Principles of Chemical

Engineering

Chapter

4 Fundamentals of
Material Balances:
Part 1
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Instructor: Dr. Mohammad Batiha
Email: mbatiha@ahu.edu.jo
Office hours: Mon & Wed (1 – 3)
1. PROCESS CLASSIFICATION

Process is a series of operations involving the physical, chemical, or

biological transformation of an input material for the purpose of achieving
a desired product material.

Process Flowsheet or Process Flow Diagram (PFD) – schematic

showing how the process streams are connected to the process units.

Process Streams – inputs and outputs to and from the process units, with
arrows showing the direction of flow.

Process Variables – species and quantities (composition, flowrates, T, P,

etc.) used to characterize the process inputs and outputs.

Chemical Process Variables – Any measurement used to characterize or

describe a chemical process.

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Example of a chemical process:

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Before writing a material balance (MB) you must first identify the type of
process in question.

1. Batch Process: no material (mass) is transferred into or out of the

system over the time period of interest (e.g., heat a vessel of water)

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2. Continuous Process: material (mass) is transferred into and out of
the system continuously (e.g., pump liquid into a distillation column
and remove the product streams from top and bottom of column).

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3. Semicontinuous (Semibatch) Process: any process that is neither
batch nor continuous (e.g., slowly blend two liquids in a tank).

4. Steady-State Process: process variables (i.e., T, P, V, flow rates) do

not change with time.

5. Transient Process: process variables change with time.

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2. BALANCES

2.1 The General Balance Equation

Suppose methane is a component of both input and output streams of a

continuous process unit. What if the mass flow rates of methane in both
streams are measured and found to be different?

1. Methane is being consumed as a reactant or generated as a product

within the unit.
2. Methane is accumulating in the unit – possibly adsorbing on the walls.
3. Methane is leaking from the unit.
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4. The measurements are wrong.
A balance on a conserved quantity in a system is:

Input + Generation – Output – Consumption = Accumulation

Input – enters through system boundaries.

Generation – produced within system.
Output – leaves through system boundaries.
Consumption – consumed within system.
Accumulation – build up within system.

Two types of balances may be written:

1. Differential balances: indicate what happening in a system at an

instant in time. Each term of the balance equation is a rate (rate of
input, rate of generation, etc.) and has unit divided by time. Applied to
continuous process.

2. Integral balances: describe what happens between two instants

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of time. Each term of the equation is an amount of the balanced
quantity. Applied to batch process.
Example 1: Each year 50000 people move into a city, 75000 people
move out, 22000 are born, and 19000 die. Write a balance
on the population of the city
Solution:

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The following rules may be used to simplify the material balance equation:

- If the balanced quantity is total mass, set generation and consumption

equal to zero. Mass can neither be created nor destroyed.

- If the balanced substance is a non-reactive species (neither a reactant

nor a product), set generation and consumption equal to zero.

- If a system is at steady-state, set accumulation = 0.

2.2 Balances on Continuous Steady-State Processes

For continuous processes at steady-state, the balance equation is

Input + Generation = Output + Consumption

If the balance is on a non-reactive species or on total mass, then

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Input = Output
Example 2: 1000 kg/h of a mixture of benzene (B) and toluene (T)
containing 50% benzene by mass is separated by
distillation into two fractions, as shown. Calculate the
unknown component flow rates in the output streams.
Solution:

The process is steady-state and no chemical

reactions occur: Input = Output

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2.3 Integral Balances on Batch Processes

The balance equation is

Initial input + Generation = Final output + Consumption

Example 3: Two methanol-water mixtures are contained in separate

flasks. The first mixture contains 40 wt% methanol, and
the second contains 70 wt% methanol. If 200 g of the first
mixture is combined with 150 g of the second, what are
the mass and composition of the product?
Solution:

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The input and output “streams” shown denote the initial and final states for
this batch process. No reaction occurs, input = output.

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2.3 Integral Balances on Semibatch and Continuous Processes

The procedure is to write a differential balance on the system and then to

integrate it between two instants of time.

