CP 105: CHAPTER 2

MATERIAL BALANCE

Recall the Law of conservation of mass: “Mass can neither be created nor destroyed but
it can only be transformed from one form to another”. Thus the mass of the universe
remains constant.

The design of a progress plant cannot be complete until it is established that the inputs
and outputs of the entire process and each individual unit satisfy the material balance
equation.

2.1 Process Classifications

Processes may be classified as follows:

 Batch process
 Continuous process
 Semi-continuous or semi-batch process

All of these processes may be steady state or Transient (unsteady).

Batch Process:
This is the process whereby no mass crosses the system boundaries between the time
the feed is fed and the time the product is removed, e.g. charging a reactor and letting it
to react for a considerable period of time and removing the product sometime latter.

Continuous Process:
In this process the inputs and outputs flow continuously throughout the duration of the
process, e.g. a pump pumping a mixture of liquids in a distillation column at a constant
rate and steadily withdrawing vapor and bottoms from the column.

Vapour

Distillat
Feed ion
Process fluid column
Pump

Bottoms

Fig. 2.1: Example of a continuous process

Semi-Batch Process
Any process that is neither batch nor continuous can be termed as semi-batch process,
e.g. Allowing the contents of a pressurized gas container to escape from the atmosphere
or slowly blending several liquids in a tank from which nothing is being withdrawn.

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Steady state:
This is a condition in the process whereby all variables in this process (e.g. temperature,
pressure, volume, flow rates, etc.) do not change with time.

Transient (unsteady) state

This is a process whereby all process variables change with time.
A continuous process plant will typically start with unsteady state operation and after a
period of time (this can take up to many days) the plant will attain Equilibrium. If the
equilibrium conditions are maintained, the plant will be said to be at steady state.

It has to be noted here that batch processes are normally used for processing of small
quantities of products whereas continuous process are suitable for large production
rates.

In material balances system boundary normally has to be defined. This is the area of
attention which circumscribe about the process itself. A system is therefore a portion of
a process that is set out for analysis. For example in Fig 2.2, the reactor could constitute
a system on itself, likewise for the separator and the extraction column. Material
balances can also be made for the whole process or the whole plant.

A
Extracti D
F P Separator B on
Reactor column

C
E

Fig. 2.2: Examples of Various Systems

The system can be open or closed.

An open system:

An open system is the one which the material is transferred a cross the system
boundaries during the time interval of interest. In other words the material enters and
leaves the system during the time interval set out for analysis. A good example of this is
a continuous process.

A Closed System:

This is the one, which there is no transfer of material during the time interval of interest.
A good example of this is a Batch process.

An Isolated System:
In this case, during the period of study; there is NO material/mass, NO heat and work
flows across the system boundaries.
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Material balance generally provides a systematic way of accounting for the material flows
and changes in inventory of materials for a particular system or process.

Thus the general equation for material balance can be presented as follows:

 Input  output 
 Accumulati on through the  through the   generation  Consumption
         
within the =  -  + within the  - within the  (2.1a)
system  system  system  System  System 
  boundaries  boundaries     
or

Accumulation = input – output + generation – consumption (2.1b)

There are two types of material balances:

1. Differential Balances
2. Integral Balances

The Differential Balances:

These are balances, which indicate what is happening in the system at an instant of
time. Each term of the balance is then a rate, e.g. rate of input, rate of generation, etc
and has balanced quantity unit divided by a time unit. (e.g. g SO2/s, etc.). These types of
balances are usually applied to continuous processes. In this case the quantities to be
balanced are expressed per unit time e.g. kmol/s, kg/h, etc.

The Integral Balances:

These are balances that describe what happens between two instants of time (say t 1 and
t2). Each term of the equation is then an amount of the balanced quantity and the
corresponding unit e.g. kg SO2, g SO2, barrels, etc. These types of balances are
normally applied to batch processes with the two instants of time being the moment after
the input takes place and the moment before the product is withdrawn.

Most of the balances in this course will be differential balances. Integral balances will be
introduced at the end of the course.

2.2 Balances on Non-Reacting Steady State Processes

For continuous steady state processes, the Accumulation term is zero,

(Accumulation = O). Also for non-reacting systems (i.e. no chemical reactions involved)
the generation and consumption terms are also zero. The general mass balance
equation reduces to:
Input – output = 0 or input = output (2.2)

This means that whatever comes in the system must go out from the system.

Example 2.1:

100 kg/h of mixture of Benzene (B) and Toluene (T) that contain 50% B by mass are
separated by distillation into two fractions. The mass flow rate of B in the top stream is

30
 450 kg/h and that of Toluene in the bottom stream is 475 kg/h. The operation is at
steady state. Calculate the unknown components in the output streams.

Solution: Take basis of 1 h of operation

Distilled
450 kg B
Q1 kg T
F = 1000 kg
50% B = 500 kg
50% T = 500kg Distillation

475 kg T
Fig. 2.3: Figure for example 2.1 Bottom Q2 kg B

Component Balance: input = output

Benzene: 500 = 450 + Q2; Q2 = 50 kg
Toluene: 500 = Q1 + 475; Q1 = 25 kg
Overall: 1000 = (450 + 25) + (475 + 50) = 1000 kg O.K.

NB: It is normally recommended to check the consistency of material balance with the
overall balance.

Example 2.2

Given that in a certain desalination plant sea water containing salt and water is
evaporated to produce pure water and concentrated brine (salt water) suppose that sea
water containing 0.0035 mass fraction salt is evaporated to produce 1000 1b/h pure
water. Determine the mass flow rate of sea water required if corrosion considerations
limit the waste brine mass fraction 0.07.

