be used as a conversion factor.

In order to calculate the density of a substance, both the mass and the volume need to be measured.

14
what occupies that mass. The density of liquids and solids does not vary significantly with the
pressure, but it changes with temperature.

The specific volume of a substance is the inverse of the density:

V L3 cm3m 3 ft3
v̂! {=} [= ] , ,
m m g kg lbm

The relative density (also known as specific weight relative) of a substance is the
quotient of the substance's density and the density of a reference substance under
specific conditions.

! sust m/L3
p.e.r. = s.g. = = " dimensionless (sg for its acronym in English specific gravity)
! ref mL3

The reference density in solids and liquids is water measured at 4°C:

! ref (H2O @ 4°C) = 1.000 g/cm3

1000 kg/m3

62.43 lbm/ft3

The symbolism used is:

25° ! density of the substance measured at 25°C

s.g.= 0.8
4° ! density substance reference (water) at 4°C

Density is a thermodynamic property of a substance that does not depend on the amount (i.e., it is
an intensive property) and the only way to estimate it is by measuring it.

The specific gravity of ethanol (C2H6O) is 0.789 (M=46.1 g/gmol):

What is its density in g/cm?3lbm/ft3, kg/m3What is the volume in ft?3that occupies 120 kg of the
Substance? How many moles are there in 200 cm?3of the substance?

2.2.3 MASS FLOW AND VOLUMETRIC FLOW

Continuous processes involve the movement of material from one point to another. The speed at which it...
the movement or transportation of this material is known as material flow: mass flow [=]
masa/tiempo, flujo volumétrico [=] volumen/tiempo, flujo molar [=] moles/tiempo. Los flujos
Volumetric, molar or mass quantities are related through density and molecular weight.
! M
volume or volumetric flow"
$# mass or mass flow"$# moles or molar flow

15
2.2.4 MASS FRACTION AND MOLE FRACTION

The mass fraction is the ratio of the amount of a specific substance divided by the
total amount of mass present.

20 g water + 50 g ethanol + 10 g acetone = 80 g total

What is the mass fraction of water in the mixture?

mA mA 10 g 10 g
X A= = = = = 0.25
mt m A+ m And+ m Ac20 g + 50 g + 10 g 80 g

If we store the prepared mixture in three different containers with the specified masses,
What is the mass fraction of water in each of the containers?

16
The numerical value of the mass fractions does not depend on the units as long as they are.
equal:

20 g of A 20 kg of A 20 lbm of A
[= ] [=]
100 g total 100 total kh 100 total lbm

moles of A
The mole fraction is defined in the same way:YA=
total moles

The mass percentage of A is 100•XA, and the molar percentage is 100•YAThe mass composition or
molar expresses the mass and molar percentages of the substances present in the mixture.

Mass fractions can be converted to a series of molar fractions (or vice versa):

• Assume a basis of calculation (mass or moles)

• Convert the mass of each component into moles (massà moles), or moles in mass (moles
à dough)

• Calculate the respective molar fraction

A mixture of gases has the following mass composition: O2à 16%, COà 4%, CO2à 17% and
N2à 63%. ¿Cuál es la composición molar? ¿Cuál es su peso molecular promedio?

Basis for calculation: 100 grams of the total mixture

Composition Fraction Table in

Compound music basic grams Moles Molar fraction

O2 16% 0.16 16 0.5 0.152

CO 4% 0.04 4 0.143 0.044

CO2 17% 0.17 17 0.386 0.118

N2 63% 0.63 63 2.25 0.686

100% 1.00 100 3.279 1.000

The average molecular weight of a mixture is the quotient of the mass of the sample divided by the
total number of moles of the mixture; it can also be calculated from the mole fraction (or
molecular weight) and their respective molecular weights:

17
 mt
M=
nt
M= y1 M1+ y 2 M2+ ...... + y n M n
n
M= !
n=1
yn M n

1 n
xn
=!
M n=1 Mn

where: mt total mass

nt total number of moles

yn mole fraction of the n-th component

xn mass fraction of the n-th component

Mnmolecular weight of the n-th component

2.2.5 CONCENTRATION

It is the amount of a certain solute over the amount of a certain solvent or solution in a mixture of two or
more compounds

Mass concentration (mass per unit volume)

g of A lbm of A kg of A
, ,
L of solution ft solution
3
m of solution
3

Molar concentration (moles per unit of volume)

gmol of A lbmol of A kgmol of A

, ,
L of solution ft of solution
3
m 3of solution
grams of solute
Molarity =
The solution
grams of solute
Molalidad =
kg of solvent

ppm = a way to express the concentration of very diluted solutions

ppm = XA ! 106mass fraction for liquids and solids

ppm = YA ! 106molar fraction for gases

18
2.2.6 TEMPERATURE

Temperature is a measure of the kinetic energy that substances possess. However, the
The kinetic energy of a substance is not a property that can be easily measured, and one resorts to
to other properties that can indeed be measured:

How the volume of a fixed mass changes: Hg thermometer.

Voltage at the junction of two metals: thermocouple.

Electrical resistance: resistance thermometers

Temperature scales are obtained by assigning numerical values to two easily measurable quantities.
Recordables. There are two relative scales and two absolute scales. The absolute scales have part of
absolute zero, the lowest temperature that is believed to exist. This temperature is related to
with the laws of ideal gases and the laws of thermodynamics.

K = °C + 273

°R = °F + 460

°F = 1.8 °C + 32

2.2.7 PRESSURE

Pressure is defined as the quotient of a force acting on a surface:

F N A
P= [ =] 2 [Pa]
A m
lbf
[ =] 2 [=] psi
ft
The fluid pressure is the minimum force that must be exerted on the stopper in order to prevent the
fluid output. However, an additional definition of fluid pressure is due to
introduce to explain the concept of atmospheric pressure. In a closed vertical container:

F W mg h mhg
P= = = !=
A A A h V
P= !gh

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 The fluid pressure at the base of the column is by definition the force exerted at the base.
divided by the area.

P= !gh As can be seen, surface A does not appear in this equation because it
which is applicable to a fluid column as thin as a capillary or as wide as a
tank.

The above leads us to express the force per unit area, it can
to express oneself as the height of a fluid. This pressure is called hydrostatic pressure.

