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ChemMat 201:
Process Engineering I: Introduction
Fundamentals of Material Balances
Dr Filicia Huang (f.wicaksana@auckland.ac.nz)

Textbook:
Felder R.M. and Rousseau R.W. (2005)
Other texts:
Himmelblau, D M “Basic Principles and Calculations in Chemical 
Engineering”.

Introduction to Material Balances
Chapter 4.1, F&R

• Fundamental law of nature:
– Conservation of mass
– Material can neither be created nor destroyed
– Exception = nuclear reactions 

Antoine‐Laurent Lavoisier

• A material balance is the application of this law to any

process
• It is one of the most vital skills you will learn as a
Chemical or Process Engineer!
• It is an important part of process design and analysis
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http://www.alibaba.com/product‐detail/small‐capacity‐strawberry‐jam‐Production‐Line_637325449.html

Expected background knowledge

• Unit conversions
• Basic mathematics (substitution, multiplication, 
log, ln, graph plotting)
• Concept of grams, moles, density
• Mass fraction, mole fraction, %mass, %mole
• Stoichiometry
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Syllabus synopsis

• Fundamentals of Material Balances:  
– Overall material balances 
– multiple‐unit processes
– Recycle, bypass, and purge 
– for systems with chemical and combustion reactions
• Material Balances With Multi‐Phase Systems:
– Phase equilibrium 
– for systems with phase change such as: evaporation, 
condensation, drying, humidification, 
dehumidification, absorption, distillation, extraction, 
crystallisation, and filtration

1. Process Classification
Learning Outcomes:
A student who successfully completes this 
section will be able to understand and explain 
the concepts of process classification, transient 
and steady‐state processes.

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Process Classification
• Processes can be classified as batch, continuous or semi‐batch
• Batch process: 
– Feed introduced at the beginning of the process, products removed at 
the end. 
– The process change occurs over time.
– Example: baking biscuits or beer fermentation
• yeast and wort added to fermentation vessel, beer and spent yeast removed 
at the end of fermentation.

Batch stirred 
tank reactor

Process Classification
• Continuous process:
– The inputs and outputs constantly flow into and out 
of the process
– example: spray drying of milk powder
• milk concentrate and air fed constantly to the dryer, 
powder and humidified air constantly removed

Continuous 
stirred tank 
reactor (CSTR) Plug flow 
reactor
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• Semi‐batch process:
– Any process that is neither batch nor continuous
– Example: dissolution of a powder
• slow addition of a powder to a solvent in a mixing vessel 
without removing any material
– Example: combustion
• continuous addition of air onto batch solid reactant

Steady vs unsteady state
• Steady state:
– all process variables constant with time 
• (temperatures, pressures, volumes, flowrates etc)
• Similar in concept to EQUILIBRIUM
• Unsteady state:
– process variables change with time
• Batch/semi‐batch processes
– must be unsteady state 
• Continuous
– may be either steady or unsteady state
– unsteady at start‐up or when a control variable 
is changed
– usually aim for steady state operation
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Steady state reached  Unsteady state

from:http://www.mathdaily.com/lessons/upload/1/13/Si
from: http://ece.gmu.edu/~gbeale/ece_421/ ne_Cosine_Graph.png
images/ess_01_03.gif

Process classification?

Batch/semi‐ Steady state/
batch/continuous transient
A balloon is filled with air at a steady rate 
of 1 g/min
A bottle of warm milk left on a table

Water drained from a tank
CO + H2O  CO2 + H2
‐ Reactants are fed into a reactor at a 
steady rate
‐ Products & unused reactants are 
withdrawn at the other end
‐ The reactor contains air at start up
‐ T of the reactor, composition and flow 
rate of the feed stream are constant
(a) Condition at initial stage
(b) After a long period of time has elapsed
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2. Material balances ~ calculation procedures

Learning Outcomes
A student who successfully completes this 
section will be able to:

• Understand and explain the degrees of 
freedom and the types of material balance.
• Construct a process description (draw and 
fully label a flowchart for single unit process) 
and solve corresponding mass balances.

