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# ECH 3102

Chapter 4

## Assoc. Prof. Dr. Mohd Halim Shah Ismail

Semester 1 - 2014/2015
Introduction to Material
Balances
Objectives:
To explain the concept of process
classification, recycles, purges,
degree of freedom analysis, fractional
conversion, yield and selectivity,
theoretical and percent excess air
To generate a flow chart, and to perform
a degree of freedom analysis

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Concept of a Material Balance
A material
balance can be considered as an accounting for material
in a process
DATE ACTIVITY DEPOSIT WITHDRAWAL BALANCE
3/1 Beginning Balance 100.00

## 3/15 ATM Withdrawal 200 2600.00

1. Initial condition = beginning balance = RM100.00
3/31 Closing Balance 2600.00
2. Inputs = deposits = RM3500.00
3. Output = withdrawal = RM1000.00
4. Final condition = closing balance = RM2600.00

## Accumulation = final condition initial condition = closing balance

beginning balance = RM2600 3
Conservation of
Mass
Mass can neither be created nor
destroyed
60C

If
If

140 Then
kPa
10C 43
C

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Material Balance can refer to a balance
on a system for the:
- Total mass
- Total moles
- Mass of a chemical compound
- Mass of an atomic species
- Moles of a chemical compound
- Moles of an atomic species
- Volume (possibly)

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input: enters through system boundaries
output: leaves through system boundaries
generation: produced within the system
(reaction)
consumption: consumed within the system
(reaction)
accumulation: buildup within the system 6
Two types of balances may be written for
any system;
differential balances and
integral balances

## Differential Balances indicate

what is happening in a system at an
instant of time. Each term is a rate and
has a unit of quantity unit per time
Integral Balances describe what
happens between two instant of time.
Each term of the equation is an amount
of the quantity with a corresponding
unit 7
Open & Closed System

## Closed system: Open system:

No mass/material enters or Water is filled up in the tank
leaves the vessel (no material (input), and used daily for
cross the boundary bathing, washing, etc.
Changes can take place inside (output)
the system Mass/material has cross the
But no mass change boundaries
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90
100
kg/min
kg/min100
100
kg/min 1000
kg/min 1000
kg
kg

Process/System: Process/System:
Rate of water addition = rate Water accumulates at a rate of 10
of water usage, water level in kg/min
tank remain constant Thus, water level in tank depends
1. All condition inside the process on the amount of time, e.g. 1 min
remain unchanged (P, T, mass, additional 10 kg, 10 minutes?
flow rate, etc.) Amount of water changes with time
2. Condition of the flowing streams Other conditions such as P, T, flow
remain constant with time rates changes with time also 9
Material Balance
Equation
Suppose methane, is a component of both
input and output of a process

## qin(kg CH4/h) Process qout(kg CH4/h)

unit
If the flow rates of input and output are
found to be different. Possible explanations
are .
1. methane is leaking
2. methane is consumed or generated in a
reaction
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3. methane is accumulating in the process
Material Balance for Single Components

(1
)
For steady state condition: 100 kg/min 500 100 kg/min
Nothing is changing with time
Accumulation = 0 H2O kg H2O
H2O
(2
)
Not all of the conditions in the process remain constant with time
Changing with time
Accumulation over time can be calculated by

(3
)11
Material Balance for Single Components

## By combining equations (1) and (3), we get

general material balance for a component in
the non-reactive system

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Material Balance for Multiple Components

## Steady-state condition: Total flow in = Total flow out (Equation 2)

But
Different components balance are called Component Balances

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Material Balance for Chemical Reactions
Reactor

## 100 L/min 100 L/min

1000
1.0 molar kg 0.5 molar
HCl H2O NaOH

200 L/min
1.0 molar
NaCl

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Rules of Material Balance
If the balancedSimplification
quantity is Total Mass,
set generation = 0 and consumption = 0

## If the balance substance is a NonReactive species,

set generation = 0 and consumption = 0

## If a system is at Steady State,

set accumulation = 0

For Steady State System with No Generation &
Consumption:

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Processes
Batch process
Feed is fed at the beginning
Product is removed at the end
Continuous Process
The input and outputs flow
continuously throughout the
duration of process
Semibatch Process
Any process neither batch nor
continuous 16
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Example 4.2-2: Continuous