If pressure is applied to the surface of the container:

P= !gh+ Po

For a mercury column, the pressure at the base of the vessel can be expressed as:

P(mmHg)= Po(mmHg)+ h(mmHg)

The analysis we have conducted can be directly applied to various devices that are used
to measure the pressure of a fluid, called manometers. The simplest of all is the
open tube manometer, the analysis is based on the application of Pascal's Principle: pressure
At a point within a stationary fluid, the pressure is the same in all directions.

The pressures mentioned so far are absolute pressures, in that an absolute pressure
equal to zero corresponds to a perfect vacuum. Many pressure measuring devices measure
the gauge pressure of a fluid, that is, the pressure relative to atmospheric pressure:

Pabsolute= Pmanometric+ Patmospheric

3. THE BALANCE OF MATTER

At the end of this section you should be able to:

6) Explicar en sus propias palabras el significado de: proceso por tandas, semintermitente,
continuous, in steady state and unsteady state, degrees of freedom.

7) Based on the description of a process: a) Draw and label the flowchart, b) Choose
an adequate calculation basis, c) Apply the principle of mass conservation to formulate the
material balances, d) For a process with multiple units, identify the subsystems in
where material balances can be applied, e) Conduct an analysis of the degrees of freedom
global and in each subsystem and f) Write and solve the equations to determine the variables

20
 unknown.

You must be able to apply the above steps in systems without and with chemical reaction.
the systems that involve chemical reaction make balances of atomic and molecular species.

When we talk about mass balance, what we do is apply the principle or law of
conservation of mass, which states that mass is neither created nor destroyed (except for
nuclear reactions). In fact, we must understand that this principle is a hypothesis that has never been
has been conclusively demonstrated; however, it is a very solid hypothesis that has never been
experimentally refuted.

The objective of this section is not only to understand the principle or fundamental concept of conservation.
of mass, but rather on how to apply this concept in problem solving, how to develop
skills to analyze and solve mass balance problems and how to devise a strategy to
solve the problem. In this section you will learn:

1. Procedures for conducting mass balance in individual units and processes in multiples
stages.

2. Methods to organize the known information about the process variables.

3. Development of mass balance equations to solve equations as a function of

unknown variables.

3.1 CLASSIFICATION OF PROCESSES

Process: it is any operation or series of operations that causes a physical or chemical change in
a material or mixture of materials. Example: chemical reactors, distillation towers, towers of
gas absorption, etc.

System: it is any portion or part of a process that is chosen arbitrarily for its
analysis. A system can be open or closed. Open: there is transfer of material through the
System boundary. Closed: no material transfer.

The processes can be:

Intermittent or batch: the feed is loaded into a container and after that
After a certain period of time, the contents of the tank are removed.

∞
t<0 t=0 t=t t=!

2. Continuous process: input and output streams flow continuously.

21
 ∞

3. Semi-intermittent processes: there is no feed and the outputs are continuous: gas cylinders.

These processes can operate in two ways:

If the value of all process variables such as T, P, flows, etc., do not undergo modifications to the
Over time, it is said that the system operates in a steady state.

2. If any of the process variables changes its value over time, it is said to be operating in
non-stationary state.

3.2 THE GENERAL BALANCE EQUATION

Let's suppose we have methane (the main component of natural gas), and that it flows through
from a gas pipeline. It is intended to determine whether the gas pipeline from the extraction point to a
point where this is being used correctly, and for this purpose the mass flows were measured
at each end of the pipeline, finding that the values were different (min≠mout):

min kg CH
4 /h mout kg CH4/h

What could be the possible explanations to justify the difference that is observed between the
flows?

a) That the gas pipeline has a leak and is losing methane somewhere.

b) That methane reacts and is consumed as a reagent.

c) That for some reason methane is produced as a product.

d) That methane is being adsorbed onto the walls of the gas pipeline and is accumulating in the
system

e) That the measurements are incorrect.

If the measurements are correct and no leaks were found, the only explanations are
generation, consumption or accumulation within the pipeline. If we express a material balance in
the system can be expressed in the following way:

22
 ENTER + GENERATE - SELL - CONSUME = ACCUMULATE (Equation 1)

A material balance is nothing more than an accounting of material. The term accumulation is the
change of the variable with respect to time. Let's imagine, for example, the city of Barranquilla.
Let's imagine that in one week 1500 people enter the city, 1200 leave, 300 are born, and die.
250. If we write a balance of the city's population:

1500 – 1200 + 300 – 250 = 350

Weekly, the population of the city increases by 350 people.

Balances can be written in two ways:

a) Differential form, which indicates what happens in a system at a given moment. It is used in
continuous processes.

b) Integral form, which indicates what happens between two moments and is used in batch processes.

For steady-state processes, the variable does not vary with time, thus the term of
accumulation in the general balance equation is set equal to zero. Equation 1 simplifies to:

ENTERS + GENERATES - SALES - CONSUMES = 0 (Equation 2)

ENTER + GENERATE = SALE + CONSUME (Equation 3)

EXAMPLE: There are two mixtures of methanol and water in separate containers. The first mixture
contains 40% by weight of methanol, while the second contains 70% by weight of
methanol. If 200 grams of the first mixture are combined with 150 grams of the
Secondly, what would be the mass and composition of the product?

3.3 PROCEDURE TO RESOLVE BALANCE PROBLEMS

MATERIAL
1) Read the problem carefully (more than once), and note what is known and what is
what is desired to be found in the problem.

2) Make a flowchart of the process in which you draw the process units and the
currents that enter and exit each unit.

3) Label all known streams indicating flow rates and compositions and note it down
all the additional information provided by the problem.

4) Label the unknown variables. The flowchart is fully labeled.

if you can express the mass or mass flow (or moles or molar flow) of each
component of each current in terms of the labeled quantities.

5) Establish the assumptions or presumptions of the problem. Choose as the calculation basis the
amount or the flow of one of the process streams. Please note that:
23
 If the amount or flow of a current is specified in the problem statement,
Generally, this is taken as the basis for calculation. The values that are calculated are based on
in this value.

If multiple quantities or currents are specified, they must all be taken as the basis for calculation.

If no quantity or current is specified in the problem statement, choose as base

an arbitrary amount or the flow of a current that provides the greatest information in its
composition and simplify the calculations

6) Convert volumetric flows into mass flows or molar flows, if necessary.

Remember that:

! M
volume dough moles

and that there are two ways to express the molar flows or the mass flows of each component.
One way is to express the mass flow with a symbol mi, where the subscript indicates the
component i, and the other way is by expressing the product of xiF, where xiit is the mass fraction
of component i, and F is the total mass flow. The same occurs with the molar flow.

