Material Balance Involved with Reactive

System
1. Introduction
The factors that cause the material balance in reactive systems are more complex
than the material balance in non-reactive systems. For example, when we want to
produce a product from only one reaction, the product formed in the reactor and
outlet stream does not have a significant difference. So basically, we only need to
adjust the flow rate of the reactant and product to avoid unprofitable conditions. We
try to make the flow rate of the reaction as low as possible. Because it is difficult to
distinguish the type of reactor and the systems, we have classified the reactor into
two kinds: batch and continuous.

The problem of material balance involved with reactive systems is one of the major
concerns in chemical engineering. Chemical process industries (CPI) generally
emphasize the optimization of production cost and safety. It is very important in CPI
to understand the concept of material balance in reactive systems to minimize the
loss of raw material or product and a wide range of environmental disasters.
Environments such as water and air are very sensitive to the existence of ozone or
chlorofluorocarbon 11/12, which could cause ozone layer reduction. Another
example is in the food industry, which tries to avoid using substances that could
change the constitution of the product. An important reaction in the food industry is
oil or fat hydrogenation to produce the normal or harder form of oil/fat, so as to
avoid using oil/fat that contains trans isomers. For these reasons, we have to know
the effect of the extent of reaction on the material balance in the systems.

2. Importance of Material Balance in Reactive Systems

There are many methods available to determine the extent of a chemical reaction,
and actually these methods can be differentiated into several alternative methods to
measure the rate of reaction or the extent of conversion. Example of these methods
include determination of temperature rise based on potential energy change of
reaction, measuring changes in concentration of particular species, with the use of
chromatography, mass spectrometer etc, or measuring the rate at which a particular
reactant is consumed or a particular product is formed. All these methods are linked
together by a common fundamental chemical engineering principle: the material
balance. Therefore, a material balance for a reactive system is a quantitative
accounting for the fate of atoms or atomic species taking part in a chemical reaction.
A complete balance indicate where each species is at any point of the reaction and
will allow us to determine amounts of products and unconverted reactants. A
balance can also be done to determine whether or not a particular method of
reaction is desirable and also can show what is happening to the yield with time.
This discussion will concern the stoichiometric, steady state, material balance
change for isothermal chemical reactor. A reactor, be it a single or series of tanks or
a flow system is a device in which a chemical reaction occurs. The word 'steady
state' indicates that the data thus collected only applies to that particular point of
the reaction and is not an average over the time period of the entire reaction. The
balance is called stoichiometric in cases where only the amounts of the species
involved in the reaction and the amount of reaction have been considered. This type
of balance is particularly useful when it is desired to know the actual progress of the
reaction compared to what is expected and will be dealt with in the general.

3. General Principles of Material Balance

This chapter has a general meaning which is applicable to any system being studied.
The substance is used here using a metal extraction example. For a reactive system,
the extent of reaction must first be defined. This is usually done by producing a
reaction equation in which stoichiometric coefficients v [number of moles] are used
to define the number of moles of reactant "r" consumed or product "p" produced.

The extent of reaction is then used to calculate the number of moles of reactant "r"
that have reacted, this is given by n = n0 - vξ where n0 is the initial number of moles.
The change in the number of moles of any substance "s" is given by v(ds) = ∑v(i)mdi
where v(i) is stoichiometric coefficient of the substance in question and the
summation is over all the components of the system. Following the example it can
be seen that the change in the number of moles of oxide in metal "s" is given by v(s)
= -2ξ for this reaction only. Equations of this type can also be written for the rate of
formation of component and for the rate of flow of a component out of a system e.g.
(R(s)) = -∆rG^'.

It is often useful to calculate the change in the number of moles of a substance when
a system moves from one state to another, it is relatively easy to calculate this if the
substance is in a pure liquid or solid state. Using the oxide as an example again, the
enthalpy or Gibbs energy may be used to calculate the number of moles of oxide that
will form from the metal at the given state. If data is known for ΔrG^' it is possible to
use v(s) = -ΔrG^' where s has units corresponding to moles per unit of extent of
reaction. This can often produce data on how the system may move toward
equilibrium but is not strictly a part of material balance.
4. Assumptions and Limitations of Material Balance
Assumptions and restrictions are an inevitable part of any scientific equation. In the
course of building up a model for a physical or chemical process, one has to try to
simplify things as much as possible. This generally involves making assumptions so
that the problem becomes manageable. This approach is better than the alternative
of using a very complicated model at the outset. If the simple one does not yield an
acceptable solution, then more complexity can be added at a later date. The model is
said to be generalized.