Solution: Basis 1h of operation

Pure water (P)

100 lb
Seawater
F=? Evaporation
XNaCl = 0.035 Waste Brine (W)
Plant
XH20 = 0.965 XNaCl = 0.07
XH2O = 0.93
Fig. 2.4: Figure for example 2.2

Component balance: input = output:

NaCl balance: 0.035F = 0.07W - (1)
H2O balance: 0.965F = P + 0.93W - (2) but P = 1000
Overall balance: F=P+W - (3)

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Equations (1) and (2) can be solved: The results are

W = 1000 lb.; F = 2W = 2000lb

Example 2.3
A mixed acid containing 65% (by weight) H2SO4, 20% HNO3 and 15% H2O is to be made
by blending the following liquids:

1) A spent acid containing 10% HNO3, 60% H2SO4, and 30% H2O.
2) A concentrated nitric acid containing 90% HNO3, and 10% H2O.
3) Concentrated sulphuric acid containing 98% H2SO4 and 2% H2O.

How many kg of each of the three must be used to obtain 1000 Kg of the Mixed Acid.

Solution: This is a mixing process; no chemical reaction involved

Basis: 1000 kg of the mixed Acid SPENTACID

10% HNO3
60% H2SO4
30% H2O
X

CONC. NITRIC ACID

90% HNO3 MIXING 1000 kg MIXED
Y
10% H2O ACID (P)
65% H2SO4
20% HNO3
Z
15% H2O

CONC. H2SO4 ACID

98% H2SO4
2% H2O
Fig. 2.5: Figure for example 2.3

In the Mixed Acid stream (P) the quantities will be:

H2SO4 = 0.65 x 1000 = 650 kg

HNO3 = 0.2 x 1000 = 200 kg.
H2O = 0.15 x 1000 = 150 kg.

Component balance: Input = Output

HNO3: 0.1 X +0.9Y = 200 - (1)

H2SO4: 0.6 X+ 0.98Z = 650 - (2)
H2O: 0.3X + 0.1Y + 0.02Z = 150 - (3)
Overall: X + Y + Z = 100 - (4)

3 Independent Equations (1-3) and 3 unknowns (X, Y, Z) so the solution can be

obtained:

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The system of Equations can be presented as follows:

0.1 0.9 0  X   200   200 

     
0.6 0 0.98  Y  =  650   650 
0.3 0.1 0.02  Z  150  150 
 

The Determinant  can be evaluated:

 = 0.1 (0 – 0.098) – 0.9 (0.012 – 0.294) + 0 = 0.244

200 0.9 0
101
X  650 0 0.98  = = 413.93 kg
0.244
150 0.1 0.02

0.1 200 0
43
Y  0.6 650 0.98  = = 176.23 kg
0.244
0.3 150 0.02

0.1 0.9 200

100
Z  0.6 0 650  = = 409.84 kg
0.244
0.3 0.1 150

Spent acid: 413.93 kg

Conc. Nitric Acid: 176.23 kg
Conc. H2SO4 Acid: 409.84 kg

1000.0 kg Acid

2.3. Analysis of Material Balance Problems

As we move on the complex material balances we need to develop some techniques

of assessing the problem if it has unique solution or not. There are problems that
might have no sufficient or less data to guarantee a unique solution.

In order to determine whether the given material balance problem has a unique
solution or not, one needs to determine the degree of freedom for the problem.

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 The degree of freedom (DF) of a system is defined as follows:

Total no. of 
Total no. of   
  independen t 
DF  independen t  -   -
stream var iables  material balance 
  equations 


Total no. of known  Total no. of 

   
specified  independen t  - Subsidiary  (2.3a)
stream var iables  relations 
   

In short:
DF = Variables – Equations – known variables – Subsidiary relations (2.3b)

If DF is positive, the problem is said to be under specified. That is, more information
is needed for the problem to have unique solution. e.g. If DF = 2: this indicates that
Two more data/equation/information is needed for the problem to have unique
solution.

If DF is Negative: The problem is said to be Over specified: That is, the problem has
too much data so that a unique solution cannot be obtained e.g. if DF= -1, this means
that one data/equation/information has to be removed so that the problem gets a
unique solution.

If DF= 0. The problem is correctly specified and has a unique solution.

NB: The degree of freedom analysis is simply a systematic mechanism for counting
all variables, material balance equations and relations that are involved in the
problem.

Example 2.4
Carry out the DF analysis for the three previous examples and deduce if they have
unique solutions.

For Example 2.1

Distillate
450 kg B
Q1 kg T

F = 1000 kg 2 independent variables

50% B = 500 kg 1 variable specified
50% T = 500kg Distillation

2 independent
variables Bottoms
2 variables specified 475 kg T
Q2 kg B
2 independent variables
1 variable specified

Fig. 2.4: Degree of freedom analysis for example 2.1

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 Number of independent stream variables =6
Number of independent material balance equations =2
Number of independent specified variables =4
Additional relations =0

DF = 6 – 2 – 4 = 0. Hence a unique solution exists

For Example 2.2

Pure water (P)
100 lb
1 independent variable
1 variable specified
Seawater
F=? Evaporation
XNaCl = 0.035 Plant Waste Brine (W)
XH20 = 0.965 XNaCl = 0.07
2 XH2O = 0.93
2 independent variables
1 variable specified 2 independent variables
1 variable specified

Fig. 2.5: Degree of freedom analysis for example 2.2

Number of independent stream variables =5

Number of independent material balance equations =2
Number of independent specified variables =3
Additional relations =0

DF = 5 – 2 – 3 = 0, Hence a unique solution exists.

For example 2.3

SPENTACID, 3 independent variables

10% HNO3 2 specified variables
60% H2SO4
30% H2O

CONC. NITRIC ACID

90% HNO3 MIXING 1000 kg MIXED
Y
10% H2O ACID (P)
65% H2SO4
2 independent 20% HNO3
Z
variables 15% H2O
1 specified variable
CONC. H2SO4 ACID 3 independent
98% H2SO4 variables
2% H2O 2 specified
2 independent variables
variables
1 specified variable
35
Fig. 2.6: Degree of freedom analysis for example 2.3

Number of independent stream variables = 10

Number of independent material balance equations = 3
Number of specified independent variables
Flows  1
 = 7
Compositio n  6

Number of additional relations = 0

DF = 10 – 3 – 7 = 0; Hence a unique solution exists.