7) Write any additional relationship given by the statement of the problem. Express these
mathematically relationships in the form of equations. These relationships can be:

Percent recovery

√Relationship of compositions

Flow reason

8) Perform an analysis of the degrees of freedom of the system (DOF).

9) Formulate the mass balances. If there are N chemical species, you can make N balances of
mass for each species and a total mass balance; that is, there are N+1 equations, but of
this system only N equations are independent. The N+1 equation is generated from the
others

10) Solve the equations to determine the value of the unknown variables. In order to
To solve the system of equations, it is necessary to have as many equations as unknowns (GL =
0). When carrying out the calculations, be organized. Visualize the problem and think about its possible solutions.
solutions. If you find different unit systems, convert them to one single system. You will be able to
solve the problems with ease yes:

a. He is careful in the analysis, which is done gradually. Have confidence and win.
experience (i.e. practice!).

b. Understand the facts and relationships well. Visualize your ideas, make diagrams, and formulate them.
questions that clarify your thoughts. Make sure you understood the problem well by repeating it.
his reading. Refer to previous experiences and examples.

24
 c. If the problem is complex, break it down into smaller parts and start the analysis and calculations.
where there is more information. The degrees of freedom will be very useful.

d. Don't guess, work on the problem.

11) Observe that the answers are reasonable and make sense, i.e., establish whether the results
obtained fit the physical reality. If they do not, determine whether the error is numerical or
conceptual.

3.3.1 ANALYSIS OF DEGREES OF FREEDOM (DF)

In general, it is known that to solve an algebraic system with N unknowns, it is necessary

have N independent equations. If we have fewer than N equations, we probably do not
it can solve all the unknown variables of the system. If there are more than N equations, it can
choose N to solve the system. However, there is a risk of errors and inconsistencies,
because the solution obtained depends on which N equations are chosen. Then the way
The correct condition is that the number of unknown variables is equal to the number of equations.
independent. Degrees of freedom is an index that measures this balance; it is a mechanism of
count all the variables, balance equations, and relationships that are involved in the system. The
variables can be extensive or intensive. Intensive variables are those that are
independent of the size of the system (e.g., temperature, pressure, density) and the variables
Extensive properties are those that depend on the size of the system (e.g. mass, volume).

The analysis of the degrees of freedom is carried out after having completely labeled the diagram.
of flow; account for the unknown variables and then count the number of equations
independents that relate these variables. Subtract the second from the first and the result is the
number of degrees of freedom of the process.

Degrees of freedom (DF) = number of unknowns - number of independent equations.

If the degrees of freedom > 0, that is to say they are positive it is said that the problem is not
completely specified (subspecified), and the value of all
the unknown variables cannot be solved.

If the degrees of freedom < 0, that is to say they are negative, it is said that the problem is about
specified, and there is information or data that is redundant.

If the degrees of freedom = 0, the system is fully specified, and all the variables
unknowns can be calculated and there is a unique solution.

The analysis of degrees of freedom is another tool to facilitate problem solving.

complex, for example problems with multiple units. In addition, they allow you to know beforehand
perform numerical calculations the following:

a) How many unknowns does the problem have and what are they?
b) What are the known data of the problem.
c) How many balances can you perform and identify which ones you will use.

25
d) Identify which and how many are the relationships established by the problem.
e) He/She indicates:

i. If you have additional data and how many.

ii. If any data is missing and how many.

iii. If there is no missing data.

iv. If you have to set a calculation base.

3.2 SYSTEM WITH MULTIPLE UNITS

So far, we have observed that even when the problems were complex, they could be
represent in a single "box", and we could point out the inputs and outputs. However, the
The majority of chemical processes consist of a sequence of several units, and in order to
design a system with multiple units, in addition to the input and output currents of the entire
plant, the flows and compositions of all streams must be known and specified
they connect the different units that make up the plant. Let's consider the following problem:

Q1
A = 0.619
B = 0.05 Q3
C = 0.331 A = 0.152
B = 0.808
C = 0.04

F= 1000 mol/h Q2
A = 0.2 A=x
I II
B = 0.3 B =y
C = 0.4 C = 1–x–y

Q4
A = 0.005
B = 0.055
C = 0.94

If unit I is viewed as a separate system, three independent balances can be made and
relate the currents F, Q1, and Q2. Similarly, unit II can be treated as a
separate system and make three independent balances to relate the currents Q2, Q3, and Q4.
Finally, the process can be seen as a single unit, so that only the
currents that enter and exit the global process; in this case, three balances can be made
independent and the equations are only associated with F, Q1, Q3, and Q4.

The balances formulated with the whole system are known as global balances, while the
Balances associated with each unit will be referred to as unit balances.

26
In the case of the previous system, if we consider unit I as a system, unit II as
system and the entire process as a single unit, this gives us two sets of equations
more a set of global balances. Each set of balance equations contains at least
three independent balances:

√3 balances Unit I
√3 balances Unit II
√3 global balances

Remember that in the case of single units that encompass N components, N can be made.
chemical species balances, but only N balances are independent, while the (N +
1) balance does not offer more information. An analogous situation develops in systems that
they contain multiple units. If the process contains M units, each of which wraps
the same N components, only M balance sets are independent. In the case of the
Example, although it is possible to make three sets of balances (one for each unit and the global process)
only two sets are independent.

Set of Balances Unit I

A (0.2)(1000) (0.619) Q1 + x Q2
B (0.3)(1000) = (0.050) Q1 + y Q2
C (0.5)(1000) (0.331) Q1 + (1 –x–y) Q2

Set of Balances Unit II

A x Q2 = (0.152) Q3 + 0.005 Q4
B y Q2 (0.808) Q3 + 0.055 Q4
C (1–x–y) Q2 = (0.040) Q3 + 0.940 Q4

Set of Global Balances

A (0.2)(1000) = (0.619) Q1 + (0.152) Q3 + 0.005 Q4
B (0.3)(1000) = (0.05) Q1 + (0.808) Q3 + 0.055 Q4
C (0.5)(1000) =(0.331) Q1 + (0.040) Q3 + 0.940 Q4

If the balances of unit I and II for component A are added, then the equation is generated.
global balance for A. The same happens with B and C.

As can be seen, only 6 of the 9 previous balances are independent, and the problem is
You can solve it using the balances from units I and II, or by choosing the balances from one of the.
units with the global balance.