Example 4: Air is bubbled through a drum of liquid hexane at a rate of

0.1 kmol/min. The gas stream leaving the drum contains
10 mole % hexane vapor. Air may be considered insoluble
in liquid hexane. Use an integral balance to estimate the
time required to vaporize 10 m3 of the liquid.
Solution:

Air does not dissolve in liquid: Accumulation = 0

Air does not react with hexane:

Generation = Consumption = 0

The balance is
Input = Output 15
The integral hexane balance (from t = 0 to t = tf) has the form:
Accumulation = – Output
Accumulation – the total change in moles of liquid hexane during time (tf)
is negative since hexane is being lost from the system.

Since the total number of moles of hexane evaporated occupied a liquid

volume of 10 m3 and the specific gravity of liquid hexane is 0.659, the
accumulation is

The output term in the balance is the rate at which hexane is leaving the
system [0.1 ǹ (kmol hexane/ min)] times the total process time. The
balance is:

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3. MATERIAL BALANCE CALCULATIONS

3.1 Flowcharts

When you are given process information and asked to determine

something about the process, it is essential to organize the information by
drawing a flowchart of the process, using boxes or other symbols to
represent process units and lines with arrows to represent inputs and
outputs.

Suggestions for labelling a flowchart to get the greatest possible benefit

from it in material balance calculations:
1. Write the values and units of all known stream variables at the
locations of the streams on the chart.
2. Assign algebraic symbols to unknown stream variables and write
these variable names and their associated units on the chart. 17
__________________________________
Homework: Solve Example 4.3-1 page 92.
3.2 Flowchart Scaling and Basis of Calculation

Suppose 1 kg of benzene is mixed with 1 kg of toluene. The output from

this process is 2 kg of a mixture that is 50% benzene by mass.

The process shown by this flowchart is balanced. The following may be

done while the process remains balanced:

- The masses (but not mass fractions) of all streams could be

multiplied by a common factor.
- The stream masses could be changed to mass flow rates.
- Mass units could be changed to mass flow rates.
- Mass units of all stream variables could be changed from kg to g or
lbm or any other mass unit.
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The procedure of changing the values of all stream amounts or flow rates
by proportional amount while leaving the stream compositions unchanged
is referred to as scaling the flowchart – scaling up if the final stream
quantities are larger than the original or scaling down if they are smaller.

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Example 5: A 60-40 mixture (by moles) of A and B is separated into
two fractions. A flow chart of the process is shown. It is
desired to achieve the same separation with a continuous
feed of 1250 lb-moles/h. Scale the flowchart accordingly.
Solution:

The scale factor is

The masses are converted to flowrates:

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The units of mole fractions in the top product stream may be changed from
mol/mol to lb-mole/lb-mole, but their values remain the same. The
flowchart for the scaled-up process follows.

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3.3 Balancing a Process

Suppose 3 kg/min of benzene and 1 kg/min of toluene are mixed. The

process flowchart might be drawn and labeled as follows:

▪ 2 unknowns (ṁ, x), so 2 equations are needed to calculate them.

▪ Material balance equation for this non-reactive process is input = output.
▪ Three possible balances can be written: on (1) total mass; (2) benzene;
(3) toluene. Any 2 provide equations needed to determine ṁ and x.

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The rules apply to non-reactive processes:

1. The maximum number of independent equations that can be derived

by writing balances on a non-reactive system equals the number of
chemical species in the input and output streams. Writing equation
more than the maximum number, you will accomplish nothing.

2. Write balances first that involve the fewest unknown variables.

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Example 6: An aqueous solution of sodium hydroxide contains 20%
NaOH by mass. It is desired to produce an 8% NaOH
solution by diluting a stream of the 20% solution with a
stream of pure water. Calculate the ratios (liters water/kg
feed solution) and (kg product solution/kg feed solution).
Solution:

1. Choose a basis of calculation (an amount or flow rate of one of the

feed or product streams) and then draw and label the flowchart.

We will arbitrarily choose a basis of 100 kg of the 20% feed solution.