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Material balances ~ calculation procedures

A. Draw flow sheet

• Fully labelled with values of known variables
B. Assign symbols to unknowns
C. Define assumptions
D. Choose a basis of calculation (e.g. production rate)
E. Unit conversions
F. Write balance equations
• for a multiple unit process, identify the subsystems for which balances
might be written
G. Perform degree of freedom analysis
H. Solve equations
• Start with those with the fewest unknowns
• Avoid simultaneous equations
I. Calculate and give the answer in appropriate units
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Material balances ~ calculation procedures

Material balances ~ calculation procedures
A. Draw a flow sheet
– Use boxes for unit processes or subsystems
– Use arrows for process streams (inputs & outputs)
– Add values of all known stream variables, i.e.
• total flow/amount of stream e.g. kg h-1
• flow/amount of each component
• component concentrations e.g. mol L-1 or mol mol-1

B. Define unknowns
• Symbols are assigned to unknown variables
– Minimise symbols used
• eg use Q and 2Q if you know one flow is twice the other
• eg use x and (1-x) if you only have two components

C. Define Assumptions
• All assumptions should be stated  for example:
assume that air contains 21% mole O2 and 79% mole N2
D. Choose a basis of calculation
– Basis of calculation is a mass or moles or flow rate (mass or
molar) of one stream or stream component in a process.
• use a given quantity as a basis of calculation  most
convenient
• or assume one if none given  for example: basis: 100 kg
feed/h
E. Unit Conversions
• Have consistent units
– if you have both masses and moles, convert to one or the other
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F. General balance equation
When material is added into a system (e.g. water
into a tank), there are several possibilities that
could happen to it:
– output: it leaves the system
– accumulation: it stays within the system
– consumption: it is converted to another species
– generation: more of the material in question may be
produced by conversion from another species

In

consumption?  = reaction
generation?
accumulation? Out

• A general material balance can be written as:

Input – output + generation – consumption = accumulation

• This can be derived for:

– total mass (mass balance), total moles (mole balance)
– components (chemical species/molecules, agglomerates, isomers, etc.)
– atomic species
• For non-reacting systems:
• generation = consumption = 0

Input – output = accumulation
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G. Degree of freedom analysis

• Draw and completely label the flowchart
• Count the unknown variables and the independent equations:
Number of degree of freedom (ndf) = number of unknowns - number of independent
balances (species)

• If:
• ndf = 0  problem can be solved

• ndf > 0  more unknowns than equations underspecified, problem cannot be

solved

• ndf < 0  more equations than unknowns over specified, problem cannot be
solved

• See: Felder and Rousseau, Example 4.3-4 p.100

Types of material balance

• Differential balance:
– Indicates what is happening in the process at an
instant in time.
– Each term of the balance equation is a flow rate
• e.g. kg/s, mol/h
– Is applied to continuous, steady state processes

• Integral balance:
– Describes what happens over a period of time
– Each term in the balance equation is a discrete amount
• e.g. kg, mol
– Usually applied to a batch process, with the time interval
being the duration of the process.
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Differential balances:
Mass balances on continuous SS processes

• At steady state:
Accumulation = 0

SS: No 
accumulation SS: No accumulation

Input + generation – output – consumption = accumulation

• Therefore the balance reduces to:

Input + generation = output + consumption
With no reactions generation & consumption = 0  Input = Output

Integral balances:
Mass balances on batch processes
• In a batch process, all mass introduced at the start
of the process will be removed at the end
– total mass balance is therefore always of the form:

Initial input = final output

• In terms of a single component, any accumulation

(or depletion) can only be due to generation or
consumption (e.g. by reaction)
– A balance on any component is therefore of the form:

Initial input + generation = final output + consumption

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Example 1: Mass balances on a continuous distillation process

A mixture of ethanol and water that contains 40% ethanol by mass is separated in a distillation
column. At steady state, the mass flow rate of water in the vapour stream is 80 kg hr‐1 and that
of ethanol in the bottom stream is 20 kg hr‐1. If the vapour stream contains 80 % ethanol, write
balances on ethanol and water to calculate the unknown component flow rates in the input and
output streams.

Example 2: Air humidification and oxygenation processes

(Example 4.3-1, F&R 2005, p 92)
Three input streams are fed into an evaporation chamber to produce an output stream with the
desired composition:
A. Liquid water, fed at a rate of 20.0 cm3/min
B. Air (21 mole% O2, the balance N2)
C. Pure oxygen with a molar flow rate one fifth the molar flow rate of stream B.
The output gas is analysed and found to contain 1.5 mole% water. Draw and label a flowchart of
the process and calculate unknown stream variables.
Molecular weight of water (H2O) = 18, density of water = 1 g/cm3
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3. Material balances with multiple unit

processes, recycles, bypasses and purges
Chapters 4.4 – 4.5, F&R (2005)

Learning Outcomes:

A student who successfully completes this section will be able to:

• Construct a process description (draw and fully label a 
flowchart for multiple unit processes) and solve 
corresponding mass and energy balances.
• Solve mass balance problems in complex systems with various 
configurations (recycle, purge, bypass streams).

