Material Balance (Purge Etc)

CHE 205 Chemical Process Principles
Section 2: F&R, Chapter 4

INTRODUCTION TO MATERIAL BALANCES
Most problems you will have to solve in CHE 205 will look something like this:
A liquid mixture containing 45.0 wt% benzene (B) and 55.0% toluene (T) is fed to a distillation
column operating at steady state. Product streams emerge from the top and bottom of the column.
The top product stream contains 95.0 wt% B, and the bottom product stream contains 8% of the
benzene fed to the column. The volumetric flow rate of the feed stream is 2000 liters/h and the
specific gravity of the feed mixture is 0.872. Determine the mass flow rate of the overhead
product stream and the mass flow rate and composition (mass fractions) of the bottom product
stream.
You can take two approaches to solving such problems:
1. Start writing and solving equations until all of the required quantities have been determined.
2. Draw and label a flow chart, do a degree of freedom analysis, lay out a solution strategy, and then
write equations and solve for the required quantities.
Students in CHE 205 almost always initially lean toward the first approach, which looks more efficient to
them. That choice has several likely consequences that you should be aware of.
Feature of Course
Problem-solving time early in
Chapter 4
Problem-solving time, most of
Ch. 4 and Ch. 59
Course grade
Writing and solving equations

Slightly faster
Slower, then much slower, then
may never get the solution
C-F (as opposed to A-C for the
other approach)
Suggestion: Start using the second approach immediately, even on the simple problems, so that youll be
used to it when the problems start getting harder (which they will very soon). This handout guides you
through the basics of that approach. We also suggest that you read through pp. 4-1 to 4-6 of the Student
Workbook. If you follow all the guidelines laid out in those pages, it may not guarantee a good grade in
the course but it will increase the odds significantly.
The labeled flow chart of the process described in the first paragraph might appear as follows:
m 2 (kg/h)
0.95 kg B/kg
0.05 kg T/kg
2000 L/h (S.G.=0.872)

m 1 (kg/h)
Distillation
Column
0.45 kg B/kg
0.55 kg T/kg
m B 3 (kg B/h) (8% of B in feed)

m T 3 (kg T/h)
Figure 1. Flow Chart of a Distillation Process
2-1
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)

We will refer back to Figure 1 throughout this handout.
Nomenclature:
Batch process: Add contents, then remove them later
Continuous process: Continuously add then remove contents
Semi-batch process: Neither batch nor continuous; e.g. allow contents of gas tank to escape;
slowly blend liquids in a tank from which nothing is withdrawn
Steady state process: Process variables (flowrates, T, P) are constant
Transient process: Process variables change with time
Balance equation
We can write a balance on any quantity entering or leaving a system mass, moles, energy, people:
(a)
Input
What
comes
in across
system
boundary
Generation
What is
produced
within the
system
(reaction)
I+GOC=A
Output
What
leaves
across
system
boundary
(4.2-1)
Consumption
What is
consumed
within the
system
(reaction)
Accumulation
Change in amount
contained in the system
Simplifications
Continuous process at steady state: A = 0

Nonreactive system, or balance on nonreactive species: G = 0, C = 0
Batch process: I = 0, O = 0, A = final value initial value
2-2
Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)

Example:
Referring back to Figure 1, write balance equations on benzene, toluene, and total mass.
Solution: The general balance equation is I + G O C = A
In all balances on the process shown in Figure 1, we may drop the terms ___, ___, and ___.
Why? _______________________________________________________________________
The balance equation therefore reduces to __________________________________________
Balance on benzene (B): _______________________________________________________
Balance on toluene (T): ________________________________________________________
Balance on total mass: _________________________________________________________
Drawing and labeling flow charts

The first step in approaching a typical CHE 205 problem is to draw and completely label the flow chart.
What does it mean to be completely labeled?
A stream on a flow chart is completely labeled when you can write an expression for the
amount (batch) or flow rate (continuous) of each species in the stream in terms of
numbers and variables written on the flow chart. A flow chart is completely labeled if
every stream on it is completely labeled.
For example, a continuous stream of natural gas containing 85 wt% methane and the balance ethane
might be labeled as:
0.85 kg CH4/kg
0.15 kg C2H6/kg
Is this stream completely labeled? (Hint: No!) Why not?

__________________________________________________________________________
(kg/s) denote the unknown mass flow rate of the stream. The labeling would then be
Suppose we let m
m (kg/s)
0.85 kg CH4/kg
0.15 kg C2H6/kg
The stream is now completely labeled, since we can express the mass flow rates of methane and ethane in
terms of what is written on the chart:
Methane flow rate: m CH 4 (kg CH 4 /s) = _____________________
Ethane flow rate: m C2 H 6 (kg C 2 H 6 /s) = _____________________
2-3