The degree of freedom analysis also applies to systems with multiple units. In addition to
degree of freedom for each unit, this applies to the entire process, and it is calculated in a manner analogous to the
case of a single unit.

27
Exercises
Following is a labeled flowchart for a steady-state two unit operation. Determine the solution order.
that you would make to determine the unknown process variables (do not resolve).

Q2 g C/s
475 g/s
x g A/g
y g B/g
800 g/s Q1 g/s 900 g/s (1–x–y) g C/g
Unit I Mixer Unit II
0.2 g A/g u g A/g vgA/g
0.8 g B/g (1–u) g B/g w g B/g
(1–v–w) g C/g Q3 g/s
0.012 g A/g
100 g A/s
0.588 g B/g
0.400 g C/g

The three distillation columns shown in the figure have been designed to separate 1000 mole/h of a
hydrocarbon feed containing 20% C1, 25% C2, 40% C3 and the rest C4 (all in a mole %). Given the
indicated compositions all in mole %, calculate all stream flow rates in the process.

Q4= 200 mol/h

C1 99%
C2
Q2
Unit II
C1
C2
C3 Q5
C1 4%
C2 76%
Q1= 1000 mol/h C3
Unit I
C1 20%
C2 25% Q6
C3 40%
C2
C4 15%
C3
Q3 C4
Unit III
C2
C3
C4 Q7= 400 mol/h
C3 94%
C4

28
Stoichiometry

At the end of this section, you should be able to:

12) Explicar con sus propias palabras el significado de: a) reactivo limitante b) porcentaje en
excess c) conversion d) yield and selectivity.

13) Write and balance chemical equations, identify the limiting reagent and calculate % of
excess and conversion %

Let’s observe the combustion reaction of propane:

C3H8 + 5O2 à 3CO2 + 4H2O

La reacción química nos ofrece información cualitativa: propano reacciona con oxígeno para formar
carbon dioxide plus water. This means that we have some reactants, which through the effect of a
chemical reaction, undergo a transformation and rearrange to obtain products.

In addition to qualitative information, the chemical reaction provides us with quantitative information.
1 mole of propane reacts with five moles of oxygen to form three moles of carbon dioxide.
carbon and four moles of water. When using this relationship, we must be sure that the reaction is
balanced. But what does it mean for a chemical reaction to be balanced? It means that the atoms
presents in each species or element on the left must be equal to the amount present on the
right. That is, the number of oxygen atoms on the left side of the reaction must be equal to
the amount of oxygen atoms on the right. The same happens with carbon and hydrogen.

What is the principle on which we base the above assertion? It is the principle of
conservation of mass, which states that mass is neither created nor destroyed, but transformed.

C3H8 + 502 à 3CO2 + 4H2O

1 mol 5 moles 4 moles 4 moles

44 g 160 g 132 g 72g

204 g 204 g

Note that the equation tells us in terms of moles (and not mass) the relationships between
reactants and products. But if we express the moles in terms of mass, then:

reactants mass = products mass

establishing a principle of equality, which is the principle of conservation of mass.

If a problem selects a basis of calculation in terms of mass, in order to use the

stoichiometric equation, the respective conversions must be made to express the mass in

29
mole terms. Subsequently, the number of moles formed can be converted to its mass.

Reactor
44 g Propane g of carbon dioxide
64 g of Oxygen g of water
M M
reaction
moles moles

The chemical reaction does not tell us how quickly a reaction occurs, nor how much takes place.
the same. The numbers that appear on the left of each element are known as the
stoichiometric coefficients. The direction of the arrow indicates the direction in which it is
taking the reactants to the products. A single arrow indicates that the reaction is irreversible,
while two arrows pointing in opposite directions indicate that the reaction is reversible.

The stoichiometric relationship of two molecular species involved in the reaction is the quotient
among its stoichiometric coefficients in the balanced equation. The stoichiometric ratio
It can be used as a conversion factor between the amount consumed (or produced) of a reactant.
(the product) based on the given amount of another reactant (or product) that participates in the
reaction:
1 mol of C3 H81 mol of C3 H81 mol of C3H85 moles of O2
, , , , etc
5 mol de O2 3 mol of CO24 moles of H2 4 moles of H2 O

In industrial reactions, it is rare to find exact stoichiometric amounts of the

materials used. Generally, for the reaction to take place or to consume a reagent
expensive, almost always excess reagents are used. For example:

C3H8 + 5O2 à 3CO2 + 4H2O

24 moles 160 moles

If we start the reaction with 160 moles of oxygen and 24 moles of propane (that is, the propane is
find in a proportion less than the stoichiometric one), the propane will disappear first or
before oxygen. The reactant that would disappear first if a reaction were to complete receives the
name of the limiting reagent; while the other reagents are called in excess.

Limiting reactant = reactant that is present in a smaller proportion than the stoichiometric.

Excess reagent = reagent (or reagents) that are present in excess relative to the reagent
limiting.

Reactor
24 moles of propane
160 moles of oxygen

Yes nA = amount of moles fed = 160 moles

30
nS = amount of moles stoichiometrically required to react with all the reagent
limiting

= 120 moles

The excess fraction is defined as:

excess moles n A! nS
=
stoichiometric moles needed to react with all the limiting reagent n S

The excess percentage is the excess fraction 100. For the example:

160! 120 40
Fraction in excess = = = 0.333
120 120

% excess = 0.3333 100! = 33.33%

It is important to highlight that the excess percentage is calculated based on what is fed, and
its value is calculated as if all the limiting reagent reacts. To calculate it we do not need
to know information about what happened with the reaction, even if the reaction occurs or not.
We are only interested in knowing the amount of the fed reactants and the balanced chemical reaction.

Generally, chemical reactions do not occur instantaneously, and in fact, they

it occurs relatively slowly,

Wait a long time to complete the reaction

∞

Design a very large reactor

In those cases, it is not practical to design the reactor for the complete conversion of the reactants.
So, the effluent comes out with some of the unreacted reagents, which will have to go through a
separation process and then it is recirculated to the feed stream. In these cases it is
It is important to know how many moles of the fed ones were consumed. The parameter that
that relationship defines us; it is the conversion.