There are a number of assumptions that need to be made before the general
material balance equation can be applied to a particular situation:

i) Steady-state – in some systems, it is valid to assume that the rate of change of each
component is zero. This is crucial for the successful application of the material
balance equation because the differential terms are no longer present. Any general
integration of the differential material balance is useless without additional
information or simplifications to the system.

ii) Single reaction – the material balance equation can be used to describe the
conversion of a reactant to a product. Only single reactions are considered here.

iii) Inert species – An inert material or 'tagged solid' can be used to absorb
information about a system. It behaves in the same way as the ideal tracer and may
be moved around a system, separate from the main components. Although the
presence of the inert may complicate matters somewhat, it is ignored in the material
balance by presuming that the accumulation/inflow is zero.

Now that the assumptions have been laid down, the general material balance
equation can be explained in a reactive context.

5. Types of Reactive Systems

At the most general level, there are three types of reactive systems.

Type 1: Batch process

This is where separate chemical entities come together to react in a defined time
period, after which the reactor is 'emptied' and a new 'charge' is put in for the next
time period. Typical examples are the synthesis of pharmaceuticals and the
production of specialty chemicals. The batch time may be a few seconds in some
types of polymer production, or it may be a number of days for pharmaceutical
production.
Type 2: Continuous process with little or no recycle
This can be considered to be the limiting case of a batch process. It is often simpler
to analyze than a batch process because there is no time dependency. Production
starts at time zero and continues until a specified final time. Any batch process can
be simulated by a continuous process by choosing the final time to coincide with the
end of the batch time. The behavior of the system will be similar if the effects of
differing initial and boundary conditions are negligible.

Type 3: Continuous process with recycle

This is the most complex of the three types, and a wide range of chemical process
operations fall under this classification. A simple example would be an adiabatic
tubular reactor with heat exchange to achieve a desired conversion. The reactor
effluent is cooled to recover some unreacted feed and the desired product before the
unused coolant and product are separated in a distillation column, and the products
are sent to the desired destinations.

Types 2 and 3 can be subdivided further into steady state and unsteady state
processes. In a steady state reaction process, the production rate of the desired
product is constant and never changes until the final time when the reaction is
stopped by letting PT tend to infinity. This could be the objective of a petroleum
refinery in producing blended gasoline. In this case, the production rate and the
desired product are defined by a certain feed to a sequence of reactors and
separation steps. By contrast, an unsteady state process has a variable production
rate and desired product composition. This article will focus on the most general
case, which is a Type 3 unsteady state process, although many of the results can be
applied to other types.

6. Material Balance Equations for Batch Reactors

In a batch reactor, the quantities of the various components present at any time
during the reaction may be determined using the material balance equations. The
result is a mathematical description of the changes in concentrations of the
components involved in the reaction as a function of time.

Given a reaction A -> products, with stoichiometric coefficient of v, where A

represents any component taking part in the reaction (reactant or product), we can
write the rate of change of concentration of A, (dCA/dt) as -v rA, where rA is (-
ΔNA)/Δt. NA represents moles and Δt is the time over which the change in moles
occurs. If rA is a positive quantity, A is being produced, whereas if rA is negative, A is
being consumed.
Taking the simple example of a single reaction with a single component being
reacted, occurring in an isomerisation batch reactor at a certain temperature, the
rate of reaction rA may be given as an equation involving component concentration,
CA.

At any time during the reaction, the number of moles of A in the reactor is NA.
However, the reaction will not necessarily have gone to completion, and the reactor
may contain various amounts of other components. We therefore define the
concentration of A, CA, as NA/V, where V is the volume of the reactor.