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Example 4.2-2: Continuous
Benzene/Toluene distillation
continuous process
no reactions occurring

## General species balance

0 0 0
input + generation output consumption
= accumulation

input = output
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input = output
Benzene balance
500 kg B/h = 450 kg B/h + m2
m2 = 50 kg B/h
Toluene balance
500 kg T/h = m1 + 475 kg T/h
m1 = 25 kg T/h
Total mass balance
1000 = 450 + m1 + m2 + 475 (all with units of
kg/h)
1000 kg/h = 1000 kg/h 22
REVISION PREVIOUS CHAPTER

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REVISION PREVIOUS CHAPTER

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REVISION PREVIOUS CHAPTER

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REVISION PREVIOUS CHAPTER

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Integral Balances on Batch Processes

## Consider the reaction N2 + H2 NH3 in a batch

reactor
at t=0, there is n0 moles of NH3 in the reactor
at t=tf, there is nf moles of NH3 in the reactor
between 0 and tf, no NH3 crosses system boundary
NH3 accumulation in system from 0 to t f is nf n0.
Therefore, for a batch process,
accumulation = final output initial input
= generation consumption
initial input + generation = final output + consumption
o Identical to continuous steady-state balance except in/out terms denote
discrete amounts instead of flow rates

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Example 4.2-3
Two methanol water mixtures are
contained in separate flasks. The first
mixture contains 40.0 wt% methanol
and the second contains 70.0 wt%
methanol. If 200 g of the first mixture
is combined with 150g of the second,
what are the mass and composition of
the product?
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If the flasks are mixed, what is the mass
and concentration of the resulting product?
no reactions, generation = consumption = 0
input = output

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Total Mass Balance
200 g + 150 g = m = 350 g
Methanol balance
0.400gCH3OH 0.700gCH3OH x gCH3OH
200g 150g m g
g g g
gCH3OH
x 0.529
g
Water balance
200(0.6) + 150(0.3) = 350(1-0.529)
165 g H2O = 165 g H2O
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Example

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Flowcharts
Normally, a Process Flow Sheets (PFS) or Process Flow Diagram
(PFD) comprises:
All major equipment/units
Lines entering or leaving the process/unit and/or lines
connecting 2 or more process equipment/units ( these are called
streams)
Flow rate of each stream
Composition of each stream
Operating conditions of each stream and/or unit/equipment
Qin
(e.g. T,P)
Energy/heat needed to be added to and /or removed from any
100
part of the 0.21
process
kg/h kg A/kg
or the entire process
m kg/h m kg/h
T=250
0.79 kg B/kg
0.3 kg A/kg
o
C 0.1 kg A/kg
100 0.4 kg B/kg P=5 0.3 kg B/kg
kg/h
1 kg C/kg 0.3 kg C/kg atm 0.3 kg C/kg
T=25oC, P=1atm 0.4 kg D/kg
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Examples of PFS
or PFD

## PFD for a Water-Softening by Ion-Exchange Process

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PFD for Ammonia Synthesis Plant 34
CHEMICAL ENGINEER!!!
One of the main responsibilities of
chemical engineers is to
create/construct/ analyse chemical
processes (or, at least, to understand
the existing processes)
The layout of a chemical process is
called process flow sheet (PFS) or
process flow diagram (PFD) PFS or
PFD can be for just a single process unit or
for the whole process, either simple or 35
Some important symbols of process equipment
are shown below:

## To create or to understand PFS or PFD, the

knowledge concerning material and energy 36
How to Label the Streams in a Flow Chart
1. The chart must be fully labeled with values of known
variables at the locations of the streams
1000mol/hr Air
OR
0.21mol O2m
/ ol 210 mol O2
0.79mol N2m
/ ol 790 mol N2
2. Assign algebraic symbols to unknown streams and write
their associated units on the chart
For unknown For unknown mass/mol
flow
rate fractions
n (mol/h) 400 (mol/h)

## 0.21 mol O2/mol y (mol O2/mol)

0.79 mol N2/mol (1 - y) (mol N2/mol)
T = 320oC, P = 1.4 atm T = 320oC, P = 1.4 atm
of y1
and y2
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Why?
How to Label the Streams in a Flow Chart (Contd)

## Unknown labelling should be kept at a

minimum to solve the balance easily

Example:

## instead of x1 kg A/kg and x2 kg B/kg x kg A/kg

and (1-x)kg B/kg for mass fraction in the stream

## If mass stream 1 is half of that stream 2, instead

of 1 and 2 and 2

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Convert all stream quantities to one basis
Only express quantities in mol or mass
If a volumetric flow rate of a stream is given,
convert to mass or molar flow rate since
balances are not normally written in volumetric
quantities
Use consistent notations for the labelling:

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Example : 2 Unit Distillation Columns

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Example : 2 Unit Distillation Columns

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Example : 2 Unit Distillation Columns

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Example : 2 Unit Distillation Columns

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Example : 2 Unit Distillation Columns

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Example : 2 Unit Distillation Columns

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Flowchart Scaling
E.g. A kilogram of Benzene is mixed with a
kilogram of Toluene. The output of this
process is 2 kilograms of a mixture that is
50% mass of each component.

## The flowchart is balanced because material

balances on both species are satisfied.
1 kg 1.0 kg CnHm/kg = 2 kg 0.5 kg
CnHm/kg
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Scaling the
flowchart
involves
changing all
values of
stream flows
by a
proportional
amount.
Note that mass
(or mole)
fractions are 47
Example 4.3-2
A 60/40 mixture (molar)
of A and B is separated
batch wise into 2 fractions.
Scale the flowchart to a
continuous 1250 lbmol/hr feed rate.
1250 lbmol hr lbmol hr
scale factor = 12.5
100 mol mol

## Feed: lbmol hr lbmol

100 mol 12.5 1250
mol hr

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A 60/40 mixture (molar)
of A and B is separated
batch wise into 2 fractions.
Scale the flowchart to a
continuous 1250 lbmol/hr feed rate.

## Top: lbmol hr lbmol

50.0 mol 12.5 625
mol hr

## Bottom: lbmolA hr lbmolA

12.5 molA 12.5 156
molA hr
lbmolB hr lbmolB
37.5 molB 12.5 469
molB hr
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A 60/40 mixture (molar)
of A and B is separated
batch wise into 2 fractions.
Scale the flowchart to a
continuous 1250 lbmol/hr feed rate.

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Basis of Calculation
Since a flowchart can always be scaled,
material balance calculations can be
performed on the basis of any
convenient set of stream amounts or
flow rates and the results can subsequently
be scaled to any desired extent.
A basis of calculation is an amount or
flow (mass or molar) of one stream or
component in a process.
The first step in balancing a process is to
chose a basis of calculation; all unknown
quantities are then determined to be
consistent with this basis. 51
If a stream amount or flow is given in a
problem statement, it is usually the most
convenient basis to use.

## If no stream amounts or flows are known,

assume a value of one, preferably for a
stream of known composition.
If mass fractions are known, set a total
mass or flow of that stream (i.e., 100 kg or
100 kg/hr) as the basis.
If mole fractions are known, choose a total
number of moles or molar flow rate (100 52
Balancing Nonreactive
Processes
For Non-Reacting processes, the material
balance takes the form: INPUT =
OUTPUT.
The maximum number of independent
equations that can be derived by writing
balances on a nonreactive system equals
the number of chemical species in the
input and output streams.
Write balances first that involve the fewest
unknown variables.
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3.0 kg
C6H6/min kg/min

1.0 kg x kg C6H6/kg
C7H8/min (1-x) kg
C7H8/kg
2 unknowns:
3 balanced equation, independent or
dependent?:
Total mass balance: 1
unknown
Benzene mass 2
balance: unknown
s
Toluene mass
2
balance:
unknown
s 54
Degree of Freedom
Analysis (DoF)
DoF procedure to determine enough information to
solve a given Material & Energy balance
1. Draw and label flow chart
2. Count the unknown variables on the flow chart,
nunknowns
3. Count the independent equations relating them,
nindep. eqns.