The flowchart appears as follows:

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2. Express what the problem asks you to determine in terms of the
labeled variables on the flowchart.

The desired quantities are V1/100 (L H2O/kg feed solution) and m2/100
(kg product solution/kg feed solution). Our task is to calculate the
variables V1 and m2.

3. Count unknown variables and equations relating them:

Unknowns: 3 unknowns (m1, m2 and V1).

Equations: 2 equations since we have 2 species (H2O and NaOH).
We can write any two balances (on NaOH, H2O, total
mass, and so on). Once we have written any two, we can
obtain NO new information by writing a third one.

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4. Outline the solution procedure: All balances for this system have
the form input = output. Looking at the flowchart, we can see that
balances on total mass and water each involve 2 unknowns (m1 and
m2), NaOH balance only involves 1 unknown (m2). So we begin the
solution by writing and solving NaOH balance for m2.

5. NaOH balance (input = output)

6. Total mass balance (input = output)

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7. Diluent water volume. The density of liquid water is approximately
constant at 1 kg/liter, hence:

8. Ratios required in problem statement

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3.4 Degree-of-Freedom Analysis

Before you do calculations, you can use a drawn and labeled flowchart to
determine whether you have enough info to solve a given problem. This
procedure is referred to as degree-of-freedom analysis.

To perform a degree-of-freedom analysis:

- Draw and completely label a flowchart,
- Count the unknown variables on the chart,
- Count the independent equations relating them, and
- Subtract the second number from the first. The result is the number of
freedom of the process.

Equations are independent if you cannot derive one by adding and

subtracting combinations of the others.

For example, only 2 of the 3 equations x = 3, y = 2, and x + y = 5 are

independent; any one of them can be obtained from the other two by
addition or subtraction.
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The number of freedom of the process is:
ndf = nunknowns – nindep eqns
There are three possibilities:
1. ndf = 0, there are n independent equations in n unknowns and the
problem can be solved.
2. ndf > 0, there are more unknowns than independent equations relating
them.
Either relations have been overlooked or the problem is
underspecified and has infinitely many solutions, hence, plugging into
calculations is a waste of time.

3. ndf < 0, there are more independent equations than unknowns.

Either the flowchart is incompletely labeled or the problem is
overspecified and possibly inconsistent relations. You can solve it
when equations and unknowns are brought into balance.
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__________________________________
Homework: Solve Example 4.3-4 page 100.
Sources of equations relating unknown process variables

1. Material balances: for a non-reactive process, usually but not

always, the maximum number of independent equations that can be
written equals the number of chemical species in the process.

2. Process specifications: Problem statement may specify how

several process variables are related.

3. Physical constraints: e.g., mass or mole fractions must add to 1.

4. Stoichiometric relations: If chemical reaction occurs, the

stoichiometric equations of the reactions provide relationships
between quantities of reactants and products..

5. Energy balance: The second half of the course.

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Example 7: Two methanol-water mixtures are contained in separate
tanks. The first mixture contains 40 wt% methanol and the
second contains 70 wt% methanol. If 200 kg of the first
mixture is combined with 150 kg of the second, what are
the mass and composition of the product?.
Solution:

Step 1: Draw a flowchart to visually organize the data

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Step 2: Determine the degrees of freedom

Number of unknowns: 3 unknowns (m3, xM3, xW3)

Number of independent equations:

Material balances: 2 equations
Physical constraint: 1 equation (∑x = 1)
----------------
Total independent equations: 3 equations

ndf = nunknowns – nindep eqns = 3 – 3 = 0

The problem is solvable.

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Step 3: Write down the equations

Material Balances (Steady-State, Non-Reactive Process):

Total Balance: m1 + m2 = m3
Methanol-Balance: m1 xM1 + m2 xM2 = m3 xM3
Water-Balance: m1 xW1 + m2 xW2 = m3 xW3

Choose only 2 equations since one of them is no longer independent.

