CHE 205 Chemical Process Principles

Section 2: EPCP, Chapter 4

2-1
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey
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 Writing and solving equations
Problem-solving time early in
Chapter 4
Slightly faster
Problem-solving time, most of
Ch. 4 and Ch. 59
Slower, then much slower, than
may never get the solution
Course grade 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:















2000 L/h (S.G.=0.872)
1
(kg/h) m
0.45 kg B/kg
0.55 kg T/kg
2
(kg/h) m
0.95 kg B/kg
0.05 kg T/kg
3
3
(kg B/h) (8% of B in feed)
(kg T/h)
B
T
m
m

Distillation
Column
Figure 1. Flow Chart of a Distillation Process
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-2
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

We will refer back to Figure 1 throughout this handout.

Balance equation

We can write a balance on any quantity entering or leaving a system mass, moles, energy, people:

(a) I + G O C = A (4.2-1)

Input + Generation Output Consumption = Accumulation
What What is What What is Change in amount
comes produced leaves consumed contained in the system
in across within the across within the
system system system system
boundary (reaction) boundary (reaction)

Simplifications

- Continuous process at steady state: A =0
- Nonreactive system, or balance on nonreactive species: G =0, C =0
- Batch process: I =0 or O =0, A =Final output initial input

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.
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-3
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

For example, a continuous stream of natural gas containing 85 wt% methane and the balance ethane
might be labeled as:



Is this stream completely labeled? (Hint: No!) Why not?
__________________________________________________________________________
Suppose we let m (kg/s) denote the unknown mass flow rate of the stream. The labeling would then be



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:
4
4
(kg CH /s) =_____________________
CH
m
Ethane flow rate:
2 6
2 6
(kg C H /s) =_____________________
C H
m
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).



Once you have one, you can always calculate the other:
In terms of m, x
1
, and x
2
, m
1
=_____________________________
In terms of m
1
, m
2
, and m
3
, m =_______________ and x
1
=__________________________
- 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% O
2
, 79%
N
2
) flows at a rate of 125 mol/s. The stream might be labeled





0.85 kg CH
4
/kg
0.15 kg C
2
H
6
/kg
(kg/s) m
0.85 kg CH
4
/kg
0.15 kg C
2
H
6
/kg
1 1
2 2
1 2 2 3 2
(kg)
(kg NaCl/kg) OR (kg NaCl)
(kg KCl/kg) (kgKCl)
(1 )(kg H O/kg) (kg H O)
m
x m
x m
x x m

2
2
2
125 mol/s
(mol SO / mol)
(1 )(mol air/ mol)
0.210 mol O /mol air
0.790 mol N /mol air
x
x
Exercise: Prove that this stream is
completely labeled.
Solution:
2
SO 2
(mol SO /s) ___________________
__________________________________
__________________________________
n =

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-4
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- 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.

Exercise: Enriching Air with O
2
.

A stream of air (21.0 mole% O
2
, 79.0% N
2
), a stream of pure oxygen, and a stream of liquid water
flowing at a rate of 20.0 cm
3
/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.











- Completely label the flow chart (including the molar flow rate of the liquid water stream),
following the rules given above.












- 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 should be
specified before any calculations are done. If the problem statement doesnt do it, you choose a
convenient basis (an amount of a stream with known composition.)



Evaporator
0.21 mol O
2
/mol
0.79 mol N
2
/mol
20.0 cm
3
H
2
O(l)/min
0.015 mol H
2
O(v)/mol

Evaporator
O
2
(g)
Air
0.21 mol O
2
/mol
0.79 mol N
2
/mol
20.0 cm
3
H
2
O(l)/min
0.015 mol H
2
O(v)/mol
20% of air flow rate
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-5
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

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 (=m
1
/m
2
in the flow chart)?







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 (m
1
=100 g):








We could then write balance equations on ethanol and water, solve for m
1
and m
2
, and determine the
requested ratio as m
2
/100. The same result would be obtained if we chose any other basis of calculation:
the values of m
1
and m
2
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:

______ 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)
= DF 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.