Example 2.5

A feed stock available at the rate of 1000 mol/h and consisting of (all concentration in
% mol) 20% propane (C3), 20% isopentane (i – C5), 30% Isobutane (i-C4) and 30%
normal pentane (C5); is to be separated into two fractions by distillation. The distillate
is to contain all propane fed to the Unit and 80% of isopentane fed to the unit and is
to consist of 40% isobutene. The bottoms stream is to contain all the normal pentane
fed to the unit. Carry out the DF analysis of this process and calculate the complete
Distillate and Bottoms analysis.

Solution: Basis: 1 h of operation.

Distillate, D
X CD3
X iD c4  0.4
F = 1000 moles X iDC5  0.6  X CD3
X CF3  0.2 X CD5  0
Distillation
X iF c4  0.3 Feed, F 4 independent
column
X iFC5  0.2 variables
2 variables
X CF5  0.3 specified
4 independent
variables
3 variables
specified
X CB3  0
Bottoms, B X iB c4
X iB C5
Fig. 2.7: Figure for example 2.5 X CB5
4 independent
Additional information: variables
1 variable
0.8 (0.2F) = D (XDi-C5) = D (0.6 – XDC3). specified

Number of Independent stream Variables = 12

Number of Independent material balance equation = 4
36
Number of specified Independent variables
(Flows = 1) + (Components = 6) = 7

Number of Subsidiary Relationship = 1

DF = 12 - 4 - 7 – 1 = 0, Hence a unique solution exists

Basis: 1 hour of operation

Component balance: Input = output

C3: 0.2F = XDC3.D = (1)

i-C4: 0.3F = 0.4D + B.XBi-C4 = (2)

i-C5: 0.2F = (0.6 – XDC3) . D + (1 – XBi-C4 – XBC5) B = (3)

C5: 0.3F = XBC5.B = (4)

Additional: 0.8 (0.2F) = D (0.6-XDC3) = (5)

So there are 5 equations and 5 unknowns (D, B, XDC3, XBi-C4 and XBC5). So the
system of equations can be solved:

Equations (1) and (5) yields D = 600 mol/h and XDC3 = 0.333

All other equations can be solved to yield:

B = 400 mol/h, XBi-C4 = 0.15, XBC5 = 0.75

Thus, once it is determined that the material balance problem is correctly specified
the pertinent equations and information can be assembled and the resulting algebraic
problem, can at least, in principle, be solved. Clearly the work involved in solving the
set of equations simultaneously, say, in linear case by using Cramer’s rule, is
considerably more than that required if we can solve the equations one at time, each
for a single unknown variable. A rule of thumb for this kind of situation is to choose
for solution that set of balances which involves the fewest unknowns per equation.
Such a set of equations will not only be the simplest but also the most likely to lend
itself to sequential solution.

2.4 Systems Involving Multiple Units

In the preceding sections, we observed that regardless of the internal complexities of

the system under consideration, the system could always be presented as a single
box which communicates with the environment via several input and output streams.
This corresponds to a macroscopic view of processing system, since we always
regard the system as a single unit within which the product materials are prepared.
However, most of systems typically consist of a sequence of processing steps, each
of which occurs within a specially designed individual unit. Clearly, in order to design
such intergraded multiunit systems, the Design Engineer must know the input and
output streams of the entire plant and also the flows and compositions of all internal
37
streams connecting the various units composing the processing system. This requires
a more detailed analysis of the system rather than our previous macroscopic view.
However it is by no means a microscopic view, since we do not dwell into the
mechanical details of the individual units but rather consider each to be an inscrutable
“black box”

2.4.1 Independent Sets of Material balance Equations

From the previous discussions it can be deduced that if there are S species
(components) in a particular system then one can make S+1 material balance
equations. However out of these only S equations are independent.

NB: One can make S component balance equations and one overall balance
equation, i.e. S + 1; however, the overall balance is not an independent
equation.

Similarly for multiple unit system, the units can be separated and unit balance
carried out.

Consider the Two Unit System shown below:

2 4

Unit
1 I Unit
II

3
5
Fig. 2.8: An example of a two - unit system

If S species are involved; then balances on Unit 1 (system 1) will give S Independent
equations. Similarly balances around Unit II (system 2) will give S independent
equations relating streams 3, 4 and 5. Finally if the overall balance is considered
(system 3), S set of equations will be made involving streams 1, 2, 4 and 5. The
stream variables associated with internal stream 3 will not appear in this set of
balance equations. So we have noted that, for this two unit system a set of 3S
equations can be written the question is whether all 3S equations can be used for
solution, i.e. whether they are all independent.

Recall that for a single unit system with S species, S + 1 equations can be written of
which only S equations are independent. The analogous situation develops for the
multiunit system. That is if a process contains M units each of which involving S
components, then only M sets of balance will be independent. Thus for the two unit
system above only two sets of Material balance equations (From Unit I and II) will be
independent.

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 2.4.2 Degree of Freedom for Multiple Units

Having established a rule for determining how many material balance equations are
available for solving the unknown stream variables in a multiunit process to update
the degree of freedom (DF) analysis that was presented for the single-unit case to
accommodate the multiunit case. This updating is rather easily accomplished
because the rules for counting stream variables and specified information remain
unchanged. Thus we define DF of a multiunit system in a form analogous to the
single – unit case as:

DF = Total number of independent stream variables

- Total number of independent material balance equation
- Total number of independent specified variables
- Total number of imposed subsidiary relations (2.4)

As before: if DF = 0; the problem is correctly specified but if DF >0: The problem is under
specified and if DF<0 then the problem is over specified.