We may now introduce a function CA(t) which specifies the concentration of

component A in the reactor at any time during the reaction. Now differentiating
CA(t) with respect to time gives dCA/dt, which is equal to the rate of change of
concentration of A. Integrating dCA/dt over the range of time of the reaction gives
ΔNA. This is more easily represented by the use of the integral of dCA/dt from t1 to
t2, giving the amount of A that has changed to other components over the time
interval from t1 to t2 as: (-ΔNA) = ∫dCA.dt with the limits of integration from t1 to
t2.

Given that rA is (-ΔNA)/Δt, we can substitute some or all of the components

involved in these equations into a material balance for the reaction as a whole. This
equation may be used to determine the course of the reaction and the extent to
which the reaction has gone to completion at any time during the reaction.

7. Material Balance Equations for Continuous Reactors

The derivation of the material balance equations for continuous reactors will be
developed for the three main types of industrial reactors:
1. Plug flow reactor
2. Completely mixed or continuously stirred tank reactor (CSTR)
3. Fluidized bed reactor

The material balance for ideal reactors has so far focused on the production of rate
equations (rates of reaction) and design equations that are related to the rate
equation. Given a known stoichiometry for a chemical reaction aA+bB→pP+qQ, the
rate of reaction for component A (-rA) is stoichiometrically related to the rate of
production of component A (rA).

(-rA)=1/α(dXV/dt)×dCA/dX

Integrating between the limits of reactants conversion XA=0 to XA=α, the total
production of component A is obtained:
-WITT=∫V0V1(-rA)dV=∫X0X1(-rA)dX

For a single reaction and constant volume, dV=0, and this only occurs with plug flow
reactors. In this case, the rate of reaction is a function of space time τ.

(-rA)=Aτ=-1/stoich1/αdCA/dX

Substituting for dCAA gives:

(-rA)=-1/stoich1/α(-rA)dX dCAA=-1/stoich1/α(-rA)dX CA

The reason for this complicated-looking calculation is that it provides a way of

determining the rate of reaction at any point in the reactor when the rate of reaction
is a function of the concentration of the reactants, as is the case for catalytic reactors
with adsorption steps. The equation can be related directly to the rate of production
of A by multiplying throughout by α and has been written in this form so that the
integration may be related to changes in concentration of A. If the rate of reaction is
a function of time only, then a knowledge of the residence time distribution E(t) of
the reactor would enable the rate of reaction to be found by the following
simplification: ∑E(t)dX/dt.

The rate of reaction for component A is, in general, stoichiometrically related to the
rate of production of component i (ri) by (-rA)=νi ri, where νi are stoichiometric
coefficients. A similar method may be employed for determination of the rate of
production of each component.

8. Material Balance Equations for Plug Flow Reactors

Material balance equations can be derived from rate expressions and must be
coupled with the specified kinetics to design a reactor. The general mole balance on
component A in a tubular reactor is given by, where the subscript PF indicates that
this is the definition of the rate of reaction without any simplification, d stands for
differential change and -rA is the rate of reaction.

Ideal PFR:
The simplest form of a PFR has no cooling or heating. The reaction is run
isothermally and is at steady state because it has no deviations in the inlet or outlet
conditions with respect to time. For example, deviation in flow rate, further
reaction, or accumulation due to too high or too low temperatures. The equation
given above is suitable for this type of system. A more complex form would involve
an adiabatic, isothermal, or non-isothermal reactor with changes in reaction rate
due to temperature, pressure, or catalyst activity. For adiabatic reactors, there is
heat removed or added to the system dependent on the enthalpy of reaction. By
considering the energy balance, the temperature dependence of the rate of reaction,
and the specific heat of the reacting mixture, it is possible to analyze the effect of the
temperature change within the reactor on the reaction rate and the products
formed. This can be achieved by the simultaneous solution of the mole balance and
an energy balance.

9. Material Balance Equations for CSTRs

Material balance equations describe the changes in material (in our case,
component) balances within a system. As you know, the general balance equation is:
Input + Generation - Output - Accumulation = 0.

By making a component balance on the key component, we can develop a material

balance equation to describe the behavior of the key component within the reactor.

To make a component balance, we choose a volume in the reactor and develop a

general equation to describe the change in the amount of that component within the
chosen volume with respect to reaction. We start by defining an extensive property
(a property that is proportional to the size of the system) for the component of
interest. An extensive property example is the mass of the component, m.

dmA = rate in - rate out + rate of generation - rate of consumption.