Rules for labeling:
You may label either a total flow rate (or amount) and component mass or mole fractions, or
individual component flow rates (amounts).
m(kg)
x1 (kg NaCl/kg)
x2 (kg KCl/kg)
(1 x1 x2 )(kg H 2 O/kg)
OR
m1 (kg NaCl)
m2 (kg KCl)
m3 (kg H 2 O)
Once you have one, you can always calculate the other:
In terms of m, x1, and x2, m1 = _____________________________
In terms of m1, m2, and m3, m = _______________ and x1 = __________________________
Label in the way that builds in given information about the stream. (For instance, if you know
or can easily calculate either a total flow rate or values of component mass or mole fractions,
label the total and fractions; otherwise label individual component flow rates or amounts
(likely to get easier algebra that way).
Suppose you know that a gas stream containing sulfur dioxide and air (21 mole% O2, 79%
N2) flows at a rate of 125 mol/s. The stream might be labeled
125 mol/s
x (mol SO2 / mol)
(1-x) (mol air/mol)
0.21 mol O2/mol air
0.79 mol N2/mol air
Exercise: Prove that this stream is

completely labeled.
Solution:
nSO (mol SO 2 / s) ___________________
2
__________________________________
__________________________________
If volumes or volumetric flow rates of streams are either given or required, include labels
both for them and for mass or molar quantities.
For practice, do Test Yourself on p. 93.
2-4

Exercise: Enriching Air with O2.
A stream of air (21.0 mole% O2, 79.0% N2), a stream of pure oxygen, and a stream of liquid water
flowing at a rate of 20.0 cm3/min, are fed to a steady-state evaporation chamber in which all of the liquid
evaporates. The flow rate of the pure oxygen is 20% of the flow rate of the air. The emerging gas stream
contains 1.5 mole% water vapor.
20% of air flow rate
O2 (g)
Air
0.21 mol O2/mol
0.79 mol N2/mol
Evaporator
0.015 mol H2O(v)/mol
20.0 cm3 H2O(l)/min
Completely label the flow chart (including the molar flow rate of the liquid water stream),
following the rules given above.
Evaporator
0.015 mol H2O(v)/mol
0.21 mol O2/mol
0.79 mol N2/mol
20.0 cm3 H2O(l)/min
Convince yourself that your labeling is complete. (For example, what is the flow rate of oxygen
in the outlet stream in terms of labeled values and variable names.)
Basis of Calculation and Flowchart Scaling. At least one stream quantity or flow rate (mass, moles,
volume) should be specified before any calculations are done. If the problem statement doesnt do it, you
should choose a convenient basis (an amount of a stream with known composition.) Having degrees of
freedom = 1 is often a reminder that you must choose a basis.
2-5

Example: A stream containing 30 wt% ethanol (E) and 70% water (W) is blended with a stream
containing 60% E and 40% W. The product contains 35% E. What is the mass ratio of Stream 1 to Stream
2 (= m1/m2 in the flow chart)?
m1 (g)
0.30 g E/g
0.70 g W/g
Mixer
m2 (g)
0.60 g E/g
0.40 g W/g
m3 (g)
0.35 g E/g
0.65 g W/g
Solution: The problem statement does not specify a stream amount or flow rate. There is enough
information to calculate the required stream ratio without specifying one, but arbitrarily choosing a basis
of calculation (an amount or flow rate of one of the streams) makes the required math easier. We might
proceed as follows:
Basis of calculation: 100 g of Stream 1 (m1 = 100 g):
100 g
0.30 g E/g
0.70 g W/g
Mixer
m2 (g)
0.60 g E/g
0.40 g W/g
m3 (g)
0.35 g E/g
0.65 g W/g
We could then write balance equations on ethanol and water, solve for m1 and m2, and determine the
requested ratio as 100/m2. The same result would be obtained if we chose any other basis of calculation:
the values of m1 and m2 might be different, but the ratio would be the same.
Read Section 4.3b to see how to scale a flow chart from one basis to another, and work through the
Test Yourself on p. 95.
Degree-of-Freedom Analysis and Solution Strategy

Once a basis of calculation has been chosen and the flow chart is drawn and fully labeled, carry out a
degree-of-freedom analysis:
______
______
______
= DF
unknowns (the number of unknown variables on the flow chart)

balances (minus the number of independent balance equations)
other equations (minus the number of other equations relating the unknowns)
degrees of freedom
DF = 0 number of equations equals number of unknowns can solve for all unknowns
DF > 0 (more unknowns than equations) either youve overlooked some equations, problem is
underspecified, or you can solve for all requested quantities without knowing all the unknowns.
DF < 0 (more equations than unknowns) either flowchart is not fully labeled or problem is
overspecified.
2-6

Here are some simple examples to illustrate:
x + y = 10
____ unknowns
- ____ independent equations
-----------------------------____ DOF
x + y = 10
xy=0
____ unknowns
- ____ independent equations
-----------------------------____ DOF
x + y = 10
2x + 2y = 20
____ unknowns
- ____independent equations
-----------------------------____ DOF
x + y = 10
xy=0
xy = 3
____ unknowns
- ____independent equations
-----------------------------____ DOF
2-7