Example 2.6

Consider a separation train consisting of two distillation columns that are designed to
separate a three-component mixture of benzene, toluene, and xylene into three streams,
each rich in one of the species. The system diagram is shown in figure 2.9. Construct a
DF analysis for this problem; and if the unique solution exists, then determine all
unknowns.

F2, X B2 , X T2 , X X2  0
3 independent variables F4
1 variable specified X B4  0.08
4 X T4  0.72
2
X X4  0.2
F1 = 1000 mol/h 3 independent
X B1  0.2 variables
X T1  0.3 2 variables
Unit
X 1X 10.5 specified
I Unit
3 independent II
variables
2 variables 3
5
specified
F3
F5
X B3  0.025
X B5  0 , X T5 , X X5
X T3  0.35
3 independent
X X3  0.625 variables
3 independent 1 variable specified
variables
2 variables specified

Fig. 2.9: Figure for example 2.6

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Total number of Independent variables = 3 x 5 = 15
Number of Independent Material balance equation

Unit I  3
 = 6
Unit II  3

Number of Independent specified variables

Flow  1
 = 9
Compositio n  8

Subsidiary Relationships = 0

DF = 15 – 6 – 9 = 0; Hence a unique solution exists.

We then start the balance by considering Unit I

Basis: 1 hour of operation, F1 = 1000 moles

Xylene balance: 0.5 x 1000 = 0.625 F3; F3 = 800 mol/h

Benzene balance: 0.2 x 100 = 0.025 (800) + X2B . F2 - (1)

Toluene balance: 0.3 x 100 = 0.35 (800) + X2T . F2 - (2)

Solving (1) and (2) gives F2 = 200 mol/h

If follows from equations (1) and (2) that X2B = 0.9 and X2T = 0.1

Balances around Unit II

Benzene: 0.025 (800) = 0.08 F4 + 0, F4 = 250 mol/h

Toluene: 0.35 (800) = 0.72 (250) + X5T.F5 - (3)
Xylene: 0.625 (800) = 0.2 (250) + X5X.F5 - (4)
Solving (3) and (4) gives, F5 = 550 mol/h

It follows from equations (3) and (4) that

X5T = 0.182, X5X = 0.818

Example 2.7

In the four-stage evaporation system shown below, a 50% by weight sugar solution is
concentrated to 65% by evaporating equal amount of water in each of the four stages.
With a total input of 50,000 kg/h a product stream of 35,000 kg/h is produced. Carry out
the DF analysis for this process and if a unique solution exists then determine all
unknowns.

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 F2 F4 F6 F8
100% 100% 100% 100%
2 vapour 4 vapour 6 vapour 8 vapour

UNIT I 3 UNIT II 5 UNIT III 7 UNIT IV

F3 F5 F7
1 Sugar Sugar Sugar 9
Water Water Water
F1 = 50,000 kg/h F9 = 35,000 kg/h
50% sugar 50% sugar
50% water 50% water

Fig. 2.10: Figure for example 2.7

Additional information: F2 = F4 = F6 = F8

Total Number of Independent stream variables

Flows  9
 = 14
Compositio n  5

Total number of Material balance equations

Unit I  2
Unit II  2
 = 8
Unit III  2 
Unit IV  2 

Total number of specified independent variables

Flows  2
 = 4
Compositio n  2 

Subsidiary Relationships = 1

DF = 14-8-4-1=+1; Hence the problem is under specified by one

variable/information and thus a unique solution cannot be obtained.

The lesson to be retained is that before attempting to solve a material balance

problem, one must first carefully determine how many unknowns there are in the
problem what information is given and how many independent material balance
equations it will be possible to make/write. With these data calculate the DF of the
problem. If the problem is correctly specified, proceed with the solution. Otherwise
the problem must be studied further to determine what information can be deleted if
the problem is over specified or else what additional information can be introduced if
the problem is under specified.

41
Rules of thumb; following rules are normally followed in solving a material balance
problem:

1. Draw a flow chart and fill in all given variable or values.

2 Choose a basis of calculation; an amount or flow rate of one of the process

stream. If one such quantity is given, it is most convenient to use it as a basis of
calculation.

3 Label unknown stream variables on the chart e.g. Mass or molar flow rates, mass
or mole fractions of stream components.

4 Do the problem book keeping, count unknowns, knowns and the relationships that
can be made in general, do the DF analysis and deduce if a solution exists.

5. Where necessary do unit conversions if the given units are mixed, e.g. Mass and
mole fractions. Convert all units into one basis.

6. Write material balance equations. Write them in order such that those involving
fewest unknowns are written first.

7. Solve the equations for unknowns to be defined, when the values of unknowns
have been calculated write them on the chart immediately.

8. If the basis chosen was not equal to the stream quantity given in the problem,
scale the balanced process streams by multiplying them by a ratio e.g. Q given/Q
calculation.

9. Check your result for consistency and accuracy usually by doing overall balance.

2.5 Balances on Reacting Systems

So far we have been dealing with systems that are non-reacting and we have been
applying the law of conservation of mass i.e. the chemical species are conserved
when they undergo purely physical processes.

In this section we shall try to deal with systems whereby chemical reactions take
place. In these types of systems the formulation of specie balance equations that
could account for the changes taking place in a chemically reacting system requires a
considerable higher degree of scientific sophistication. In particular it requires the
establishment of molecular formulas for chemical compounds, understanding of the
chemical transformation, in terms of rearrangement of the atoms, and presentation of
chemical reaction in terms of the now familiar stoichiometric reaction equations. Let
us start this section with the combustion reactions. In dealing with problems involving
combustion, one needs to be familiar with few special terms:

a) Flue or stack gas

This includes all gases resulting from the combustion process including the
water Vapour. Sometimes it is known as Wet analysis.