ƒ = conversion fraction = moles consumed / moles fed

% conversión = moles consumidas/moles alimentadas *100

A 10 moles of A nA! nS100! 10 90

ƒ= = = = 0.9
90 moles of B nA 100 100
100 moles
A! B
% conversión = 90%

31
 moles of A consumed 0.9 moles of A consumed 0.1 moles of A not consumed
0.9 ! !
moles of A fed 1 mole of A supplied 1 mol of A fed

The conversion is based on the limiting reagent. If we consider the reaction Aà 2B:

A moles of A
moles of B
100 moles A! 2B
f=0.75

0.75 moles consumed

100 moles of A supplied! = 75 moles of A consumed
moles of A fed

nS100 - 75 = 25 moles of A out

2 moles of B formed
75 moles of A consumed! = 150 moles of B formed
1 mol of A consumed

Now let's consider the following reaction:

C2H2+ 2H2à C2H6

and suppose that 20.0 kgmol of acetylene (C2H250 kgmol of hydrogen and 50 kgmol of ethane are
feed a reactor in batches. Let's assume that after a certain time has passed,
30 kgmol of hydrogen reacts; how much of each species will be present in the reactor?
moment? If we represent the kg-mol of the reactants and products as follows:

t=0 t=t

C2H2 20 1
20! 30" = 5
2

H2 50 50 - 30 = 20

C2H6 50 1
20+ 30! = 65
2

If we generalize and consider thatβ kgmol of hydrogen reacts, then in general form
we can write:

t=0 t =t

C2H2 (nC2 H 20) 1

nC2 H 2 = (n C2 H 20) ! "
2

32
 H2 (n) H 20 n=H 2(n)! " H 20

C2H6 (nC2 H 60) 1

nC2 H 6 = (n C2 H 60) + !
2

If you know how much of any of the species involved in the reaction reacted, then
we can calculate the moles of all the species present after a certain amount of time has passed
reaction.

Now let's generalize these results for any chemical reaction. Let's suppose we have
the following chemical reaction:

aA + bBà cC + dD

where A, B, C, and D correspond to the chemical formulas and a, b, c, and d are the coefficients
stoichiometric, positive numbers that balance the reaction. The species on the left are
are called reactants, while those on the right are products. Another way in which the reaction
the previous chemistry can be written as:

! 1A+1! A" 2!A+

2 !A 3 3 4 4

where now A1, A2, A3y A4they are the chemical formulas, and! , ! , 1! y! they
2 are
3 the coefficients
4
stoichiometric. The convention used is thatνithey are positive for products and negative
for reagents (νi= + products;νiReactives). Theνiaccompanied by their signs are called
stoichiometric numbers. For example for the reaction

CH4+ H2Theà CO + 3H2

! CH4 = "1! H 2O = "1,! = CO

+1Hy 2! = +If there are inert species presentνI= 0

Now, if n i0 (ó n i0 it is the moles or the molar flow of species i that is fed into a reactor by
tandas (o continuo) en un proceso en estado estacionario, entonces:

n i= n+ i!0 " i o n if= n i0+ ν I ξ

The amountξ, which has the same units as n, is called the reaction progress. If
we know the supplied quantities, and one of the values is known we can calculateξ,
ni the
n i Then we can get to know
progress of the reaction, starting from the component of which is known
how much reacted of any of the species involved in the reaction and in passing know the
total moles present at the end of the reaction. The progress of the reaction is then a variable
extensive that describes the progress of a chemical reaction, expressed in terms of amount of
substance, i.e., moles or moles/time.

We can express the conversion of the limiting reagent as a function of the progress of the reaction:

33
 n!iOn i n!iO(n+ " iO
#) i
ƒ= =
ni0 ni0

" i#
ƒ= !
ni0

For example, let's consider the following reaction:

H2 + Br2à 2HBr

100 50 50

n=H 2(n)+ ! H 20" H2 !H

=2"1 n=H 2100! "

n Br2 = (n)+
Br20! " Brr ! Br2 = "1 n=Br50!
2
"

n HBr = (n HBr )0+ ! HBr" ! HBr = 2 n HBr = 50+ 2!

It is known that 70 moles of H are produced.2:

! = 100" 70= 30 n Br2 = 50! 30= 20 n HBr = 50+ 60= 110

In most chemical reactions, the reactants are mixed to form the desired product.
in a reaction ( A + Bà C + D). However, the reactants can combine in more than one
shape, or the formed products can in turn react to form something less desirable. The
términos rendimiento y selectividad se emplean para poder describir el grado en que predomina una
desired reaction regarding the side reactions that compete with it (non-reactions
desired) :

moles formed of the desired product

Couldyoupleaseclarifyyourequest?=
moles fed by the limiting reagent

moles formed of the desired product

Selectivity=
moles formed from the unwanted product

Performance and selectivity are fundamental parameters when it comes to measuring viability.
economic in a process and the design of equipment.

Analysis of systems with chemical reaction. Degrees of freedom.

Working in systems where a chemical transformation takes place brings with it certain
complications in the resolution of mass balances. So far, our mass balances
The total or of each species in non-reactive systems was limited to the equation IN = OUT. The
the appearance of the stoichiometric equation imposes certain restrictions, and thus the balances of
Chemical species will not remain balanced if we do not take into account the generation terms.

34
and consumption. In the following example, material balances in systems will be analyzed and solved.
what happens in a chemical reaction.

Methane is burned with oxygen to produce carbon dioxide (CO2) and2water. It is fed to a
Reactor 100 kg-mol/h of a feed stream that consists of 20% CH, 60% O, and 20% 4 2
of CO,2 resulting in a conversion of 90% of the limiting reagent. Calculate the composition
molar of the product current.

100 kg - mol / h
REACTOR
CH4= 0.2 CH4= ṅCH 4

CO 2= 0.2 CO 2= n CO˙
90% conversion 2

O2 = 0.6 H 2 The= n ˙ H2 O
O2 = ṅO 2

CH4 + 2O 2!"! CO 2 + 2H 2 O

The analysis of the degree of freedom is carried out in the same way as in systems without chemical reaction.
The main difference lies in the balance equations. An independent balance can be made.
for each species passing into the system; such species can be an atom, an ion, or a
molecule. The experience of working with different situations will help to identify such species.

System
Number of variables 4
unknown
Number of balances 3 (C, O, H)
independents
Number of relationships 1 (Conversion)
____________
Degrees of freedom 0

From the flows of each species fed, we determine the limiting reagent. For
inspection, we observed that the stoichiometric ratio of O2/CH4=2/1, and that the relationship of
nutrition is O2/CH4=60/20=3/1; therefore, the limiting reactant is methane, while the
The excess reagent is oxygen. Since the outlet flow of the reactor is not known, neither the
In compositions, it is more convenient to express the molar flows of each species individually.