In this course, dont start writing equations until you have zero degrees of freedom.
- For a non-reactive process, the number of independent material balance equations equals the number
of independent species involved in the process.

Mixer
m
1
(g)
0.30 g E/g
0.70 g W/g
m
2
(g)
0.60 g E/g
0.40 g W/g
m
3
(g)
0.35 g E/g
0.65 g W/g

Mixer
100 g
0.30 g E/g
0.70 g W/g
m
2
(g)
0.60 g E/g
0.40 g W/g
m
3
(g)
0.35 g E/g
0.65 g W/g
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-6
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)


Example. Reconsider the earlier distillation process. The basis of calculation is 2000 L/h of the feed
stream (exact, not 1 significant figure). Suppose we are asked to calculate the mass fraction of benzene in
the bottom product and the ratio (kg overhead product/kg feed).










In terms of the labeled quantities, the quantities requested in the problem statement are





Degree-of-freedom analysis (count only variables labeled on the chart, not x
B
and R
OF
):

__ 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:
1 1
2000 L _____________ kg
(kg/h) (2000)(0.872)
h L
m m = = (1)
8%:
3
_____________________
B
m = (2)
Mass balance:
1 2 3 3 B T
m m m m = + + (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 Solver to determine the three unknown quantities.
2000 L/h (S.G.=0.872)
1
(kg/h) m
0.45 kg B/kg
0.55 kg T/kg
2
(kg/h) m
0.95 kg B/kg
0.05 kg T/kg
3
3
(kg B/h) (8% of B in feed)
(kg T/h)
B
T
m
m

Distillation
Column
kg B
Mass fraction of benzene in bottom product:
kg
Mass ratio of overhead product to feed:
B
OF
x
R
| |
=
|
\ .
=

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-7
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Equations:
m1 =2000*0.872
mB3 =0.08*m1*0.45
m1 =m2 +mB3 +mT3
m1*0.45 =m2*0.95 +mB3


Scale the flow chart: Now suppose we are asked to calculate the volumetric feed rate needed to produce
2500 lb
m
/day of overhead product. The scale factor (see Example 4.3-2) is the desired value of the
specified quantity (overhead product rate =2500 lb
m
/day) divided by the value of the same quantity
corresponding to the original basis of calculation (=760 kg/h).


m m
3 m m
1 1
2500 lb /day lb /day
Scale Factor (SF) = 3.29
760 kg/h kg/h
lb /day lb feed kg
( ) ( ) 1744 3.29 5.74 10
h kg/h day
new old
m m SF
=
| |
| |
= = =
| |
\ .
\ .



- Work through Instructional Tutorial #2 on the CD.
- Work through Problem 4.11 in the Student Workbook. Follow every step. Fill in the blanks yourself,
then check the solutions.

1 2 3 3
3 2
3 3 1
kg kg kg B kg T
1744 , 760 , ,
h h h h
kg B kg overhead
=0.0638
kg kg feed
=62.8 =921
, 0.436
B
B T
B
OF
B T
m m
x
m m
m m
R
m m m
= =
= = =
+




CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-8
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

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.

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
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-9
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Splitting Point. A stream containing two species is split into two streams.
1
1
100 mol/s 60 mol/s
0.70 mol A/mol (mol A/mol)
0.30 mol B/mol (1 )(mol B/mol)

x
x
2
2
2
(mol/s)
(mol A/mol)
(1 )(mol B/mol)


m
x
x

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 0.70 mol A/mol
0.30 mol B/mol 0.30 mol B/mol

2
(mol/s)
0.70 mol A/mol
0.30 mol B/mol


m


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 (have them do it & see what happens)

2
2 2
2 2
Mass balance:100 60
A balance:100(0.70) 60(0.70) (0.70) 100 60
B balance:100(0.30) 60(0.30) (0.30) 100 60
m
m m
m m
= +
= + = +
= + = +

(Same equation)

- Go through Example 4.5-1 on p. 110.
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-10
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- 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.

- 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.