42
b) Orsat analysis or Dry basis analysis:
This includes all gases resulting from the combustion process excluding water
Vapour.

c) Theoretical Air (or theoretical Oxygen):

This is the amount of air (or Oxygen) required to be brought into the progress
for complete combustion. Sometimes it is called Stoichiometric amount of air
(or Oxygen).

d) Excess air (or oxygen):

This is the amount of air in excess of that required for complete combustion
i.e. In excess of the stoichiometric amount.

It is important to note that the calculated amount of excess air does not depend on
how much material is actually burned but it depends on what can be burned.
Even if only partial combustion takes place, e.g. Carbon burning to CO and CO2,
the excess air (or oxygen) is computed as if the process of combustion produced
CO2. The percent excess air is identical to the % excess O 2. In almost all
Combustion problems air is considered to be 79% mol N2 and 21% mol O2; the
g air
average molecular weight of air is  29.0
g mol Air

 excess air   excess 02 / 0.21 

% Excess air = 100   = 100   (2.5a)
 required air   requiredO / 0.21 
 2 

 O2 entering process  O2 required 

% Excess air = 100  
 (2.5b)
 O2 required 
or

excess O2
% Excess air = (2.5c)
O2 Entering  Excess O2

Example 2.8

Fuels for motor vehicles other than gasoline are being eyed because they
generate lower levels of pollutants than what the gasoline does. Compressed
propane has been proposed as a source of economic power for vehicles.
Suppose that in a test 20 kg of C3H8 is burned with 400 kg of air to produce 44 kg
of CO2 and 12 kg of CO. What was the % excess air?

43
Solution:
?
F = 20 kg 44 kg CO2
C3H8 Combustion
12 kg CO

Air = 400 kg
Excess air = ? 21% mol O2
79% mol N2

Fig. 2.11: Figure for example 2.8

Basis: 20 kg of C3H8.

Reaction: C3H8 + 5O2 3CO2 + 4H2O

Mol. wts. 44 32 44 18

Since the definition of % excess air is based on complete combustion of C 3H8 to

CO2 and H2O; the fact that the combustion was not complete cannot influence the
definition of Excess Air.

Theoretical O2 = 20 kgC3 H8 1kgmol C3H8 5 kg mol O2

44 kg C3H8 1kg molC2H8

= 2.27 kg mol O2

Moles of O2 entering = 400 kg Air 1 kg mol Air 21 kg mol O2

29 kg Air 100 kg mol Air

=2.90 kg mol O2

2.90  2.27
% Excess air = % excess O2 = x 100 = 27.8%
2.27

Example 2.9

Ethane (C2H6) is initially mixed with oxygen to obtain a gas containing 80% C 2H6
and 20% O2 that is then burned in an Engine with 200%excess air. 80% of C 2H6
goes to CO2, 10% goes to CO and 10% remains unburned. Calculate the
composition of the exhaust gas on a wet basis and also on the dry basis (Orsat
analysis).

44
Solution:

Fuel
FG CO2  ?
Combustion CO  ?
F=? 
Flue gas
80% C2H6 C 2 H 6  ?
20% O2 
P = ? Air O2  ?
N 2  ?
21% O2 
79% N2 200% Excess  H 2 O  ?

Fig. 2.12: Figure for example 2.9

Basis: 100 kg mol of Fuel:

Expected reactions are:

7
C2H6 + O2  2CO2 + 3H2O (1)
2

5
C2H6 + O2  2CO + 3H2O (2)
2

Given: 80% of C2H6 goes to CO2 = 0.8 x 100 x 0.8 = 64 kgmol C2H6

10% of C2H6 goes to CO = 0.1 x 100 x 0.8 = 8 kgmol C2H6

10% of C2H6 remains unburnt = 0.1 x 100 x 0.8 = 8 kgmol C2H6

For complete combustion of C2H6, The theoretical O2 is

80 kg mol C2 H 6 7
2 kg mol O2
= 280 kgmol O2
1kg mol C2 H 6

Since the feed contains 20 kgmol O2; Then theoretical O2 required

(to be supplied) = 280 – 20 = 260 kg mol.

 200 
O2 Entering the system =  260  260   = 260 x 3
 100 
= 780 kgmol O2

780 kg mol O2 79 kgmol N 2

N2 supplied = = 2934 kgmol N2
21 kgmol O2

45
 Now consider Reaction 1

64 kg mol C2 H 6 2 kg mol CO2

CO2 produced = = 128 kgmol CO2
1 kg mol C2 H 6

64 kg mol C2 H 6 3 kg mol H 2O
H2O produced = = 192 kg mol H2O
1 kg mol C2 H 6

Now consider reaction 2

8 kg mol C2 H 6 2 kg mol CO
CO formed = = 16 kg mol CO
1 kg mol C2 H 6

8 kg mol C2 H 6 3 kg mol H 2 0
H2O formed = = 24 kg mol H2O
1 kg mol C2 H 6

O2 Used up by the reactions

64 kg mol C2 H 6 7
2 kg mol O2
Reaction 1: = 224 kg mol O2
1 kg mol C2 H 6

8 kg mol C2 H 6 5
2 kg mol O2
Reaction 2: = 20 kg mol O2
1 kg mol C2 H 6

O2 consumed = total 244 kg mol O2

Oxygen balance:
(O2 input – O2 Consumed) = O2 out

(780 + 20) – 244 = 556 kg mol O2

From from consumed out (in flue gas)

Air feed

Total H2O produced = 24 + 192 = 216 kg mol H2O

(From reaction 2) (From reaction 1) In flue gas

The balances can then be summarized as shown in Table 2.1:

46
Table 2.1: Summary of results for example 2.9

Fuel Air Exhaust % mol in % mol in

Component [kgmol] [kgmol] Gas Exhaust Exhaust
[kgmol] Gas Gas
(wet basis) Dry basis

C2H6 80 - 8 0.2 0.22

O2 20 780 556 1441 15.27

N2 - 2934 2934 76.05 80.56

CO2 - - 128 3.32 3.51

CO - - 16 0.41 0.44

H2O - - 216 5.60 -

TOTAL 100 3714 3858 100.00 100.00

Dry basis 2342 (excluding water)

Example 2.10

Ethane (C2H6) is burned with 50% excess air. The percentage conversion of
Ethane is 90%; of the ethane burned, 25% reacts to form CO and the balance to
form CO2. Calculate the composition of the flue gas and the ratio of water to dry
flue gas.