There are two ways to solve problems with chemical reactions. Based on the balance of species.
molecular and based on balances of atomic species.

35
Balance of molecular species.

The general balance equation in steady state for molecular species is:

ENTRA + GENERATE - SALE – CONSUME = 0

Methane balance:

E+ G/ = S+ C! E = S+ C" E# C= n CH ˙ 4

kg – mol of CH4knowledge
Enter = (0.2)(100) = 20
h

kg - mol of CH 40.9 kg – mol of CH4cons

Consume = 20 !
h 1 kg – mol of CH4alim

kg - mol of CH4cons
= 18
h

kg – mol of CH4
ṅ CH=4 2
h

36
Carbon dioxide balance:

E+ G= S+ C!/ E+ G= S " E+ G= n CO ˙ 2

kg - mol of CO 2knowledgeable
Enter = (0.2)(100) = 20
h

kg – mol of CH4consume 1 kg – mol of CO2generate

Genera=18 !
h 1 kg – mole of CH4cons

kg – mol of CO2generate
= 18
h

kg – mol of CO2
ṅ CO=2 38
h

Water balance:

/ G= S+ C!/ G= S" G= nH
E+ O
˙ 2

kg – mol of CH4consumes 2 kg - mol of 2HThe gene

Generate = 18 !
h 1 kg – mol of CH4cons

kg–molofH2 The gender

= 36
h
kg - mol of H2 O
ṅ H 2 O= 36
h

Oxygen balance:

/ S+ C! E–C= S" E–C= n O

E+ G= ˙ 2

kg - mol of O2alim
Input = (0.6)(100) =60
h

kg – mol of CH4consume 2 kg - mol of cons

2O
Consume = 18 !
h 1 kg - mole of CH4cons

kg – mol of O2cons
= 36
h
kg - mol of O2
ṅ The2= 24
h

37
In summary, the output flows and the molar fractions are:

kg–mol/h XA

ṅ CH4 2 0.02

ṅ CO2 38 0.38

ṅ H2O 36 0.36

ṅ O 2 24 0.24

100 1.00

As can be seen, the output flow is equal to the input flow (100 kg-mol/h). This is due to
that for this particular equation the moles of reactants are equal to the moles of product (see
the stoichiometric equation). This is rather a curiosity, as in most of the
chemical reactions this does not occur, and as a rule, it must be assumed that the molar flow of entry! flow
outlet molar, which means that a total mole balance can never be performed in systems
with chemical reaction.

Balance of atomic species.

The general balance equation in steady state for atomic species is:

ENTRA - SALE = 0

since atoms cannot be created or destroyed, hence the terms of generation and consumption
from the general balance equation are set to zero.

Carbon balance:

kg – mol of CH4 1 kg – mole of C kg – mol of CO2 1 kg – mol of C

20 ! + 20 ! =
h 1 kg - mole of CH4 h 1 kg – mol of CO2
kg – mol of CH4 1 kg – mol of C kg – mol of CO2 1 kg – mol of C
ṅ CH 4 ! + n˙ CO 2 !
h 1 kg – mol of CH4 h 1 kg – mol of CO2

40= n˙CH+ 4nCO˙ 2

38
Balance of O

kg – mol of O22 kg – mol of O kg - mol of CO 2 2 kg – mol of O

60 ! + 20 ! =
h 1 kg – mole of O2 h 1 kg - mol of CO 2
kg - mol of O22 kg – mol of O kg - mol of CO2 2 kg - mol of O
ṅ O 2 ! + n˙ CO 2 !
h 1 kg - mole of O2 h 1 kg – mole of CO2
kg – mol of H2 O 1 kg – mol of O
+ n˙H !
2O
h 1 kg – mol of H2 O

160= 2n˙The+2 2n CO˙+ n2H ˙ 2O

Balance of H:

kg – mol of CH4 4 kg – mol of H

20 ! =
h 1 kg – mole of CH4
kg - mol of CH 4 4 kg - mol of H kg – mol of H2 O 2 kg – mol of H
ṅ CH 4 ! + n˙ H 2 O !
h 1 kg – mole of CH4 h 1 kg – mole of H2 O

80= 4n˙CH+ 42n H ˙ 2O

With the three equations, and the conversion relationship, the molar flows can be calculated.
The results obtained are equal to those shown in the table. In the case of atomic species, it can
It can be noted that it was not necessary to use the stoichiometric equation. Generally, it is used.
balance of atomic species when the stoichiometric equation is not known and when it occurs
several reactions occurring simultaneously. If only one chemical reaction is involved, the balances for
atomic or molecular species can be used interchangeably, and the one that involves the
most efficient solution.

Exercises

The reactions

C 2 H 6!"! C 2 H 4+ H2
C 2 H 6+ H2!"! 2CH4

take place in a continuous reactor operating at steady state. For the operation, the desired product is
ethylene and methane formation is not wanted; however, some methane is always formed. The feed
to the reactor contains only ethane and nitrogen. The product stream has the following mole percent
composition

Compound %

39
 C2H6 28.3

C2H4 28.9

H2 26.9

CH4 4.1

N2 11.8

Calculate: a) The molar composition of the fed

b) The fractional conversion of ethane to ethylene and methane

c) The fractional yield of ethylene.

A benzene –air gas mixture passes through a 500 lb batch of mixed acid (51.8% H2SO4,
2 4 40%
HNO,3 8.20% H2O), and its benzene content is completely consumed in the reaction:

C 6 H 6+ HNO3 !"! C 6 H 5 NO2+ H 2 O

The nitrobenzene layer is insoluble in the mixed acid, but the water is absorbed by the acid.
sulfuric acid content, after the reaction, is 58.1%. Calculate the fraction of the nitric acid consumed.

Combustion reactions

Combustion, that is, the reaction of a fuel with oxygen, is perhaps the most
important at an industrial level, despite the fact that the products obtained are of little or no value.
The importance of burning fuel with oxygen lies in the large amount of heat it generates.
which is used to produce steam, which in turn moves the turbines that generate most of
of electrical energy that is used. In most combustion reactions, coal is used (the
which is composed of carbon, hydrogen, sulfur, and non-combustible inert materials,
bunker fuel (mainly heavy hydrocarbons), gaseous fuels such as natural gas
(fundamentally methane) and liquefied gas (generally composed of propane and butane).