Looks like 3 unknowns 3 equations (balances on CH
4
, O
2
, N
2
) =0 D.F., but it wont work. Write
balances on O
2
& N
2
& see what happens.
O
2
balance:
N
2
balance:
- Stoichiometry (4.6a) the proportions in which chemicals combine in reaction. Stoichiometric
equation:
2SO
2
+O
2
2SO
3

3 2
2 2
2 mol SO generated 1 mol O consumed
, , etc.
2 mol SO consumed 2 mol SO 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
SO
3
are produced in the reaction

2
3 2
2
O
3
50 mol SO formed 1 mol O consumed
mol O consumed
( ) 25
s 2 mol SO formed
s
consumed
n = =
Work through Test Yourself on p. 117.
- Limiting and excess reactants (4.6b)
Feed reactants in stoichiometric proportion (e.g., 2 mol SO
2
/1 mol O
2
) all reactants run out at the
same time. What if theyre not in stoichiometric proportion?


100 mol SO
2
/s
1
n (mol SO
3
/s)
90 mol O
2
/s
2
n (mol SO
2
/s)

3
n (mol SO
2
/s)
2SO
2
+O
2
2SO
3
(Sulfuric acid production, acid rain)

Gas blender
100 mol CH
4
/s
1
(mol air/s) n
0.21 mol O
2
/mol
0.79 mol N
2
/mol
2
1 4
1
2
2
(mol/s)
(mol CH /mol)
(1 )(mol air/mol)
0.21 mol O /mol air

0.79 mol N /mol air
n
x
x

`
)

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-11
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)


Limiting reactant: reactant that runs out first, fed in less than stoichiometric proportion to all other
reactants. In example, SO
2
limits. (Stoichiometric proportion =2 SO
2
: 1 O
2
, actual feed proportion =
10 SO
2
: 9 O
2
)
Excess reactants: all other reactants but limiting one. In example, O
2
is in excess.
Theoretical (stoichiometric) requirement of an excess reactant: How much would be required to react
completely with the limiting reactant.
Theoretical oxygen =
2 2
2
2
100 mol SO fed 1 mol O
50 mol O (theoretical)
s 2 mol SO
=
Percent excess of a reactant: (Amount fed theoretical amount)/(theoretical amount) x 100%
%XS O
2
=
2 2
2
2
90 mol O 50 mol O
100% 80% excess O
50 mol O

= (=80%XS air if O
2
comes from air)
Suppose you are told that oxygen is now fed in 60% excess (instead of at a rate of 90 mol/s). Then
2 2 2 2 2
2
O fed O theoretical O excess O theoretical O theoretical
O theoretical 2 2
( ) ( ) ( ) ( ) 0.60( )
( ) (1 0.60) 1.60 (50 mol O /s) 80mol O /s
n n n n n
n
= + = +
= + = =

or in general, if A is fed in excess,
fed theoretical
%
( ) ( ) 1
100
A A
XS
n n
| |
= +
|
\ .


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

=



100 mol SO
2
/s 80(mol SO
3
/s)
90 mol O
2
/s 20 mol SO
2
/s
50 mol O
2
/s

SO
2
:
2
SO 2
100 mol in/s 20 mol out/s
0.80 mol SO react/mol fed
100 mol in/s
f

= =
(Percentage conversion of SO
2
=100
2
SO
f =80%)
O
2
:
2
O 2
90 mol in/s 50 mol out/s
0.44 mol O react/mol fed
90 mol in/s
f

= =
(Percentage conversion of O
2
=100
2
O
f =44%)
2SO
2
+O
2
2SO
3

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-12
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Exercise





(a) The limiting reactant is ____________________________
(b) The percentage excess of the other reactant is __________________________________
(c) The theoretical amount of NH
3
produced is _______________________________________
Now suppose the percentage conversion of nitrogen is 25%
(d) (d) n
1
=______________________ , n
2
=____________________________ , n
3
=_________
(e) The percentage conversion of hydrogen is ________________
(f) The reactor had _____ degrees of freedom after the conversion of nitrogen was specified



200 mol N
2

300 mol H
2
n
1
(mol N
2
)
n
2
(mol H
2
)
n
3
(mol NH
3
)
N
2
+3H
2
2NH
3

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-13
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Balances on Reactive Processes (4.7)
- Molecular species balances. Look again at the flow chart:


100 mol SO
2
/s
1
n (mol SO
3
/s)
90 mol O
2
/s
2
n (mol SO
2
/s)

3
n (mol O
2
/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.
However, lets say we are now told that
2
n =20 mol SO
2
/s.