In this course, when you have zero degrees of freedom, the problem can be solved.
For a non-reactive process, the number of independent material balance equations equals the number
of independent species involved in the process.
Independent molecular species: We discussed this in the context of how many balances we can do
around a process. If two molecular species are in the same ratio everywhere in the process and the
ratio is incorporated in the flowchart labeling, the species are not independent, and neither are
balances on them.
100 mol CH4/s
n1 (mol air/s)
Gas blender
0.21 mol O2/mol

0.79 mol N2/mol
n2 (mol/s)
x1 (mol CH 4 / mol)
(1 x1 )(mol air / mol)
0.21 mol O 2 / mol air
0.79 mol N 2 / mol air
Looks like 3 unknowns 3 equations (balances on CH4, O2, N2) = 0 D.F., but it wont work. Write
balances on O2 & N2 & see what happens.
O2 balance:
N2 balance:
2-8

Example. Reconsider the distillation process shown again below. The basis of calculation is 2000 L/h of
the feed stream (exact, not 1 significant figure).
m 2 (kg/h)
2000 L/h (S.G.=0.872)

m 1 (kg/h)
Distillation
Column
0.45 kg B/kg
0.55 kg T/kg
0.95 kg B/kg
0.05 kg T/kg
m B 3 (kg B/h) (8% of B in feed)

m T 3 (kg T/h)
Degree-of-freedom analysis (count only variables labeled on the chart):
__ unknowns
__ balances
1 ___________________
1 ___________________
= 0 DOF
(_______, ________)
All unknowns can be calculated
Since the problem is solvable, we may proceed to write out the equations. All balances have the form
(_________).
Feed density: m 1
2000 L _____________ kg
m 1 (kg/h) (2000)(0.872)
h
L
(1)
8%: m B 3 _____________________
(2)
Mass balance: m 1 m 2 m B 3 m T 3
(3)
Benzene balance: ________________________________________________
(4)
Either do the algebra and arithmetic manually (easy in this problem, not so easy in problems to come) or
use Excels APEx or Solver to calculate the unknown quantities.
Equations:
m1 = 2000*0.872
mB3 = 0.08*m1*0.45
m1 = m2 + mB3 + mT3
m1*0.45 = m2*0.95 + mB3
m 1 1744
kg
h
, m 2 760
kg
h
B 3 =62.8
, m
kg B
h
T 3 =921
, m
kg T
m B 3
m
kg B
kg overhead
= 0.0638
xB
, ROF 2 0.436
kg
kg feed
m B 3 m T 3
m 1
2-9

Scale the flow chart: Now suppose we are asked to calculate the volumetric feed rate needed to produce
2500 lbm/day of overhead product. The scale factor (see Example 4.3-2) is the desired value of the
specified quantity (overhead product rate = 2500 lbm/day) divided by the value of the same quantity
corresponding to the original basis of calculation (= 760 kg/h).
Scale Factor (SF) =
2500 lb m /day
lb /day
3.29 m
760 kg/h
kg/h
lb /day
kg
3 lb m feed
(m 1 )new (m 1 )old SF 1744 3.29 m
5.74 10
h
kg/h
day
Work through Problem 4.11 in the Student Workbook. Follow every step. Fill in the blanks yourself,
then check the solutions.
2-10

Multiple-unit balances (Section 4.4)
Weve looked at processes represented by single boxesmixer, distillation column. Think about plants
youve seen from the highwayall those towers & stacks & pipes running all over the place.
How do you analyze something like that?
Overall system: large box around system enclosing all units, recycle & bypass streams. Subsystems:
individual units or combinations of units, stream mixing points & stream splitting points. DOF
analyses as with single units.
Go through Ex. 4.4-1.
Work through Prob. 4.29.
Go through Ex. 4.4-2 on your own or in groups. If you just read it you think you get it but you dont.
Ask questions about each step, dont go on until you can answer it.
2-11

Problem 4.4-1: A Two-Unit Process.

A labeled flowchart of a continuous steady-state two-unit process is shown below. 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. First, fully label the chart and mark systems about which balances might be written.
2-12

Degree-of-freedom analysis:
Overall system:
Mixing point:
_______ Unknowns:
_______ Unknowns:
_______ Independent balances:
=
_______ Degrees of freedom
Unit 1:
Mixing point (after solving unit 1)
_______ Unknowns:
_______ Unknowns:
=
Therefore, we will solve the problem by:
2-13

Overall mass balance:
Overall balance of A:
Mass Balance on Unit 1:
Balance of A on Unit 1:
Mass balance on Mixing Point:
Balance of A on Stream Mixing Point:
2-14

Recycle & Bypass (Section 4.5).
Sell
100 kg B/min
10 kg A/min
200 kg A/min
100 kg A/min
100 kg B/min
Dump
90 kg A/min
Whats wrong with this picture? How would you redraw it to be more cost efficient and environmentally
conscious?
Notes:
Real reaction and real separation are always less than perfect. There is always some
unreacted raw material, and some unwanted material in the product.
Recycling is not free (requires pumping, pipes, etc.) but is only a one-time cost and usually
pays for itself quickly
Reasons to recycle:
o Recovering a catalyst
o Diluting a process stream
o Controlling a process variable
o Circulating a working fluid
o Increasing the overall percent conversion of a reaction
Sometimes a stream might bypass a process unit, where a fraction of the stream is diverted around the
unit and combined with the output stream. This allows us to vary the composition and properties of the
product stream. A stream that bypasses a unit introduces a splitting point in which a stream is split into
two streams.
2-15