NB: In this example we shall demonstrate how to do the balances using atomic
species. In this problem the species that need to balanced are C, H, O and N and
since the species are conserved, then inputs = outputs.

Let us take a basis of 100 mol of ethane fed.

100 moles C2H6 Flue gas x C2H6

Combustion y O2
z N2
a CO
b CO2
Air, 50% Excess d H2O
21% O2
79% N2

Fig. 2.13: Figure for example 2.10

47
Reactions are:

7
C2H6 + O2  2CO2 + 3H2O (1)
2
5
C2H6 + O2  2CO + 3H2O (2)
2
100 mol C2 H 6 7
2 mol O2
Theoretical O2 = = 350 mol O2
1mol C2 H 6

O2 fed = 350 x 1.5 (50% excess) = 525 mol O2 fed

525 mol O2 79 mol N 2

N2 fed = = 1975 mol N2 fed
21 mol O2

C2H6 Reacted = (0.9) (100) = 90mol C2H6 reacted

C2H6 Balance: output = Input – Consumption

C2H6 out (X) = 100 – 90 = 10 moles C2H6

 X = 10 moles C2H6

N2 balance: Input = output, N2 = 1975 moles N2

Z = 1975 moles N2

0.25 x 90 mol C 2 H 6 reacted to CO 2 mol CO formed

CO produced:
1 mol C 2 H 6 reacted

a = 45 moles CO

Now let us make the carbon balance

Input = Output
C (in C2H6) = C(in C2H6) + C(in CO) + C(in CO2)

100 mol C 2 H 6 2 mol C

= X (2) + a (1) + b (1)
1 mol C 2 H 6

200 = 2 (10) + 45 (1) + b (1); b= 135 moles CO2

Let us make the Hydrogen balance

H (in C2H6)input = H (in C2H)output + H (in H2O)output

100 mol C 2 H 6 6 mol H

= 6 (x) + 2 (d)
1 mol C 2 H 6

600 = 6 x 10 + 2d; d = 270 moles H2O

48
Let us make the Oxygen balance

O (input) = O (in CO2)output + O (in CO)output + O (in O2)

525 mol O2 input 2 mol O

= 1050 moles O
1 mol O2

O out = 2b + a + 2y + d = 1050

2 (135) + 45 + 2y + 270 = 1050, y = 232.5 moles O2

The analysis of the flue gas can now be summarized as follows:

Table 2.2: Summary of results for example 2.10

Component Moles % dry basis

x C2H6 10 0.42
y O2 232.5 9.70
z N2 1975 82.38
a CO 45 1.88
b CO2 135 5.63
Total 1397.5 100.01

Ratio of water to dry flue gas

270 mol H 2O
=
2397.5 mol dry flue gas

mol H 2 O
= 0.113
mol dry flue gas

Reactions other than Combustion Reactions

These also follow similar kind of analysis:

Example 2.11

The stoichiometric H2 – N2 mixture (75% H2, 25% N2) for synthesizing ammonia is
made by mixing producer gas (78% N2, 20% CO, 2% CO2) and water gas (50%
H2, 50% CO). The carbon monoxide, which acts as synthesis catalyst poison, is
removed by reacting this gas mixture with stream to form CO2 and H2 via the shift
reaction:

CO + H2O  CO2 + H2

The CO2 is subsequently removed by scrubbing with a suitable absorbent.

Assuming that all compositions are in moles % and that just enough steam is
added to completely convert all CO. Calculate the ratio in which the producer and
water gas streams ought to be mixed.

49
Solution:
CO2
100% CO2
4

1
Producer
gas 78% N2, 20% CO Reactor
2% CO2 5 Products
(shift reactor)
2
Water 75% H2
gas 25% N2
50% H2 3 Steam
50% CO 100% H2O

Fig. 2.14: Figure for example 2.11

Quick analysis of the process above reveals that N2 is a tie-component; it passes

through the process without being affect. A balance of N 2 allows deducing quickly
stream 5.

Let us start with a basis of 100 moles of Producer gas

F1 = 100 moles: 78 moles N2; 20 moles CO and 2 moles CO2.

N2 balance: 78 = 0.25 F5; F5 = 312 moles

CO balance: Input – consumption = output

(20 + 0.5 F2) – consumption =0 (1)

H2O balance: F3 – consumption =0 (2)

Let r represent the consumption term, from the reaction

CO + H2O  CO2 + H2, the stoichiometric coefficients

Suggest that rco = rH2O = r

Thus equation (1) and (2) can be written as:

20 + 0.5 F2 – r = 0 (1)
F3 – r = 0 (2)
Similarly we can make balances of CO2 and H2 in this case the species are
generated.