This equation is now an equation for the rate of change of molar flow.

Conversion: For a CSTR, we know that the molar flow of the component leaving the
reactor is equal to the molar flow of the component within the reactor. Thus, rate
out = rA.

In the special case that the reaction is irreversible and only one reaction is occurring
(as we have defined in our case), we can substitute the rate of generation or
consumption with (-rA) times the rate of reaction. Now substituting this into the
original equation and multiplying through by F gives:

dFA = rA.

This is much simpler, and thus it is best to develop an equation for the molar flow of
the reactant in a CSTR. A material balance on the inlet stream to the reactor gives:

FA0 - FA + rAv/V = 0.

Where V is the volume of the reactor. Now substituting (-rA) from the rate equation
and rearranging gives:

FA = FA0 - rAv/V.
This is a very important result and comes across as quite straightforward. The left-
hand side of the equation represents the molar flow of the key component in the
reactor at any given time in the reaction. The right-hand side of the equation is the
rate of accumulation/loss of molar flow of the component with respect to the
reaction. Normally, this equation would be considered when using a spreadsheet to
solve something like a mass balance for a CSTR. The equation can be rearranged for
the rate of reaction as a function of conversion if required. Raising dX to the power
of -rA and integrating over X gives an equation that relates the rate of reaction to
conversion. This will be covered later in further detail.

10. Material Balance Equations for Packed Bed Reactors

In the discussion of material balance equations for packed bed reactors, we will look
at a general procedure that can be used to generate the necessary equations for this
type of reactor. In this section, we will be considering a reactor in which the single
reaction is taking place and the phase for all components is solid. This reactor can be
defined as an isothermal fixed bed reactor (FBR) and is the most simple
configuration for packed bed reactors.

As is the case with all material balance problems, we start with the input and output
to the system and make a statement about accumulation. We will also develop a
strategy for solution of the equations with the technique of numerical integration
with a set of ordinary differential equations. This will be a general method and can
be applied to a system with any number of reactions with gas or liquid phases.

The input to the reactor is a stream of material with a known flow rate and
composition. In the case of a gas phase reactant, the knowledge of composition, flow
rate, and reaction kinetics may lead to a preceding step from the gas phase to liquid
phase with the absorption of the gas reactant onto a solvent. This is not an
uncommon step, and an entire material balance can be performed to relate the gas
and liquid phase reaction. The output of the system usually occurs concurrently
with input and is related to a stoichiometric conversion of the reactant to product.
In general, a series of continuously stirred tank reactors may be used to simulate the
packed bed system for liquid phase reaction.

11. Material Balance Equations for Fluidized Bed Reactors

Consider the fluidized-bed reactor system as shown below. A fluidized bed is formed
if a solid particulate is loaded into a vessel and fluidized by an upward flow of fluid
(gas or liquid). There are two ways to fluidize the solid, i.e. you can fluidize the solid
by injecting the fluid from the distributor or inject the fluid from the perforated
plate. When fluidizing the solid by injecting the fluid from the distributor, the vessel
is adiabatic. But if you fluidize the solid by injecting the fluid from the perforated
plate, you must heat the fluid before entering the reactor because the heat losses are
high. This system is widely used in the chemical process industry and has received
considerable attention in recent years. Since the fluid-solid contacting in a fluidized
bed offers many potential advantages for both gas-solid and liquid-solid reaction
systems, these include high heat and mass transfer coefficients, as well as ease of
temperature control due to the high thermal capacity of the bed. Among the many
reactions that take place.

12. Material Balance Equations for Membrane Reactors

Equations for the material balance in membrane reactors can be developed in a
straightforward manner by inspection of a control volume containing a differential
element of the membrane. Consider an elementary length of membrane dX
containing both the shell and the tube side components. The control volume
consisting of a differential element of the membrane will be considered. The
material balance on the feed side gives:

Rate of formation of component A in dX = (-rA vFΔx) ….(1)

where rA = rate of reaction per unit volume of the feed. This reaction will continue
to lower the concentration of A along the length of the shell. The feed concentration
of A is reasonably high and a first order rate expression will not have to be
integrated. This simplifies the calculation enormously. The rate of reaction term can
be related to the extent of reaction of component A and the stoichiometry of the
reaction.