Splitting point: A stream is split into two streams.
100 mol/s
0.70 mol A/mol
0.30 mol B/mol
60 mol/s
x1 (mol A/mol)
(1 x1 )(mol B/mol)
m 2 (mol/s)
x2 (mol A/mol)
(1 x2 )(mol B/mol)
Do a degree-of-freedom analysis:
Did you get 1 DOF? Wrong. If all were doing is splitting a stream, the compositions of the outlet
streams must be the same as that of the feed stream.
OK, so heres the revised flow chart.
100 mol/s
60 mol/s
0.70 mol A/mol

0.30 mol B/mol
0.70 mol A/mol

0.30 mol B/mol
m 2 (mol/s)
0.70 mol A/mol
0.30 mol B/mol
Before we do the formal D.F. analysis, how many degrees-of-freedom do we have?
Q: We know there should be 0. What went wrong?

A: We are only allowed 1 balance.
Q: Why?
A: Because # balances = # independent species, which A and B are not in this case. Try writing the
possible balances
Mass Balance:
A Balance:
B Balance:
2-16

Go through Example 4.5-1 on p. 110.

Note reasons for recycling on p. 112.
Go through Ex. 4.5-2. If you can do that without looking at solution, you can handle recycle
problems.
Further practice: Workbook problems 4.32, 4.36.
Example 4.5-2: An Evaporative Crystallization Process.

The flowchart of a steady-state process to recover crystalline potassium chromate (K2CrO4) from
an aqueous solution of this salt is shown below.
Forty-five hundred kilograms per hour of a solution that is one-third K2CrO4 by mass is joined
by a recycle stream containing 36.4% K2CrO4, and the combined stream is fed into an
evaporator. The concentrated stream leaving the evaporator contains 49.4% K2CrO4; this stream
is fed into a crystallizer in which it is cooled (causing crystals of K2CrO4 to come out of solution)
and then filtered. The filter cake consists of K2CrO4 crystals and a solution that contains 36.4%
K2CrO4 by mass; the crystals account for 95% of the total mass of the filter cake. The solution
that passes through the filter, also 36.4% K2CrO4, is the recycle stream.
1. 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)
2. Suppose that the filtrate were discarded instead of being recycled. Calculate the production
rate of crystals. What are the benefits and costs of the recycling?
Solution.
1. First, fully label the chart and mark systems about which balances might be written.
2-17

Degree-of-freedom analysis:
Overall system:
Recycle-fresh feed mixing point:
_______ Unknowns:
_______ Unknowns:
_______ Additional relations:
=
Evaporator:
Crystallizer/filter:
_______ Unknowns:
_______ Unknowns:
=
Therefore, we will solve the problem by:
2-18

Overall K2CrO4 balance:
Overall total mass balance:
95% specification:
Mass balance around crystallizer:
Water balance around crystallizer:
Mass balance around recycle-fresh feed mixing point:
2-19

4.6. Chemical Reaction Stoichiometry
Stoichiometry (4.6a) the proportions in which chemicals combine in reaction. Stoichiometric

equation:
2SO2 + O2 2SO3
2 mol SO3 generated

1 mol O2 consumed
,
, etc.
2 mol SO 2 consumed 2 mol SO2 consumed
The stoichiometric coefficients define conversion factors from moles of one species consumed or
formed in the reaction to moles of another species consumed or formed. For instant, if 50 mol/s of
SO3 are produced in the reaction
oxygen consumed
50 mol SO3 formed 1 mol O2 consumed

mol O 2 consumed
25
s
2 mol SO3 formed
s
Work through Test Yourself on p. 117.
Limiting and excess reactants (4.6b)
Feed reactants in stoichiometric proportion (e.g., 2 mol SO2/1 mol O2) all reactants run out at the
same time. What if theyre not in stoichiometric proportion?
2SO2 + O2 2SO3 (Sulfuric acid production, acid rain)
n1 (mol SO3/s)
n2 (mol SO2/s)
n3 (mol O2/s)
100 mol SO2/s

90 mol O2/s
Limiting reactant: reactant that runs out first, fed in less than stoichiometric proportion to all other
reactants. In example, SO2 limits. (Stoichiometric proportion = 2 SO2 : 1 O2, actual feed proportion =
10 SO2 : 9 O2)
Excess reactants: all other reactants but limiting one. In example, O2 is in excess.
Theoretical (stoichiometric) requirement of an excess reactant: How much would be required to react
completely with the limiting reactant.
Theoretical oxygen =
100 mol SO2 fed 1 mol O2