CO2 balance: input + generation = output

2 +r = F4 (3)

H2 balance: 0.75 (312) = 0.5 F2 + r (4)

50
Adding Equations (1) and (4), Eliminates r,

20 + 0.5 F2 + 0.75 (312); F2 = 214 moles

r can therefore be evaluated as: from equation (4)

r = 0.75 (312) – 0.5 (214) = 127 moles
From Equations (2) and (3) it follows that
F3 = 127 moles; and F4 = 139 moles

F1 100 mole F1
The Required Ratio: = = 0.467
F2 214 mole F2

2.6 Balances on Special multiunit Configurations (Recycle, By Pass and

Purge streams)

Recycle stream:
This is simply a stream that is split off from the outlet of a unit and sent back as
the input of an upstream unit. Thus the unit with recycle may be viewed as a
three unit process composed of a mixer, the inner process unit and a flow splitter
or divider as shown in Fig. 2.15.

Recycle stream

Fresh feed Products

Process unit

Mixer Splitter/divider

Fig. 2.15: Example of recycle stream arrangement

A by-pass stream is a stream, which is split off from another so as to avoid

processing. The stream is then mixed downstream with the stream coming from
the processing unit. As for the case of recycle stream, the By-pass unit can be
viewed as a unit consisting of a splitter, the process unit and a mixer as shown
Fig. 2.16.

By-pass stream

Fresh feed Products

Process unit

Splitter/divider Mixer

Fig. 2.16: Example of by-pass stream arrangement

It can be noted that for the recycle and By Pass Process Units Material balances
can be written on each individual unit as well as an overall balance around the
51
entire process. As we observed for multiunit systems, only three of the four sets
of balances will be independent.

Another process which is commonly encountered in process industries is a unit

consisting a purge or bleed stream. This is a four-unit system consisting of a
mixer, a process unit and two splitters as shown Fig. 2.17.

Recycle stream Splitter/divider

Purge stream

Fresh feed Products

Process unit

Mixer Splitter/divider

Fig. 2.17: Example of purge stream arrangement

By pass ad recycle stream are typically applied for:

1. Recovering and re-using unreacted reactants. Thus maximizing the

utilization of reactants.

2. Recovery of a catalyst. Catalysts are expensive, if they can be separated

and re-used this could be a good practice and would serve money for
purchasing the catalyst.

3. Dilution of a process stream; suppose a slurry is fed to a filter, if the

concentration of solids in the slurry is too high, the slurry is difficult to
handle and the filter will not operate properly. Thus rather than diluting the
feed with fresh liquid, a portion of the filtrate can be recycled to dilute the
feed to the required solid concentration.

4. Control of a process variable: Suppose a reaction releases an extremely

large amount of heat making the reactor difficult and expensive to control.
The rate of heat generation can be reduced by lowering the reactant
concentration that can in turn be accomplished by recycling a portion of
reactor effluent to the inlet. In addition to acting as a diluent, for the
reactants, the recycle material also serves as capacitance (Heat storage)
for the heat released. The greater the mass of the reaction mixture the
lower the temperature to which that mass will be raised by a fixed amount
of heat.

5. Circulating of a working fluid: The most common example of this

application is the refrigeration cycle used in household refrigerators and air
conditioners. In these devices, a single material is re-used indefinitely, with
only small make-up quantities being added to the system to replenish
working fluid (e.g. Refrigerant) that may be lost through leakages and
spillages.
52
6. Heat recovery of the outgoing hot stream. Hot air (flue gas) from boiler or
combustion chamber is normally recycled to Dryers or Kilns for drying or
calcining the lime in Cement factories.

7. To improve performance of the equipment: example in H 2SO4 production,

SO3 cannot be easily dissolved in oleum to produce H 2SO4. Hence
unreacted sO3 is normally separated from the acid stream and recycled
back.

The purge stream can be used to reduce or remove unwanted materials from the
system. Example for a system utilizing Air and recycling the air stream, At some
point it is necessary to purge out gases such as Argon, CO2, etc (gases
considered as in out in the process) which may accumulate in the system. A
typical example is in the production of ammonia from Air and Hydrogen.

It can be noted that in all three special configurations discussed above, only one
unit in the system requires special attention i.e. the splitter or divider. A flow
splitter is simply a device in which a given input stream is divided flow-wise into
two or more smaller streams. Since the division is purely on the basis of flow
(unless otherwise stated), the composition of all branches into which the main
stream is split must be the same. This condition is called ‘’splitter restriction’’.

Recycle in processes with chemical Reaction

In these systems two terms are normally used. These are defined below;

a) Overall fraction conversion;

This is defined as {Mass (moles) of reactant in fresh feed} – {Mass (moles)
of reactant in output of overall process} divided by Mass (moles) of reactant
in fresh feed. (2.6)

b) Single pass (once – through) fraction conversion:

This is defined as the {Mass (moles) of reactant fed into the reactor} –
Mass (moles) of reactant exiting the reactor} divided by Mass (moles) of
Reactant fed into the reactor (2.7)

When the fresh feed consists of more than one material, the conversion must be
stated for a single component usually the limiting reactant or the most expensive
reactant or similar compound.

It is import to note the distinction between fresh feed (This is the feed that is not
mixed with the recycle stream) whereas the feed to the process unit refers to the
feed that is mixed with recycle.

53
Example 2.12

Consider the recycle stream consisting of a distillation column, and its condenser
as shown in Fig 2.18:

Suppose that the column is used to separate a three-component mixture

consisting of 7% acetone (A), 61.9% acetic acid (AA) and 31.1% acetic anhydride
(AH). The column is designed to yield a bottoms stream consisting no acetone
and a Distillate containing 10% acetone and 88% Acetic Acid. If the column is
operated such that 60% of the overhead is returned as reflux, calculate all
unknown flows and compositions, assuming all compositions are in mol% and that
700 mol/h of distillate is to be produced.