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Multiple unit processes

• Involve several unit processes

• Define a system boundary by identifying material flows
between units (process inputs/outputs)
• Draw a box around the system of interest
• Thus we can write balances over
For:
– individual units
• Total balances
– Mixing or separation points • Species balances
– the whole process (overall balance) • Atom balances

Q, x, y Q, a, b, x, y
Plug flow 
reactor
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Example of multiple unit processes

http://www.inclusive-science-engineering.com/manufacture-of-h2so4-by-chamber-process/

Multiple unit processes

Feed 2

Feed 1 Product 3
Unit 1 Unit 2

Product 1 Product 2 Feed 3

Figure 4.4‐1 F & R

For the above system, a number of different system boundaries can be drawn:
• A = Overall mass balance
• B = Feed stream mixing point mass balance
• C = Mass balance on Unit 1
• D = Splitter mass balance
A given input stream is divided into 2 or more smaller streams, same compositions
(composition Stream I = composition Stream III = composition Product 2), only flow rates are
different
• E = Mass balances on Unit 2
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• Procedure for each type of balance is exactly the same as described

previously, except:
– Sub-systems: You may need to perform the balance on several sub-
systems to define all the unknowns!
• This is because the outputs of one system define the
inputs to the next. Therefore, you may need to solve
several systems systematically to define all variables.
• Choose system boundaries which contain the least
number of variables at each step – this makes solving
possible!
– Overall balance: Usually we perform the overall balance first to fully
define the input (feed) and output (product) streams

Example 3: A continuous two‐unit process 
Example 4.4‐1 p. 105, F&R (2005)
A labelled flow chart of a continuous steady-state two-unit membrane separation
process is shown below. Calculate the unknown flow rates and compositions of streams
1, 2 and 3.
40 kg/h 30 kg/h
0.9 kg A/kg 0.6 kg A/kg
0.1 kg B/kg 0.4 kg B/kg
100 kg/h
0.5 kg A/kg Membrane 1 Membrane 2
0.5 kg B/kg
1 2 3

30 kg/h
0.3 kg A/kg
0.7 kg B/kg
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Example 4 (Problem 4.9 Felder and Rousseau)
Strawberries contain about 15 wt% solids and 85 wt% water. To make strawberry jam,
crushed strawberries and sugar are mixed in a 45:55 mass ratio, and the mixture is
heated to evaporate water until the residue contains one-third water by mass.
(a) Draw and label a flowchart of this process
(b) Calculate how many pounds of strawberries are needed to make a pound of jam.
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Processes with recycle

• In many processes, a portion of an output stream is returned to the

inlet of a process unit  recycle
• This often occurs after the separation of a desired compound, like
the product or catalyst
• Used for:
– re-use of catalyst
– recirculation of working fluid
– dilution of feed
– improved control
– increased conversion
• Boundaries are drawn and sub balances calculated as before

Fresh feed Product 
Reactor

Separator
(here a membrane)

Recycle stream

• Overall balance
– When the system is at steady state, there is no accumulation
– Thus:
fresh feed = product
• Reactor balance
– The feed to the reactor is the sum of the recycle and fresh feed, thus

reactor feed = fresh feed + recycle stream

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Purge
Product 

Fresh feed
Reactor
Separator

Recycle stream Purge

• A purge is sometimes required when you have a recycle

• Purging prevents build-up of an inert component which would
have no other way of leaving the system
– Prevents accumulation
– Allows steady state to be attained
• Stream compositions into and out of purge are all identical
• Calculations similar to recycle

Bypass

Fresh feed Process unit Product 

Bypass stream

• Bypass is where a portion of the feed to a process unit is

diverted around the unit and combined with the output
stream.
– It bypasses the process unit!
– It is used to control the product composition and properties
• Calculations are similar to recycle
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Example 5:
Extraction of Soya bean oil
Soya beans containing 10 wt% oil and 90 wt% solids are ground and fed to a stirred
tank, where they are suspended in liquid hexane. The feed ratio is 3 kg hexane (kg
beans)-1. All of the oil in the beans is extracted by the hexane. The mixer effluent
passes to a filter where the bean solids are separated. The filter cake contains 75 wt%
bean solids with the balance being oil and hexane (in the same ratio in which they are
fed to the filter). The filter cake is discarded and the liquid filtrate fed to a vacuum
evaporator, in which the hexane is vaporised, leaving pure oil. The hexane vapour is
condensed and recycled to the stirred tank.
Calculate the stream flows (relative to mass of beans processed) and compositions.