The combustion gases that are formed during the reaction consist essentially of CO, CO, 2
H2O, N,2 O 2without reacting and gaseous fuel that did not react. Also, if the fuel is
solid or liquid, it will remain combustible without reacting and inorganic non-combustible material or
ashes.

When a fuel is burned, carbon reacts to form CO and CO; hydrogen forms2
H2O, while sulfur forms SO. A combustion 2 reaction that only produces CO is 2

40
is known as complete combustion, while that which forms CO is known as combustion.
incomplete.

2H 2+ O 2!"! 2H 2 O Combustion of H 2

C+ O 2!"! CO 2 Complete combustion of carbon

C+ 1The
2 !"
! CO
2 Incomplete combustion of carbon

C 3 H 8+ 502!"! 3CO2+ 4H 2 O Complete combustion of propane

C 3H+8 7The2!" 3CO+

2 4H O 2 Incomplete combustion of propane

The source of oxygen in most combustion reactors is air. Remember

that the air has a simplified composition of 79% nitrogen and 21% oxygen, and a weight
average molecular of 29.

The gaseous product that comes out of a reactor or combustion chamber is known as combustion gases.
chimney (flue gases). The term wet basis composition is often used for
indicate the mole fractions of the components of a gas that contains water, while
dry basis composition or Orsat analysis (a common technique for chimney gas analysis)
it means the molar fractions of the components of the same gas without water.

Conversion from wet basis to dry basis.

100 moles of a flue gas contains 60% molar of N, 15% of CO,2 10% of O and2 the rest 2
H 2O. Calculate the molar composition on a dry basis.

moles B.H. moles B.S. ydry base

N2 60 60 60/85=0.706

41
 CO2 15 15 15/85=0.176
O2 10 10 10/85=0.118
H2O 15
100 85

Conversion from dry basis to wet basis.

An Orsat analysis gives the following composition results on a dry basis: N2 60%
CO2 14%
CO 11%
O2 10%

A humidity measurement shows that the molar fraction of water in the chimney gas is 0.07.
Calculate the composition of the flue gas on a wet basis for every 100 moles of dry gas.

1 mol of [Link].
100 moles of G.S.! 107.5 moles [Link].
0.93 of G.S.

moles B.H. ywet base

N2 65 65/107.5=.6045
CO2 14 14/107.5 = 0.1302
CO 11 11/107.5=.1023
O2 10 10/107.5=.0930
H2O 7.5 7.5/107.5=0.0700
107.5

Theoretical amount of oxygen and in excess (or theoretical amount of air and in excess)

Theoretical oxygen is the amount in moles (or molar flow) of oxygen needed for combustion.
complete with all the fuel fed, assuming that all the carbon burns to CO and 2
all the hydrogen is burned to H 2O. Theoretical air is the amount of air that contains the oxygen
Theoretical. Excess oxygen is the amount of oxygen supplied that exceeds the theoretical oxygen.

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The calculated amount of excess air or oxygen does not depend on how much material is burned, or if
a complete or incomplete combustion occurs; it depends only on the amount of O2 necessary to
who burns all the fuel fed to produce only CO. 2

moles of O2alim! moles of O2theory

% excess air = % excess O = 2
moles of O2theory

Exercises

A pure, low molecular weight hydrocarbon gas is burned in a furnace producing a flue gas containing
10.8% CO,23.8% O and 2 the remainder nitrogen. Calculate the atomic ratio H/C, and from this, the
formula of the fuel. Note that the analysis is on dry basis.

A furnace is fired with a coke containing nothing but carbon and inorganic ash. The carbon
constitutes 90% of the coke. The ash pit residue, after being wet down with water, analyzes 10%
casbon, 40% ash, and the rest water. The flue gases analyze 14% CO,21% CO, 6.4% O and 2 the
remainder nitrogen. In analyzing the performance of this furnace, calculate:

a) Moles of flue gas per ton of coke charged to the furnace

b) The percentage of excess air used

c) Percentage of the combustible charge which is lost in the ash

RECIRCULATION, DERIVATION AND PURGING

Our objectives in this section are:

1. Apply the material balance problem-solving strategy in the processes where

intervening recirculation, bypass, and purge flows.

2. Understand and apply the concepts of single-step conversion (or conversion in the reactor) and
global conversion in problems with recirculation and purging.

3. Understand the purpose of recirculation, bypass, and purge flows.

EXAMPLE

Ethylene oxide is produced from the catalytic oxidation of ethylene.

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 2C2H4+ O2à 2C2H4O (Rxn 1)

However, simultaneously an unwanted reaction occurs, the combustion of ethylene:

C2H4+ 3O2à 2CO2+ 2H2O (Rxn 2)

The feed to the reactor contains 3 moles of ethylene per mole of oxygen. The conversion of ethylene
in the reactor (or single-step conversion) is 20% and for each mole of ethylene consumed in
The reactor, 0.9 moles of ethylene oxide emerge in the reactor outlet stream (i.e., Y = 90%).
A set of separation units is available, from which three streams are obtained: ethylene
and the oxygen that does not react, pure ethylene oxide and CO2and the H2Oh, as shown in the
Figure. Perform an analysis of the degrees of freedom and calculate the molar flows of all the streams.
(assume a calculation base in the input current to the reactor).

It will be assumed as a basis for calculation a feed to the reactor of 100 moles/h of O2(N2 = 100
moles/h).

Analysis of degrees of freedom:

Global system: 6 unknowns (N1, N8, N9, N10, N11, N12) - 3 independent balances (C, H, and
O) - 1 flow relationship at the reactor inlet (N1 = 3N2)è 2 degrees of
freedom. There are not enough equations to solve the number of unknowns in
the global system.

U. Separación: 10 desconocidas (N3, N4, N5, N6, N7, N8, N9, N10, N11, N12) – 5 balances
independents (C2H4, O2, C2H4Oh, CO2, H2O) è 5 degrees of freedom. There are none.
sufficient information.

Reactor: 6 unknowns (N1, N3, N4, N5, N6, N7) – 3 independent balances (C, H, and O)
– 1 flow relationship at the reactor inlet (N1 = 3N2) – single conversion
paso (ƒ = 0.2) – rendimiento (Y = 0.9) è 0 degrees of freedom. We can start the
calculations at this point and determine the unknown values.