50 mol O 2 (theoretical)
s
2 mol SO2
Percent excess of a reactant: (Amount fed theoretical amount)/(theoretical amount) x 100%

%XS O2 =
90 mol O 2 50 mol O 2
100% 80% excess O 2 (=80%XS air if O2 comes from air)
50 mol O 2
2-20

Suppose you are told that oxygen is now fed in 60% excess (instead of at a rate of 90 mol/s). Then
(nO2 )fed (nO2 ) theoretical (nO2 )excess ( nO2 ) theoretical 0.60( nO2 ) theoretical
( nO2 ) theoretical (1 0.60) 1.60 (50 mol O 2 /s) 80 mol O 2 /s
% XS
or in general, if A is fed in excess, (n A )fed (n A ) theoretical 1
100
Note: The theoretical and excess quantities depend only on the feed amounts and the stoichiometric
reaction, not on what actually happens in the reactor.
Fractional conversion of a reactant:
moles reacted moles in moles out
mole fed
moles in
2SO2 + O2 2SO3
100 mol SO2/s

90 mol O2/s
SO2: fSO2
80(mol SO3/s)
20 mol SO2/s
50 mol O2/s
100 mol in/s 20 mol out/s

0.80 mol SO 2 react/mol fed
100 mol in/s
(Percentage conversion of SO2 =100 fSO2 = 80%)

O2: f O2
90 mol in/s 50 mol out/s

0.44 mol O 2 react/mol fed
90 mol in/s
(Percentage conversion of O2 =100 f O2 = 44%)
2-21

Exercise
N2 + 3H2 2NH3
n1 (mol N2)
n2 (mol H2)
n3 (mol NH3)
200 mol N2
300 mol H2
(a) The limiting reactant is ____________________________

(b) The percentage excess of the other reactant is ___________________________
(c) The theoretical amount of NH3 produced is
____________________________________________________
Now suppose the percentage conversion of nitrogen is 25%
(d) n1 = _____________________ , n2 = _____________________ , n3 = _________________
(e) The percentage conversion of hydrogen is ________________
2-22

Balances on Reactive Processes (4.7). There are three approaches:
1. Molecular species balances. Look again at the flow chart:

2SO2 + O2 2SO3
n1 (mol SO3/s)
n2 (mol SO2/s)
n3 (mol O2/s)
100 mol SO2/s

90 mol O2/s
We have three unknowns and three species ( 3 balances), so it looks like we should have zero
degrees of freedom. We dont, howeverno matter how hard you try, you cant calculate any of
those unknown variables without getting more information. Try using 0 = In-Out+Gen-Con
However, lets say we are now told that n2 = 20 mol SO2/s.

2SO2 + O2 2SO3
n1 (mol SO3/s)
20 mol SO2/s
n3 (mol O2/s)
100 mol SO2/s

90 mol O2/s
If molecular species balances are used (there are alternatives), then

DOF = #unknowns (2) #independent molecular balances (3) #other equations (0)
+ #independent reactions (1) = 0
Independent reactions (Section 4.7b). Chemical reactions are not independent if we can get one in
terms of the other by adding, subtracting, and multiplying them.
AB
2A 2B
(1)
(2)
(1) and (2) are not independent [ (2) = 2x(1)]
A 2B
BC
(1)
(2)
(1) and (2) are independent, but
A 2C
(3)
(1), (2), and (3) are not [(3) = (1) + 2x(2)]
2-23

SO 2 balance : I G O C A C I O 80
mol SO 2 consumed
s
SO 3 balance : I G O C A O G
n1
80 mol SO 2 consumed
___ mol SO3 generated
___ mol SO 2 consumed
_____
mol SO3
s
O 2 balance : I G O C A O I C
n3 90
mol O 2
s
80 mol SO 2 consumed
___ mol O 2 consumed
___ mol SO 2 consumed
50 mol O 2 / s
The original system must therefore have had ________ degree(s) of freedom.
2. Extent of reaction (p. 119)

For 2SO2 + O2 2SO3, if 10 mol SO3/s are formed, 10 mol SO2/s & 5 mol O2/s must react. Moles
formed & reacted are always proportional to stoichiometric coefficients.
mol SO 3 generated mol SO 2 consumed mol O 2 consumed
= (mol/s) (pronounced zi)
2
2
1
where (mol/s) is the extent of reaction (same for all species, must be positive). It follows that
(nSO2 )final (nSO2 )initial 2

(nO2 )final (nO2 )initial
(nSO3 )final (nSO3 )initial 2
For any single reaction,
ni nio i (Batch)
ni nio i (Continuous, steady - state)
(4.6-3)
where i is the stoichiometric coefficient of species i (+ for products, for reactants). One of these
equations may be written for every independent molecular species involved in the process. For
nonreactive species ( = 0), the equation reduces to ni nio ).
Q: What is ?
A. Its a dummy variable that reflects how far each reaction proceeds. It reflects the stoichiometry
of the reaction and helps us keep up with generation and consumption.
2SO2 + O2 2SO3
n1 (mol SO3/s)
20 mol SO2/s
n3 (mol O2/s)
100 mol SO2/s

90 mol O2/s
2-24

DOF = #unknowns (2) #extent of reaction equations (3) #other equations (0)
+ #independent reactions(1) = 0
Apply extent of reaction equation ( ni nio i ), starting with the species we know most about:
SO2: 20 mol/s = 100 mol/s 2 = 40 mol/s
O2: n3 = ___________________________________________= 50 mol O2/s
SO3: n1 = __________________________________________ = 80 mol SO3/s
3. Atomic species balances. Same process once more.