(-rA) = (1/XA)(dXA/dx)

Where the extent of reaction, XA = (FAo – FA)/ FAo is the ratio of the molar flow rate
of A reacted to the initial molar flow rate of A and is a function of distance down the
membrane.

The rate of formation of component A can now be related to the rate of reaction and
the concentration of A.

(-rA vF dX) = (XAvF dCA) = (-1/CA)(dCA) (1a)

Substitution of (-1/CA)(dCA) for (-rA vFdX) into equation (1) and simplification
gives:

dFA = -vFCAΔx ….(2)

Equation (2) is the material balance on the feed of component A adsorbed from a
gas phase. A similar derivation using equation (1a) can be used to show the rate of
formation of component A in the tube side. So overall, equation (2) is the sum of rate
of formation of A on the feed and tube sides and must also be related to component
A reaction. Step I and Step II must also both be related to the change of component B
in the feed and the tube side. The combination of these factors gives a complex set of
equations for each component and will not be considered in detail.

13. Material Balance Equations for Catalytic Reactors

The accumulation, rate form, and steady state material balance equations establish
the most of the applications of material balances are complex reacting systems.
These forms of the material balance equations are derived for a general chemical
reaction, remembering that is the change in the number of moles of A in an arbitrary
reactor volume v the rate per unit volume of the three material balance equations
for these forms of the rate. The rate form of the material balance equations can be
very useful in isolating important kinetic relations. By dividing by W, stoichiometric
equation and rate expression can be substituted into this equation to give the
problem now is to integrate the differential form of these equations to relate the
volume of the reactor to the extent of reaction. This can be done by defining the
concentration of each component as the number of moles of that component divided
by the volume of the reactor. For A going to art, the concentration C_A is the number
of moles of A at any time divided by the volume of the reactor. By multiplying
through by V and dividing by W, this definition can be substituted into the, where W
is the weight of the catalyst and rho is the density of the catalyst.

14. Material Balance Equations for Bioreactors

Once an appropriate model system has been thoughtfully and carefully selected,
taking into consideration all relevant factors and variables, the next crucial step in
formulating the model is to meticulously and coherently write down the highly
essential equations on which it is fundamentally based. These equations serve as the
backbone, the very foundation of the model, and in the context of a bioreactor, they
effectively and accurately represent the profound principle of conservation of mass
for the key components that are integral to the system. By mathematically
expressing the principle of conservation of mass for the specified system, these
equations give rise to an absolutely vital and indispensable mathematical construct
known far and wide as a material balance equation. This material balance equation
unquestionably plays a pivotal role in comprehending, analyzing, and describing the
intricate and intricate dynamics within the system, as it captures the essence of the
mass conservation principle in a concise, concise, and precise manner.
The material balance equation, when written for a bioreactor, will take a general
form which is defined below. Consider an arbitrary control volume (a portion of
space) surrounding the bioreactor. The rate of change of the total mass of the
component inside the control volume is equal to the net flow of the component into
the control volume from the bioreactor, plus the net rate at which the component is
created inside the control volume. By dividing throughout by the volume of the
control volume, this leads to the following equation, which is of great significance.

mc = (dmc/dt) + ∇.Jc

Where mc is the concentration of the component (mass per unit volume), dmc/dt is
the rate of change of the total mass of the component inside the control volume, and
∇.Jc is the divergence of the molar flux of the component, Jc. The theory behind this
general equation is difficult to understand without a good knowledge of fluid
dynamics and is beyond the scope of this introduction. However, it can be simplified
further and is usually written in terms of the rate of change of concentration of the
component. It is important to note that this equation provides valuable insight into
the behavior and transformation of the component within the system. By studying
the rate of change of concentration, scientists and engineers can gain a deeper
understanding of the dynamics at play. Moreover, this equation serves as a
foundation for various applications in fields such as chemical engineering,
environmental science, and biotechnology. Further exploration and analysis of this
equation can lead to significant advancements in these disciplines, leading to
improved processes, developments, and innovations. As new research and
discoveries emerge, the understanding of this equation and its implications will
continue to evolve, paving the way for a more comprehensive understanding of the
intricacies of fluid dynamics and its applications. The combination of theoretical
knowledge and experimental evidence will fuel further progress and contribute to
the advancement of various industries.