100 mol SO
2
/s
1
n (mol SO
3
/s)
90 mol O
2
/s 20 mol SO
2
/s

3
n (mol O
2
/s)
If molecular species balances are used (there are alternatives), then
DOF =#unknowns #independent molecular balances #other equations +#independent reactions

For this case:
2 unknowns 3 indep. molecular balances 0 other equations +1 independent rxn =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.

A B (1)
2A 2B (2) (1) and (2) are not independent [ (2) =2x(1)]

A 2B (1)
B C (2) (1) and (2) are independent, but
A 2C (3) (1), (2), and (3) are not [(3) =(1) +2x(2)]
2SO
2
+O
2
2SO
3

2SO
2
+O
2
2SO
3

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-14
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)


2
2
3
3
2
2 3
1
2
_____
mol SO consumed
SO balance: 80
s
SO balance:
80 mol SO ___ mol SO generated
mol SO

s ___ mol SO consumed
s
O balance:

consumed

I G O C A C I O
I G O C A O G
n
I G O C A O I C
+ = = =
+ = =
=
+ = =
=
2
2 2
3 2
2
80 mol SO consumed ___ mol O consumed
mol O
90 50 mol O
s ___ mol SO consumed
s

/

n s = =

The original system must therefore have had ________ degree(s) of freedom.

- Atomic species balances. Same process once more.


100 mol SO
2
/s
1
n (mol SO
3
/s)
90 mol O
2
/s 20 mol SO
2
/s

3
n (mol O
2
/s)
Instead of writing balances on the molecular species involved in the process (SO
2
, O
2
, SO
3
), 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)
2 2 1 3
2 2 3
1 3
2 2
2
100 mol SO ___ mol S 20 mol SO ___ mol S (mol SO ) ___ mol S
S balance:
s 1 mol SO s 1 mol SO s 1 mol SO
80 mol SO /s
100 mol SO ___ mol O 90 mol O ___ mol O
O balance:
s 1 mol SO
n
n
= +
=
+

1 3
2 3
(mol SO ) ___ mol O
=
s 1 mol O s 1 mol SO


+
n
+

3 2
50 mol O / s n =

- 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.
2SO
2
+O
2
2SO
3

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-15
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

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.
- Extent of reaction (p. 119)
For 2SO
2
+O
2
2SO
3
, if 10 mol SO
3
/s are formed, 10 mol SO
2
/s & 5 mol O
2
/s must react. Moles
formed & reacted are always proportional to stoichiometric coefficients.

mol SO generated
2
mol SO consumed
2
mol O consumed
1
3 2 2
= = = (mol/s)

(pronounced zi)
where (mol/s)

is the extent of reaction (same for all species, must be positive). It follows that

2 2
2 2
3 3
SO final SO initial
O final O initial
SO final SO initial
( ) ( ) 2
( ) ( )
( ) ( ) 2
n n
n n
n n

=
=
= +

For any single reaction,

n n
n n
i io i
i io i
= +
= +
v
v
(Batch)
(Continuous, steady- state)


where v
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 (v =0), the equation reduces to
i io
n n = ).

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.

2SO
2
+O
2
2SO
3


100 mol SO
2
/s
1
n (mol SO
3
/s)
90 mol O
2
/s 20 mol SO
2
/s

3
n (mol O
2
/s)

DOF =#unknowns (2) #extent of reaction equations (3) #other equations (0)
+#independent reactions(1) =0


Apply extent of reaction equation (
i io i
n n v = +

), starting with the species we know most about:
(4.6-3)
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-16
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

SO
2
: 20 mol/s =100 mol/s 2

=40 mol/s
O
2
:
3
n =___________________________________________=50 mol O
2
/s
SO
3
:
1
n =__________________________________________ =80 mol SO
3
/s


