ChE 111

CHEMICAL ENGINEERING CALCULATIONS

Module 2

CHAPTER 2

FUNDAMENTALS OF MATERIAL BALANCES

This module outlines procedures for writing material balances on individual process units and multiple-
unit processes. In this chapter we present methods for organizing known information about process variables,
setting up material balance equations, and solving these equations for unknown variables.

At the end of this module you are expected to ab able to do the following:

 Briefly and clearly explain in your own words the meaning of the following terms: (a) batch,
semibatch, continuous, transient, and steady-state processes
 Given a process description, (a) draw and fully label a flowchart; (b) choose a basis of
calculation; (c) write in order the equations you would use to calculate specified process
variables
Practice exercises (PE) are given at the end of each particular topic. You are expected to solve them
and submit to the professor on/before the due date.

LESSON 4:
PROCESS CLASSIFICATION
Chemical processes may be classified as batch, continuous, or semibatch and as either steady-state
or transient. Before writing material balances for a process system, you must know into which of these
categories the process falls.
1. Batch process
- The feed is charged or fed into a vessel at the beginning of the process and the vessel content
are removed sometime later. No mass crosses the system boundaries between the time the
feed is charged and the time the product is removed.
- Commonly used when relatively small quantities of products are to be produced on a single
occasion.
- Example: Rapidly add reactants to tank and remove the products and unconsumed reactants
sometime later when the system has come to equilibrium
2. Continuous process
- The inputs and outputs flow continuously throughout the duration of the process.
- Better suited to large production rates.
- Example: Pump a mixture of liquids into a distillation column at a constant rate and steadily
withdraw product streams from the top and bottom of the column.
3. Semibatch process
- Any process that is neither batch nor continuous.
- Example: Allow the contents of a pressurized gas container to escape to the atmosphere; slowly
blend several liquids in a tank from which nothing is withdrawn.

 If the values of all the variables in a process (i.e., temperatures, pressures, volumes, flow
rates) do not change with time, except possibly for minor fluctuations about constant mean
values, the process is said to be operating at STEADY STATE.
 If any of the process variables change with time, TRANSIENT or UNSTEADY-STATE
operation is said to exist.
 Continuous processes are usually run as close to steady state as possible. Unsteady state
(transient) conditions exist during the start-up of a process and following changes –
intentional or otherwise – in process operation conditions.
 By their nature, batch and semibatch processes are unsteady-state operations, whereas
continuous processes may be either steady-state or transient.
Practice exercises. Classify the following processes as batch, continuous or semibatch, and transient or
steady-state and explain your answer.
1. A balloon is filed with air at a steady rate of 2 g/min.
2. A bottle of milk is taken from the refrigerator and left on the kitchen table.
3. Water is boiled in an open flask.
4. Carbon monoxide and steam are fed into a tubular reactor at a steady rate and react to form carbon
dioxide and hydrogen. Products and unused reactants are withdrawn at the other end. The reactor
contains air when the process is started up. The temperature of the reactor is constant, and the

1
 composition and flowrate of the entering reactant stream are also independent of time. Classify the
process (a) initially and (b) after a long period of time has elapsed.
THE GENERAL BALANCE EQUATION (Steady State Concept)

 The basis for all material balances or mass balances is the Law of Conservation of Mass,
which states that mass can neither be created nor destroyed.
Suppose methane is a component of both the input and output streams of a continuous process unit,
and that in an effort to determine whether the unit is performing as designed, the mass flowrates (ṁ) of methane
in both streams are measured and found to be different (ṁ in ≠ ṁout).