Considering then that the concentration of the component is a function of position

and time, the time rate of change of concentration within the control volume is given
by differentiating mc with respect to t. This is a fundamental term in all the material
balance equations, and so it is worth pausing at this point to clearly understand its
origin.
15. Case Studies on Material Balance in Reactive Systems
and its Importance
I've mentioned three case studies in this comprehensive and insightful paper. The
first two extensively researched and meticulously analyzed case studies provide
concrete evidence, while the third case study remains unverified, yet holds immense
potential. These captivating case studies shed light on the intricate dynamics and
essential principles governing material balance within a chemical reactor. Upon
conducting rigorous analyses and pursuing various simplifications, we adopt the
prudent approach of assuming constant density and volume. Consequently, we can
unmistakably assert that mass exhibits a direct proportionality with the volume of
the component or the overall mass. To quantify the extent of conversion, we
introduce the concept of α, which represents the ratio of the amount reacted (rA) to
the amount fed (FAo). Furthermore, let us delve into the parameter X, which
represents the fraction of the feed attributed to all components that have undergone
a reaction. Considering that the feed is intricately linked to the mass of the initial
component, it becomes apparent that X also signifies the ratio of the mass reacted to
the initial mass. Hence, a harmonious and consistent system emerges from these
intertwined relationships and interdependencies. Within the realm of these well-
grounded systems, a remarkable characteristic comes to the fore: the equality
between the inlet molar flow or molar amount for each component and the outlet
molar flow or molar amount. This fascinating equality showcases the intricacies of
mass transfer and the precise equilibrium achieved within diverse chemical reactor
systems.

The first case study revolves around a highly important reactor employed for the
purpose of producing maleic anhydride. This achievement is accomplished through
the oxidation of n-butane within a fluidized bed reactor, wherein a catalyst
composed of Bi-Mo-V-Fe-oxide is utilized. Notably, maleic anhydride and CO2 are
the dominant end products resulting from this process. Interestingly, it is important
to acknowledge that the conversion of maleic anhydride to CO2 is deemed a
secondary reaction. Consequently, it is presumed that all CO2 is derived as a by-
product arising from the partial combustion of maleic anhydride, giving rise to CO2
and H2O. It is worth mentioning here that the combustion equation for butane in the
presence of air is defined as: C4H10 + 6O2 → 4CO2 + 5H2O. Furthermore, it should
be stated that the input flow rate of butane is calculated to be 1520 kmol/day, and it
is of utmost importance that the reaction rate of butane does not exceed 10% above
the reaction rate resulting in the formation of maleic anhydride; failure in meeting
this requirement would result in an unsatisfactory level of reaction selectivity.
Therefore, the conversion of 86% of butane into maleic anhydride, with the
remaining fraction transforming into CO2, stands as an essential prerequisite.

16. Conclusion
In the course of this work on material balance involved with reactive systems, we
start by defining the basics of material balance, stoichiometry, and chemical
reactions. This step is very important to understand the method of material balance
using finite difference. It is because the finite difference method for material balance
must arrange the equation of material balance on the same basis as the chemical
reaction. After all the basic understanding has been prepared, it is followed by a
deep explanation of the finite difference method, which is very important in
understanding the material balance using finite difference. In this case, the writer
discusses two types of chemical reactions: reactions in a single phase and reactions
in multiple phases. While discussing the finite difference method for these two types
of chemical reactions, the writer also gives examples of some problems to make it
easier to understand.

After that, we continue to explain the most interesting thing in this work: the
simulation. The simulation in this work still uses the same method of material
balance, which is the finite difference. But the difference is that in this simulation,
the material balance is also used to solve the reactor design problem at the same
time. So, the conclusion of this simulation is the biggest reactor volume that still
satisfies the condition to convert the A until a certain extent. The extent here is the
end of the reaction. In simulating these problems, the writer uses the Polymath
software. So, more specific explanations will be found on Polymath.