F2 Splitter
X A2 , X AA
2 2
, X AH
3 Distillate
F3 = 700 mol/h
2 condenser
10% A
4
88 % AA
2% AH
Feed 1
F4 = 0.6F2
F1 10% A
7% A 88 % AA
61.9 % AA 2% AH
31.1% AH F5
X A5  0 , X AA
5 5
, X AH

5 Bottoms

Fig. 2.18: Figure for example 2.12

Let us take a basis of 1 h operation

Balances around the splitter:

A balance; X2A F2 = 0.1 (700) + 0.1 (F4) (1)

AA balance; X2AA F2 = 0.88 (700)+ 0,88 ( F4) (2)
AH balance; X2AH.F2 = 0.02 (700)+0.02 (F4) (3)
F4 = 0.6 F2 (4)
Overall balance; F2 = F4+700 (5)
700
From equation (4) and (5); F2 = = 1750 mol and hence
0.4
F4 = 0.6 x 1750 = 1050 mol
It follows immediately that X2A = 0.1, X2AA = 0.88 and X2AH = 0.02

Now making balances around the column

Total balance: F1 + F4 = F2 + F5 (6)

A acetone (A) : 0.07F1 + 0.1F4 = 0.1F2 (7)
AA balance: 0.619F1 + 0.88F4 = 0.88F2 + X5AA.F5 (8)
With F4 = 1050 mol, and F2 = 1750 mol; Equation (7)
54
 F1 = {0.1 (1750) – 0.1 (1050)}/0.07 = 1000 mol
Equation (6) gives F5 = 300 mol
Equation (8) gives X5AA = 0.01 and hence X5AH = 0.99

Example 2.13
The process for production of concentrated juice is as shown in Fig. 2.19:
suppose that 10% of the feed to such process is used as a “cut back” and that the
evaporator is operated to produce an outlet concentrate containing 80% dissolved
solids. If the process feed rate is 10,000 kg/h fresh juice calculate the rate at
which water must be evaporated and the composition of the final product.

F2 F4
88% water 100% water
12% solids 4 vapour
12% solids
Splitter mixer
Fresh juice 1 Products
2 Evaporator 5 6
F1 = 10,000 kg/h
88% water F6=?
F5 Water =?
12% solids 3
20% water Solids =?
Cut back
80% solids

F3
Fig. 2.19: Figure for example 2.13 88% water
12% solids
Let us take a basis of 1 h of operation:

Balances around the splitter:

Total mass balance: F1 = F2 + F3 or 100,000 = F2 + F3 (1)
Solids balance: 0.12 (10,000) = W 2S.F2 + W 3 S.F3 (2)
Water balance: 0.88 (10,000) = W 2H2OF2 + W 3H2O.F3 (3)

Or F3 + F2 = 10,000 - (1)
0.12 F2 + 0.12 F3 = 1,200 - (2)
F3 = 0.1F1 (Cut back fraction) - (3)

If follows that; F2 = 9,000 kg; F3 = 1,000 kg

Balances around the Evaporator

Solids balance: 0.12 (9,000) = 0.8 F5 , F5 = 1350 kg

Water balance: 0.88 (9,000) = F4 + 0.2 (1350); F4 = 7650 kg

Balances around the mixer

Total balance: F5 + F3 = F6 (4)

Solids balance: 0.8 (1350) + 0.12 (1000) = W 6S.F6 (5)

From Equation 5, F6 = 1350 + 1000 = 2350 kg

55
 Equation 6 yields W6S = 1200 = 0.51
2350

And hence W6H2O = 1 – 0.51 = 0.49

Example 2.14

Immobilised glucose is used as a catalyst in producing Fructose (f) from glucose

(g) in a fixed bed reactor (water is the solvent). The process is shown in Fig 2.20.
What percent conversion of glucose results on one pass through the reactor when
the exit stream / recycle stream ration in moles is equal to 8.33. The reaction is:

C6H12O6  C6H12O6
d-glucose d-fructose
F4 =?
Recycle stream 4 X g5 =?, X w5 =?,
X 5f  ?

Fresh feed 1 Products

2 Fixed bed 3
reactor 5
F1 = 100 kg
40% glucose (g) Mixer Splitter
F2 =? F5 =?
60% water (w) F3 =?
X g2 =?, X w2 =?, X g5 =?, X w5 =?,
X g3 =?, X w3 =?,
X 2f  0.04 X 5f  ?
X 3f  ?

Fig. 2.20: Figure for example 2.14

Let us take 100 kg of fresh feed:

It is assumed that the % given in the problem are mass %.

Let us make an overall balance on the process:

F1 = F5 = 100Kg. We can now make use of the Ration given in the problem:

F5
= 8.33 [Note that since F4 and F5 have same composition, the mole ratio of
F4
F5
will be the same as the Mass ratio].
F4

100 100
= 8.33; F4 = = 12.00 kg
F4 8.33

Now, water is a solvent, it is not generated or consumed in this process. So we

can make overall water balance.

100
Water balance: 0.6 F1 = X5W . F5, X5W = 0.6 x = 0.6
100
56
Balances around the mixer
Total balance: F1 + F4 or 100 + 12 = 112 = F2, F2 = 112 kg

Glucose balance: 100 (0.4) + 12 (X4g) = 112.X2g - (1)

Fructose balance: 0 + 12 (X4f) = 0.04 (112) - (2)

From Equation (2) X4f = 0.373

Now balance of the splitter restrictions, the composition of F5 should be the same
as that of F4. Hence we can find X5g as = 1 – 0.6 – 0.373 = 0.027 from equation
(1), it follows that:

X2g = {100 (0.4) + 12 (0.027)} 112 = 0.36

Balances around the splitter

Glucose: X3g .112 = 0.027.(100) + (0.027 x 12); X3g = 0.027

Water: X3w.112 = 0.6 (100) + 12 (0.6); X3w = 0.6

 Mass of glucose fed to the reactor = 0.36 (112) = 40.32Kg

Mass of glucose Exiting the reactor = 0.027 (112) = 3.024Kg

 40.32  3.024 
One pass conversion of glucose =   x 100 = 92.5%
 40.32 

57