Chemical Equilibrium Calculations (Section 4.6c).
A +2 B 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)
C
2
H
6
C
2
H
4
+H
2
(Ethylene is the desired product, hydrogen is a byproduct)
C
2
H
6
+H
2
2CH
4
(Methane is an undesired byproduct)
C
2
H
4
+C
2
H
6
C
3
H
6
+CH
4
(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, H
2
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
B D
B: Desired product, D: Unwanted byproduct
20 mol A
100 mol A 120 mol B
80 mol C
40 mol D

Maximum possible B produced =_______ mol (All A fed reacts, no side reaction)
Yield (Eq. 4.6-4): Y
B
=_____________________________________
Selectivity B/D (Eq. 4.6-5): S
BD
=_____________________________________

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-17
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- 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:


Extents of reaction for systems with multiple reactions
0
0
Batch: [ (mol), i=species, j=independent reactions]
Cont., St.State: [ (mol/s), i=species, j=independent reactions]
i i ij j j
j
i i ij j j
j
n n
n n
v
v
= +
= +

(4.6-6)
Recall v is positive for products, negative for reactants, and ZERO for inerts (N
2
, etc.) that go
through the process without reacting.


Example:
A 2B +C [Rxn 1] v
A1
=1, v
B1
=+2, v
C1
=+1
B D [Rxn 2] v
B2
=1, v
D2
=+1 (All others =0)

100 mol A/s n
A
(mol A/s)
20 mol B/s n
B
(mol B/s)
10 mol I/s n
C
(mol C/s)
n
D
(mol D/s)

I
n (mol I/s)
1
100 , __________________________, ____________________
____________________, ____________________
A B C
D I
n n n
n n
= = =
= =

DOF: 5 unknowns ( , , , ,
A B C D I
n n n n n ) 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 EZ-Solve.)
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-18
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Summary: Balances on reactive systems
- Three ways to write balances on reactive processes:
Form #DF
Molecular
species
balances
(#unknowns on chart)
+(#independent reactions)
(#independent molecular species balances
a
)
(#other equations)
Atomic species
balances
(#unknowns on chart)
-- (#independent atomic species balances
b
)
(#other equations)
Extents of
reaction
(#unknowns on chart)
+[#independent reactions: (1 per reaction)]
(#independent species balances
a
)
(#other equations)

a
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. (To be on the safe side, use both.)
- Balances:
Dont use molecular species balances for reactive species (because it is complex)
Hand calculationsatomic balances
E-Z solve or chemical equilibriumextents of reaction. (Be sure reactions are independent)
- Note: You can use one method for the DOF analysis & another for the calculations.

CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-19
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

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 for composition. Avoid A-F, all X
i
,
all M
i
. 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.
- 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.
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.
A fed to process A leaving process
Overall conversion of A =
A fed to process
=

We must specify whether a given conversion is overall or single-pass.




CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-20
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

- 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
(b) Purge
- Look at Fig. 4.7-2 on p. 138production of ethylene oxide from ethylene. N
2
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 (one equation only in
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 in CHE 205. The key is flowcharting & systematic DOF
analysis.


CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-21
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

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 CO
2
, all H forms H
2
O, all S forms SO
2

Partial combustion: Some C forms CO
Air: Actual composition given on p. 143. For most of our purposes, assume 21.0 mole% O
2
, 79.0% N
2

3.76 mol N
2
/mol O
2
, 4.76 mol air/mol O
2
.
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







Q: Is the flow chart balanced?


Q: What reaction(s) are taking place?



Q: What is the percent excess air fed to the reactor?







100 mol CH
4
/s
1190 mol air/s
0.21 mol O
2
/mol
0.79 mol N
2
/mol
20 mol CH
4
/s
95 mol O
2
/s
940 mol N
2
/s
70 mol CO
2
/s
10 mol CO/s
160 mol H
2
O/s
CHE 205 Chemical Process Principles
Section 2: EPCP, Chapter 4

2-22
Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2009)

Q: What about the fact that not all the methane reacted and some CO was formed?


Q: What are the wet-basis and dry-basis compositions of the product gas?






- 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. A question on
the next test will be related to the list in Part 2 of the solution.