2SO2 + O2 2SO3
n1 (mol SO3/s)
20 mol SO2/s
n3 (mol O2/s)
100 mol SO2/s

90 mol O2/s
Instead of writing balances on the molecular species involved in the process (SO2, O2, SO3), lets do it
on the atomic species (S, O). Since atomic species are neither generated or consumed (except in
nuclear reactions, which we dont consider), all balances reduce to I = O.
With atomic species balances,
DOF = #unknowns (2) #independent atomic balances (2) #other equations (0)
S balance :
100 mol SO 2
___ mol S
1 mol SO 2
20 mol SO 2
___ mol S
1 mol SO 2
90 mol O 2
___ mol O
1 mol O 2
n1 (mol SO3 )
___ mol S
1 mol SO3
n1 80 mol SO3 / s
O balance :
100 mol SO 2
___ mol O
1 mol SO 2
n1 (mol SO3 )
___ mol O
1 mol SO3
+
n3 50 mol O 2 / s
Independent atomic species: If two atomic species are in the same ratio everywhere in the process,
they are not independent. Look at TY #1 on P. 128.
Q: How many independent atomic balances are there?
A: Two. Write balances on C and H and see what happens.
For more practice, do the Test Yourself on p. 119.
2-25

Summary: Balances on reactive systems
Three ways to write balances on reactive processes:

Form
Molecular
species
balances
Atomic species
balances
Extents of
reaction
#DF
(# unknowns on chart)
+ (# independent reactions)
(# independent molecular species balancesa)
(# other equations)
-- (# independent atomic species balancesb)
(# other equations)
+ [# independent reactions: (1 per reaction)]
(# independent species balancesa)
(# other equations)
If two molecular species are in the same ratio everywhere in the process
and the ratio is incorporated in the flowchart labeling, the species are not
independent
b
If two atomic species are in the same ratio everywhere in the process,
they are not independent
Which approach to use?
DOF: If youre confident about independence of atomic species, use the atomic species balance
approach, & if youre more confident about independence of reactions, use the extent of reaction
approach. Note that all DOF approaches should give the same answer, so if youre unsure, use
more than one to confirm.
Balances:
Dont use molecular species balances for reactive species (especially for multiple reactions
it gets hairy fast)
Hand calculationsatomic balances
Solver or chemical equilibriumextents of reaction. (Be sure reactions are independent)
Note: You can use one method for the DOF analysis & another for the calculations.
Work through Test Yourself on p. 134
Work through Example 4.7-1 on p. 131. If you fully understand the solution, you can solve any
single-unit reactive balance problem you are likely to encounter on homework and tests.
2-26

Chemical Equilibrium Calculations (Section 4.6c).
A + 2B C
If you are given an initial composition of a mixture of A, B, and C and an expression for the equilibrium
constant K(T), and you are told that the reaction proceeds to equilibrium at a final temperature T, you can
calculate the final composition using extents of reaction. See Example 4.6-2 for an illustration.
Multiple reactions (4.6d)
C2H6 C2H4 + H2
(Ethylene is the desired product, hydrogen is a byproduct)
C2H6 + H2 2CH4 (Methane is an undesired byproduct)

C2H4 + C2H6 C3H6 + CH4 (Propylene is an undesired byproduct)
The second and third reactions both consume ethylene and so are undesired. Sometimes byproducts
can be sold, and at other times they are worthless and possibly hazardous and have to be disposed of
(another cost).
Yield = mole of desired product / [moles that would have been formed if there were no side reactions
and the reaction went to completion (the limited reactant was completely consumed)]
Selectivity = moles of desired product / moles of undesired product

(note, selectivity always refers to selectivity of desired A with respect to undesired B)
If yield and selectivity are high, then we have successfully suppressed the undesired reactions.
Note: in the ethylene example, H2 is not an undesired byproduct. An undesired byproduct is the
result of a competing reaction that results in less of the desired product.
A 2B + C
BD
B: Desired product, D: Unwanted byproduct
20 mol A
120 mol B
80 mol C
40 mol D
100 mol A
Maximum possible B produced = _______ mol (All A fed reacts, no side reaction)
Yield (Eq. 4.6-4): YB = _____________________
Selectivity B/D (Eq. 4.6-5): SBD = _____________________________________
A process engineer might take two different approaches to this reaction system:
Maximize yield: Get most B you can, even if it means producing more D.
Maximize selectivity: Hold down production of D, even if it means producing less B.
Q: Why would you want to suppress production of a byproduct if it means getting less of the product
youre selling? (Think of several possible reasons.)
A:
2-27