## ndf = nunknowns nindep. eqns.

If ndf=0, the problem is solvable
If ndf>0, the problem is underspecified, need to provide
If ndf<0, the problem is over specified, more equations 55
Sources of
Equations
Material Balances
For a non reactive process, no more than
nms independent equations may be written
where nms is the number of molecular
species (e.g. CH4, O2) involved in the
process
Energy Balance (Ch. 7-9)
Process Specifications
Physical Properties or Laws (e.g.
Ideal Gas Law)
Physical Constraints (yi = 1.0)
Stoichiometric Relations (for Reactive 56
Sources of Equations Relating Unknown Process
Variables
1. Material Balances
For non-reactive process, no more than number of molecular
species (nms) independent material balance may be written.
E.g. if only Benzene and Toluene in the streams, then n ms=2
nindep. eqns. = 2

## 2. Energy Balance (Chapter 7-9)

Energy balance can provide a relationship between outlet and
inlet material flows and temperature
Normally information on energy exchange is given (e.g. heat,
work, etc.)

3. Process Specification
Specification of how several process variables are related
E.g. Acetone fed is m1 in condenser, 40% appears in a
condensate stream
m2=0.4m1
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Sources of Equations Relating Unknown Process
Variables
4. Physical Properties and Laws (Chapter 5 & 6)
Two unknown variables may be the mass and volume, where
the SG is given in tables or an equation of state
E.g. Saturation or equilibrium conditions for the stream are
given which may provide needed relations

5. Physical Constraints
E.g. Total mole/mass fraction is 1.
If stream contains components of A, B and C, then the
fractions are xA, xB dan (1-xA-xB)

## 6. Stoichiometric Relations (Section 4.7)

If chemical reaction occur in the system, the stoichiometric
equations provide relationships between the quantities of the
reactants consumed and of the products generated

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A General Strategy for Solving
1. Understand the problem.
Material Balance
reactive or non-reactive

## 2. Choose a basis of calculation

If given any of the amount or flow rate, then use it
If several streams amount or flow rate given, use them
collectively
If none, take a basis based on known variables, e.g. given mass
fraction, use mass or mass flow rate (100 kg or 100 kg/h)

3. Draw the block flow diagram describing the problem and fill in all
the variables including assumed and unknowns
Should include either
. Total mass or mass flow rate and mass fractions of ALL
stream components, or
. Total moles or molar flow rates and mole fractions of ALL
stream components, or 59
A continuous mixer mixes NaOH with H2O to produce an aqueous
solution of NaOH. Determine the composition and flow rate of the
product if the flow rate of NaOH is 1000 kg/hr and the ratio of the
flow rate of the H2O to the product solution is 0.9.
3

## 1000 kg H2O kg/h

Mixer
NaOH/h

kg/h

x kg
NaOH/kg
(1-x) kg
0 H2O/kg

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4. Express what the problem statement asks you to determine in
terms of the labeled variables
Help to identify number of unknown variables

## A continuous mixer mixes NaOH with H2O to produce an aqueous

solution of NaOH. Determine the composition and flow rate of
the product if the flow rate of NaOH is 1000 kg/hr and the ratio of
the flow rate of the H2O to the product solution is 0.9.
4

## 1000 kg H2O kg/h

Mixer
To find:
NaOH/h
a) Flow rate product ()
b) Mass fraction of
NaOH (x) and H20 (1-
kg/h
x)
x kg
NaOH/kg
(1-x) kg
H2O/kg
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5. If given mixed mass and moles units for a stream, convert all
quantities to one basis using methods of Section 3.3

## 6. Do the degree-of-freedom analysis

Count the unknown and identify independent equations the
relates them
Six types listed in section 4.3d

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DOF analysis
Number of unknowns: 2 (,
1000 kg H2O kg/h x)
Mixer
NaOH/h Number of equations to
relate: 2
i) total balance
kg/h ii) NaOH balance
iii) H2O balance
x kg ndf = nunknowns - nindep eqns
NaOH/kg
(1-x) kg = 2-2 = 0
H2O/kg 62
Problem is solvable
7. If ndf=0, then write the equations in efficient order
simultaneous equations containing 2 unknown variables
DO NOT attempt to calculate anything ye

7
Total Mass
1000 kg H2O kg/h Balance
Mixer
NaOH/h

NaOH Component
kg/h Balance
x kg
NaOH/kg
(1-x) kg
H2O/kg 63
8. Solve the equations and calculate the quantities requested in the
problem
8

## Total Mass NaOH Component

Balance Balance

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QUIZ: Mixing of
Methanol-
Water Mixtures
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Example
QUIZ: Mixing 1 Steady state Mixtures
of Methanol-Water

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ASSIGNMENT 1
Question 1

Question 2

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HOMEWORK
Question 1

Question 2

Question 3

Question 4