Physical Constraint (applied to mixture 3):

xM3 + xW3 = 1

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Step 4: Solve the unknowns (m3, xM3, xW3)

Always start with the equation with the least number of unknowns if
possible and minimize solving equations simultaneously.

Total Balance (m3): m3 = 200 kg + 150 kg = 350 kg

↓
Methanol Balance (xM3): 200 kg × 0.4 + 150 kg × 0.7 = 350 g × xM3
xM3 = 0.529
↓
Physical Constraint (xW3): xW3 = 1 – xM3 = 1 – 0.529 = 0.471

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4. BALANCE ON MULTIPLE-UNIT PROCESS

Industrial chemical processes rarely involve just one process unit. Before
we analyze such processes, we must take a closer look at what we mean
by a system.

System is any portion of a process that can be enclosed within a

hypothetical box (boundary). System may be:
- The entire process.
- Interconnected combination of some of the process units.
- Single unit.
- Point at which two or more process streams come together or one
stream splits into branches.

The inputs and outputs to a system are the process streams that intersect
the system boundary.

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A flowchart for a two-unit process is shown.

Five boundaries drawn about portions of the process define systems on

which balances may be written:

Boundary A: Encloses the entire process (Feed streams 1, 2, and 3 and

Product Streams 1, 2, and 3). Balance on this system is the
overall balance.
Boundary B: Encloses a feed stream mixing point.
Boundary C: Encloses Unit 1.
Boundary D: Encloses a stream splitting point. 36

Boundary E: Encloses Unit 2.

Example 8: A labeled flowchart of a continuous steady-state two-unit
process is shown. Each stream contains two components,
A and B, in different proportions. Three streams whose
flow rates and/or compositions are not known are labeled
1, 2, and 3. Calculate the unknown flow rates and
compositions of streams 1, 2, and 3.
Solution:

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The systems about which balances might be written are shown on the
following flowchart:

C B

A B

Boundary A Outer: comprises entire process streams that enters and

leave the process.
Boundary B Interior: comprise individual processes.
Boundary C Junction point: comprises stream junction point.
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Degree-of-freedom analysis:

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40
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__________________________________
Homework: Solve Example 4.4-2 page 107.
5. RECYCLE AND BYPASS
5.1 Recycle

Suppose we have the following chemical reaction taking place in a

reactor,
A→B
Since it is rare for any chemical reaction to proceed to completion, some
of A will remain in the product stream.

This is not a desirable situation as some unreacted A leaves in the

product stream and this is undesirable for two reasons:
(1) It is wasteful ($), and,
(2) The final product is not very pure in B. How can we improve this
situation? 42
Recycle is a common feature of chemical processes. There are several
reasons for using recycle a chemical process:

1. Recovery and reuse of unconsumed reactants.

2. Recovery of catalyst: catalyst is expensive and is used to

increase reaction rate.

3. Dilution of a process stream: Suppose a slurry is fed to a filter. If

the solid concentration is high, slurry is difficult to handle and filter
will not operate properly. Rather than diluting the feed with fresh
liquid, a portion of filtrate can be recycled.

4. Circulation (recovery and reuse) of a working fluid: e.g.,

refrigeration fluid.

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Example 9: The flowchart of a steady-state process to recover
crystalline potassium chromate (K2CrO4) from an aqueous
solution of this salt is shown.

Calculate the rate of evaporation, the rate of production of

crystalline K2CrO4, the feed rates that the evaporator and
the crystallizer must be designed to handle, and the
recycle ratio (mass of recycle / mass of fresh feed).
Solution:

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Let K denote K2CrO4 and W denote water.

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 ṡ = ṁ4 + ṁ5
ṡ – solids flow rate.
0.95 ṡ = 0.95 (ṁ4 + ṁ5)
ṁ4 = 0.95 (ṁ4 + ṁ5)

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5.2 Bypass

Bypass: a fraction of the feed to a process unit is diverted around the unit
and combined with the output stream, thus varying the composition and
properties of the product.

Chemical processes involving bypass streams are treated in exactly the

same way as processes containing recycle streams.

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