PROCESS
UNIT
ṁin (kg CH4/h) ṁout (kg CH4/h)

There are several possible explanations for the observed differences between the measured flow rates:
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.
4. The measurements are wrong.
If the measurements are correct and there are no leaks, the other possibilities – generation or
consumption in a reaction and accumulation within the process unit – are all that can account for a
difference between the input and output flow rates.
A balance on a conserved quantity (total mass, mass of a particular species, energy, momentum) in a
system (a single process unit, a collection of units, or an entire process) may be written in the following
general way:
Input + Generation - Output - Consumption = Accumulation
(enters (produced within (leaves through (consumed within the (buildup within the
through the system) system system) system)
system boundaries)
boundaries)

Example 1.1 The General Balance Equation

Each year 50,000 people move into a city, 75,000 people move out, 22,000 are born, and 19,000 die.
Write a balance on the population of the city.
Solution: Let P denote people

input + generation−output−consumption=accumulation(2.1)
P P P P P
50,000 +22,000 −75,000 −19,000 =A ( )
yr yr yr yr yr
P
A=−22,000
yr
** Each year the city’s population decreases by 22,000 people.
The following rules may be used to simplify the material balance equation:

 If the balanced quantity is total mass, set generation = 0 and consumption = 0. Except in
nuclear reactions, mass can neither be created nor destroyed.
 If the balanced substance is a nonreactive species (neither a reactant nor a product), set
generation = 0 and consumption = 0.
In this case, equation (1) reduces to:

input−output=accumulation(2.2)
 If a system is at steady state, set accumulation = 0, regardless of what is being balanced.
By definition, in a steady-state system nothing can change with time, including the amount
of the balanced quantity.
Hence, equation (1) reduces to:

input−output=0
2
 Or

input=output (2.3)
LESSON 5:
PROCESS FLOWCHART
When you are given process information and asked to determine something about the process, it is
essential to organize the information in a way that is convenient for subsequent calculations. The best way to do
this is to draw a flowchart of the process, using boxes or other symbols to represent process units (reactors,
mixers, separation units, etc) and lines with arrows to represent inputs and outputs. Simple boxes are perfectly
adequate to represent process units on the flowcharts.
Example 2.1 Suppose a gas containing N2 and O2 is combined with propane in a batch combustion chamber in
which some (but not all) of the O2 and C3H8 react to form CO2 and H2O, and the product is then cooled,
condensing the water. The flowchart of this two-unit process might be shown in Figure 2.1 below.

100 mol C3H8 50 mol C3H8 50 mol C3H8

750 mol O2 750 mol O2
COMBUSTION
CONDENSER
CHAMBER
1000 mol O2 3760 mol N2 150 mol O2
3760 mol N2 150 mol CO2 3760 mol N2
200 mol H2O

200 mol
H2O
Figure 2.1 Flowchart of a combustion-condensation process.

When used properly, the flowchart of a process can help get material balance calculations started and
keep them moving. To do so, the chart must be fully labeled when it is first drawn, with values of known process
variables and symbols for unknown variables being written for each input and output stream. Thereafter, the
chart functions as a scoreboard for the problem solution: as each unknown variable is determined its value is
filled in, so that the chart provides a continuous record of where the solution stands and what must still be done.
Suggestions to follow for labeling a flowchart:
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.

Note:
Although any symbol may be used to represent any variable, having a consistent notation can aid
understanding. For this course we will generally use the following notations:
m = mass
ṁ = mass flow rate
n = moles
ṅ = molar flow rate
V = volume
Ṿ = volumetric flow rate
x = component fractions (mass or mole) in liquid streams
y = component fractions (mass or mole) in gas streams