Extents of reaction for systems with multiple reactions
Batch:
ni ni 0
ij
[ j (mol), i=species, j=independent reactions]
ij
[ j (mol/s), i=species, j=independent reactions]
Cont., St.State: ni ni 0
(4.6-6)
Recall is positive for products, negative for reactants, and ZERO for inerts (N2, etc.) that go
through the process without reacting.
Example:
A 2B + C
BD
[Rxn 1]
[Rxn 2]
A1 = 1, B1 = +2, C1 = +1
B2 = 1, D2 = +1
(All others = 0)
n A
n B
n C
n D
100 mol A/s

20 mol B/s
10 mol I/s
(mol A/s)
(mol B/s)
(mol C/s)
(mol D/s)
nI (mol I/s)
n A 100 1 ,
nB ____________________, nC ____________________
nD ____________________,
nI ____________________
DOF: 5 unknowns ( n A , n B , nC , n D , n I ) 5 equations + 2 reactions = 2 DOF.

Specify any 2 of the 7 variable values, fractional conversion of A, yield of B, or selectivity of
B/D, & calculate the others. (Write equations, solve with Excel Solver.)
2-28

Product Separation and Recycle (Section 4.7f)
Talk through flowchart on p. 135

Identify fresh feed, recycle, feed to the reactor
What is the percentage conversion of A?
Depends on the definition of conversion:
Single pass conversion: based on what goes into and comes out of the reactor. In this case
it is 75%.
A fed to reactor A leaving reactor
Single-pass conversion of A =
A fed to reactor
=
Overall conversion: Based on what comes in and out of the overall process.
Overall conversion of A =
A fed to process A leaving process

A fed to process
=
We must specify whether a given conversion is overall or single-pass.
Do Test Yourself on p. 135. Work through Example 4.7-2.
Note: only 10% of the propane entering the reactor is converted to propylene in a single pass.
99% of the unconsumed propane is recovered in the separation unit and recycled back, where it
gets another chance to react. Net result = 95% of propane entering the process is converted to
propylene and 5% leaves with final product.
To achieve high conversion:

1. Design the reactor to achieve a high single-pass conversion
o Requires very large residence time in reactor, large reactor volume, expensive
2. Design the reactor to achieve a low single-pass conversion, follow with a separation unit to
recover and recycle unconsumed reactant.
Decreased reactor cost
Incur cost of separation process and cost of recycle line
2-29

(b) Purge
Inert gases (e.g. nitrogen, argon) are used in processes because they undergo chemical reactions
under given conditions
Using an inert gas in a system prevents undesirable chemical reactions from occurring (e.g. oxidation,
hydrolysis, combustion)
Purging with nitrogen minimizes fire hazards of residual solvents or process fluids
If an inert gas is introduced to the system and it doesnt react, it has to exit the system somewhere
otherwise, it builds up and would shut down the process
Look at Fig. 4.7-2 on p. 138production of ethylene oxide from ethylene. N2 is an inert. How did it
get in the process?
Purge stream: note it also contains ethylene and O2. Why are we throwing away product and
reactant?
Note there is a cost to discard. But there is also a cost to separate and recycle the last little bit. Gas
separation is hard and expensive. Engineers must evaluate the options based on economics,
environmental regulations, etc. Note that purge stream take-off is a splitter (we can only write one
balance one equation in the DOF).
Work through Example 4.7-3. If you understand Example 4.7-3, you know how to do recycle
problems, which are the hardest problems to solve. The key is flowcharting & systematic DOF
analysis.
General Strategies and Tips for Problem Solving
1. Break the problem down into small sub-problems when possible.

2. Even if the DOF analysis is not asked for, do it. Thats your roadmap and confirmation that the
problem is solvable. (5 minutes on the DOF analysis can save hours of trying to solve an
impossible problem.)
3. For multiple unit processes or system with split, mix, recycle, purge, etc., do DOF for each
subprocess. 10 equations and 10 unknowns for the entire process is literally correct, but if it
doesnt converge you dont have a clue as to where to start looking for the error.
4. Use standard nomenclature: m for mass, n for moles, and x or y for composition. Avoid A-F, all
Xi, all Mi. Someone may have to decipher your solution later. You may have to decipher it later.
Save your creativity for solving the problem, not labeling it.
5. Clearly label your equations and the basis for the DOF analysis. This helps remind you and
anyone checking your work what you have done.
6. Reality check: negative flowrates, negative compositions are a signal. Very small or very large
numbers relative to others are also suspicious.
7. Always show complete units on the flowsheet and in calculations.
2-30

Combustion Processes (Section 4.8)
Combustion: Rapid reaction of a fuel with oxygen (usually but not always in air)
Complete combustion: All C in fuel forms CO2, all H forms H2O, all S forms SO2
Partial combustion: Some C forms CO
Air: Actual composition given on p. 143. For most of our purposes, assume 21.0 mole% O2, 79.0% N2
3.76 mol N2/mol O2 , 4.76 mol air/mol O2.
Percent excess oxygen (= percent excess air): Based on complete combustion of fuel, regardless of
whether all fuel actually reacts and whether some CO is formed.
Wet-basis and dry-basis product gas compositions: Mole fractions of components with water included
and not included, respectively.
Example
100 mol CH4/s
1190 mol air/s

0.21 mol O2/mol
0.79 mol N2/mol
20
95
940
70
10
160
mol CH4/s
mol O2/s
mol N2/s
mol CO2/s
mol CO/s
mol H2O/s
Q: Is the flow chart balanced?