The solution to the problem begins by performing the balances in the reactor, and then continuing with the
condenser. The procedure is as follows:

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Analysis in the reactor:

N2 = 100 moles/h \ N1 = 3 (100) = 300 moles de etileno/h.

20% conversion of C2H4in the reactor: (à 80% does not react and comes out in the output current.
of the reactor)

0.8 moles of C H2 not

4 consumed
N3 = 300 moles of C H2 fed
4x = 240 moles/h C H2 4
1 mol of C H
2 fed
4

Balance of C2H4:C=E–S

Moles of C2H4consumidos = ( 300 – 240 ) = 60 moles/h de C2H4consumed

Balance of C2H4O: G = S (Starting from a performance of 90%)

60 moles/h of ethylene were consumed, of which 54 were consumed in the oxidation reaction.
(Rxn 1) the moles consumed in the combustion reaction (Rxn 2) = 60 – 54 = 6 moles/h of
C2H4consumed in Rxn 2.

CO balance2: G=S

Balance of H2O: G = S

Balance of O2: E-C=S

N4 = 100 – (27 + 18) = 55 moles/h O2

Analysis in the separation units:

45
Starting from the molecular balances Entry = Sale

C Balance2H4N3 = N11 = 240 moles/h

Balance of C2H4O: N5 = N12 = 54 moles/h

CO balance2: N6 = N8 = 12 moles/h

Balance of H2O: N7 = N9 = 12 moles/h

Balance of O2: N4 = N12 = 55 moles/h

It can be observed that 240 moles of C2H4they would be 'throwing themselves' after the separation. Like
this could not happen in reality (since we would be wasting money), the most logical thing is that the
material sea recovered (along with oxygen) and is recirculated to the input of the reaction system. The
the process diagram would look like this:

The strategy for solving mass balance problems with recycle streams is similar.
to the already known. In this case, the system is subdivided into subsystems (as in the previous case),
pero incluiríamos un nuevo subsistema: el punto de mezclado entre la corriente de recirculado y la
fresh power supply. We can also integrate the process globally. In this
In this case, we can establish 3 sets of balances in each subsystem and one set of balances in
global form. But let's remember that out of the 4 sets of balances, only 3 are independent.
We must be careful when analyzing subsystems in which chemical reactions occur.
(the global system and the reactor), we will account for balances of atomic species; while in
subsystems where no chemical reaction occurs (the separation units and the mixing point)
we will count balances of molecular species.

Let's solve the exercise now taking into account the recirculation current (we will assume the same
calculation base that in the previous part, i.e., 100 moles/h of O2(N2 = 100 moles/h). To the analysis of
the degrees of freedom would need to include the mixing point of the fresh feed with the
recirculation flow, while the analysis in the global system would look like this:

46
Global system: 5 unknowns (NA, NB, N8, N9, N10) – 3 independent balances (C, H, and
O)è 2 degrees of freedom. There are not enough equations to solve the
number of unknowns in the global system.

Mixing point: 5 unknowns (NA, NB, N1, N11, N12) - 2 independent balances (C2H4,
O2) è 3 degrees of freedom. There would not be enough information.

The analysis of the problem would be similar to the previous case, but in this case we would need to calculate the
fresh feed flows from C2H4and O2fed (i.e., NA and NB), which can
to be calculated from the balances of each species at the mixing point:

Analysis at the mixing point:

From the molecular balances Entra = Sale

C Balance2H4:NA + N11 = N1 N1 = 300 moles/h y N11 = 240 moles/h

NA = N1 – N11 = 60 moles/h

Balance of O2: NB + N12 = N2 N2 = 100 moles/h y N12 = 55 moles/h

NB = N2 - N12 = 45 moles/h

In chemical reaction systems with recirculation, it is important to note that there are two values
for the conversion. The value of the conversion in the reactor or single-step conversion (which in this
the case is 20%), while if we do a global analysis and calculate the conversion it would give us:

The overall conversion is 100%. This value indicates that there is a perfect separation in the process.
of multiple separation units. What does not react is completely recirculated to the reactor. If
If some of the reactant appears in the output stream of the process, then the overall conversion will be
less than 100%, although this value will always be greater than the value of a single conversion
step.

In problems with recirculating currents, it is common to find an additional problem.

Let's suppose that a certain material, which enters with the fresh current and does not react (i.e., acts as
inert), remains completely in the recirculation flow, instead of exiting in one of the
output streams of the process. In this case, the substance will be continuously entering the process,
and there will be no way out, so the steady state would never be reached and it
would accumulate in the system. To prevent this situation, part of the recirculating current is
purge to eliminate the substance or inert present. Consequently, a purge is a flow that is
used to eliminate an accumulation of inert or undesirable substances that otherwise would

47
would accumulate in the system:

On the other hand, in certain processes there may be a leakage current, which is a current
that is derived, does not go through the process and goes directly to another later stage. (Think and give
examples of processes where I would consider a bypass current to be necessary):

The term AF corresponds to fresh feed, and does not include the recirculation current.
while the feed to the reactor (AR) includes the fresh feed plus the stream of
recirculated.

Exercise 1.

Propane is dehydrogenated to form propylene in a catalytic reactor.

C3H8à C3H6+ H2

The process is to be designed for a 95% overall conversion of propane. The reaction products are
separated into two streams: the first, which contains H2, C3H6, and 0.555% of the propane that
leaves the reactor, is taken off as product; the second stream, which contains the balance of the
unreacted propane and 5% in the first stream, is recycled to the reactor. Calculate the composition of
the product, the ratio (moles recycled)/(mole fresh feed), and the single-pass conversion.

Exercise 2.

Methanol is produced in the reaction of carbon dioxide and hydrogen.

CO2+ 3H2à CH3OH + H2O

The fresh feed to the process contains hydrogen, carbon dioxide, and 0.400 mole% inerts (I). The
reactor effluent passes to a condenser that removes essentially all of the methanol and water formed
and none of the reactants and inerts. The latter substances are recycled to the reactor. To avoid
buildup of the inerts in the system, a purge stream is withdrawn from the recycle.

48
The feed to the reactor (not the fresh feed to the process) contains 28.0 mole% CO. 270.0 moles of H2,
and 2.00 mole% inerts. The single-pass conversion of hydrogen is 60.0%. Calculate the molar flow
rates and the molar composition of the fresh feed, the total feed to the reactor, the recycle stream,
and the purge stream for a methanol production of 155 kmol CH3OH/h.

49