LESSON 6:
GENERAL BALANCE PROCEDURE
Summary of problem-solving approach in material balance calculations given a description of a process, the
values of several process variables, and a list of quantities to be determined:
1. Choose as a basis of calculation an amount or flow rate of one of the process streams.
2. Draw a flow chart and fill in all known variable values, including the basis of calculation. Then label
unknown stream variables on the chart.
3. Express what the problem statement asks you to determine in terms of the labeled variables.
4. If you are given mixed mass and mole units for a stream (such as a total mass flow rate and component
mole fractions or vice versa), convert all quantities to one basis or the other.
5. Do the degree-of-freedom analysis. Count unknowns and identify equations that relate them.
3
 6. If the number of unknowns equals the number of equations relating them (i.e., if the system has a zero
degrees of freedom), write the equations in an efficient order (minimizing simultaneous equations) and
circle the variables for which you will solve. Start with equations that only involve one unknown variable,
then pairs of simultaneous equations containing two unknown variables, and so on. Do no algebra or
arithmetic in this step.
7. Solve the equations, either manually or using equation-solving software. Manual solution should go
smoothly since you already worked out an efficient solution procedure.
8. Calculate the quantities requested in the problem statement if they have not already been calculated.
9. If a stream quantity or flowrate n g was given in the problem statement and another value n c was either
chosen as a basis or calculated for this stream, scale the balanced process by the ratio n g / nc to obtain
the final result.

NUMBER OF DEGREES OF FREEDOM (ndf)

- It refers to the number of variables in a set if independent equations to which values must be
assigned so that the equation can be solved.
- The differences between the number of variables whose values are unknown and the number of
independent equations.

 You have too many equations or not enough variables in the problems.
 Either the flowchart is incompletely labeled or the problem is over specified with redundant
or possibly inconsistent relations.

Sources of equations relating unknown process stream variables:

1. MATERIAL BALANCES
- For a nonreactive process, no more than nms independent material balances may be written
(nms = number of molecular species)
Example:
If benzene and toluene are the species in the streams entering and leaving a distillation column,
you would write balance on benzene, toluene, total mass, atomic C, atomic H, etc. But at most, two of those
balances are independent; if additional balances are written, they will not be independent of the first ones
and so will not provide new information.
2. ENERGY BALANCES
- If the amount of energy exchanged between the system and its surroundings is specified or if it
is one of the unknown process variables, an energy balance provides a relationship between
inlet and outlet material flows and temperatures.

3. PROCESS SPECIFICATIONS
- The problem may specify how several process variables are related.
Example:
Acetone fed to a condenser has a mass flow rate, ṁ 1 = kg acetone/s. 40% appears in a
condenser stream, flow rate, ṁ2 = kg acetone/s. A system equation would be: ṁ2 = 0.40ṁ1

4. PHYSICAL PROPERTIES AND LAWS

Example:
Mass and volume may be the unknown variables, in which case, a tabulated specific gravity for
liquids and solids or an equation of state for gases would provide an equation relating the two variables.

5. PHYSICAL CONSTRAINTS
Example:
If the mole fractions of the 3 components of a stream are labeled X A, XB, XC, then a relation
among these variables is XA + XB + XC = 1. If XC is labeled 1 - XA - XB, then you will have one less
equation to worry about.

6. STOICHIOMETRIC RELATIONS
- If chemical reactions occur in a system, the stoichiometric equations (ex: 2H 2 + O2  2H2O)
provides relationship between the quantities of the reactants consumed and of the products
generated.
** Equations are independent if you cannot derive one by adding and subtracting combinations of the others.
Example: x = 3; y = 2; x+y = 5
only two of these equations are independent
only one of them can be obtained from the other two by addition or subtraction

4
In solving the practice exercises, you can solve using yellow papers or coupon bonds, then take a clear shot of
your solutions and submit them to my email ad: cephmina1426@gmail.com. Solutions using MS word or any
other means are also accepted.

 Due date for online submission of solution to practice exercises will be on/before 8:00 PM of August
16, 2020.

 First long exam schedule:

2A: August 18, 2020 8:30 – 9:30 AM
2B: August 17, 2020 10:00 AM – 12:00 NN
2C: August 17, 2020 2:30 – 3:30 PM

References:
R.M.Felder and R.W. Rousseau, Elementary Principles of Chemical Process, 2nd edition. New York:
Wiley, 1986
W.I. Jose, Introductory Concepts in Chemical Engineering, 2004
H.S. Stoker, Introduction to Chemical Principles, 2nd edition. New York: Macmillan, 1986

Prepared by:

ENGR. MARIA TERESA M. MINA, MSChE

Subject Professor