A: Yes. (C: 100 = 20 + 70 + 10; H: 400 = 80 + 320; O: 500 = 190 + 140 + 10 + 160: N2: 940 = 940)
Q: What reaction(s) are taking place?
7
2
A1: 2CH4 +
O2 CO + CO2 + 4H2O
WRONG! If that really were the reaction, what would the ratio of CO to CO2 in the product be?
A2:
CH4 + 2O2 CO2 + 2H2O

CH4 +
3
2
O2 CO + 2H2O
Q: What is the percent excess air fed to the reactor?

A: CH4 + 2O2 CO2 + 2H2O
Theoretical air
%XS air
100 mol CH 4 2 mol O 2

s
1 mol CH 4
4.76 mol air

mol air
952
1 mol O 2
s
1190 mol fed/s 952 mol required/s

100% 25% excess air
952 mol required/s
2-31

Q: What about the fact that not all the methane reacted and some CO was formed?
A: Doesnt matterby definition, the percent excess air is based on complete combustion.
Q: What are the wet-basis and dry-basis compositions of the product gas?
A: Wet: (20+95+940+70+10+160) = 1295 mol/s, xCH 4
Dry: (20+95+940+70+10) = 1135 mol/s, xCH 4
20 mol CH 4 / s
mol CH 4
, etc.
0.0154
1295 mol/s
mol
20 mol CH 4 / s
mol CH 4
, etc.
0.0176
1135 mol/s
mol
Do Test Yourself on p. 146
Most material balance problems on combustion reactors are no different from those on any other
reactor. Go through Example 4.8-3 for an illustration.
Sometimes composition of fuel may be unknown, but if you know the atomic constituents of the fuel
you can determine their ratio. Example 4.8-4 illustrates such a computation.
Read Section 4.9. It outlines the differences between this course and the real world.
2-32

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CHE 205 Chemical Process Principles

Section 2: F&R, Chapter 4

Writing and solving equations

2000 L/h (S.G.=0.872)

m B 3 (kg B/h) (8% of B in feed)

Figure 1. Flow Chart of a Distillation Process

CHE 205 Chemical Process Principles

Batch process: Add contents, then remove them later

Continuous process: Continuously add then remove contents

Steady state process: Process variables (flowrates, T, P) are constant

Transient process: Process variables change with time

Continuous process at steady state: A = 0

CHE 205 Chemical Process Principles

Drawing and labeling flow charts

Is this stream completely labeled? (Hint: No!) Why not?

CHE 205 Chemical Process Principles

Exercise: Prove that this stream is

For practice, do Test Yourself on p. 93.

CHE 205 Chemical Process Principles

0.015 mol H2O(v)/mol

20.0 cm3 H2O(l)/min

CHE 205 Chemical Process Principles

Degree-of-Freedom Analysis and Solution Strategy

unknowns (the number of unknown variables on the flow chart)

CHE 205 Chemical Process Principles

CHE 205 Chemical Process Principles

0.21 mol O2/mol

0.79 mol N 2 / mol air

CHE 205 Chemical Process Principles

2000 L/h (S.G.=0.872)

m B 3 (kg B/h) (8% of B in feed)

Degree-of-freedom analysis (count only variables labeled on the chart):

All unknowns can be calculated

Benzene balance: ________________________________________________

CHE 205 Chemical Process Principles

Scale Factor (SF) =

CHE 205 Chemical Process Principles

Go through Ex. 4.4-1.

Work through Prob. 4.29.

CHE 205 Chemical Process Principles

Problem 4.4-1: A Two-Unit Process.

Calculate the unknown flow rates and compositions of streams 1, 2 and 3.

CHE 205 Chemical Process Principles

_______ Independent balances:

_______ Independent balances:

_______ Degrees of freedom

Mixing point (after solving unit 1)

_______ Independent balances:

_______ Independent balances:

_______ Degrees of freedom

Therefore, we will solve the problem by:

CHE 205 Chemical Process Principles

Overall mass balance:

Mass Balance on Unit 1:

Mass balance on Mixing Point:

Balance of A on Stream Mixing Point:

CHE 205 Chemical Process Principles

CHE 205 Chemical Process Principles

0.70 mol A/mol

0.70 mol A/mol

Before we do the formal D.F. analysis, how many degrees-of-freedom do we have?

Q: We know there should be 0. What went wrong?

CHE 205 Chemical Process Principles

Go through Example 4.5-1 on p. 110.