4 Material Balances

Fundamentals of
Material Balances
Ch E 201
Material and Energy Balances
Objectives
Classify processes as batch, semibatch, continuous,
transient, and steady-state.
Define: recycle, purge, degrees of freedom, fractional
conversion of a limiting reactant, percentage excess
of a reactant, yield, selectivity.
Draw and label process flowcharts.
Select a calculation basis.
Perform a degree of freedom analysis.
Define/solve equations to calculate process variables.
Perform combustion calculations.
Process Classification
Batch process
No mass crosses system boundaries between the time
feed is charged and the time product is removed.
Typically used for making small quantities, particularly
those products of sparatic manufacture.
Continuous process
Feeds and effluents continously flow across the system
boundary through the duration of the process.
Suited for the production of large quantities.
Semibatch process
Any process that is neither batch nor continuous.
Process Operation
Steady state
There is no change in the value of all process variables
(temperature, pressure, flowrates, heat-transfer rates)
except for minor flucctuations about the mean value.
Continuous processes may be steady-state.
Transient (Unsteady-State)
The values of process variables change with time.
Batch and semibatch process are transient by nature.
Continuous processes may be transient.
Process Operation
Pseudo Steady State
A transient process for which the rate of change of
particular process variables is small may be considered to
operate at close to a steady state over short time periods.
Classification is assumed in the development
mathematical relationships that permit the design or
describe the performance of unit operations that involve
fundamental phenomena such as heat or mass transfer,
heterogeneous catalysis, phase equilibrium, etc.
Classify this!
Filling an empty swimming pool with water.
Leave the milk on the counter.
Cook pasta in boiling water in a dutch oven.
Filling a full swimming pool with water.
Drinking beer at a party all night on a Friday.
Baking a pizza.
Operation of a photovoltaic cell.
Other examples?
The General Balance Equation
Consider the following continuous process unit for
which methane is a component of both the input
and output, but the measured methane inlet and
outlet mass flowrates are not the same.

Maybe methane is
consumed as a reactant, or generated as a product within
the process unit; or
accumulating within or leaking from the unit; or
the measurements are wrong (though we will assume they
are correct).
A balance of a conserved quantity (mass, energy,
momentum) in a system may be written generally as:

input + generation output consumption = accumulation

input: enters through system boundaries
generation: produced within the system
ouput: leaves through system boundaries
consumption: consumed within the system
accumulation: buildup within the system
Each year, 50,000 people move into a city; 75,000
move out; 22,000 are born; 19,000 die. Perform a
balance on the population of the city (system).

input: 50,000 people/year
generation: 22,000 people/year
ouput: 75,000 people/year
consumption: 19,000 people/year
accumulation: unknown
Each year, 50,000 people move into a city; 75,000
move out; 22,000 are born; 19,000 die. Perform a
balance on the population of the city (system).

50,000 P/yr + 22,000 P/yr - 75,000 P/yr - 19,000 P/yr = A

A = -22,000 P/yr

the citys (system) population is decreasing by 22,000
people each year.
Balance Types
Differential balances
Indicate state of various rates occuring in a system at an
instant in time. Typically applied to a continuous process.

Integral balances
indicate total amounts of a balanced quantity between
two instants of time. Typical applied to a batch process.
Rules of MB simplification
If the balanced 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
Continuous steady-state system

input + generation = output + consumption

If the balance is for a nonreactive species or on total
mass, the generation and consumption terms equal
zero, and the balance reduces as

input = output

0
Benzene/Toluene distillation
continuous process
steady-state operation
no reactions occurring

General species balance


input = output
0 0 0
input = output
Benzene balance
500 kg B/h = 450 kg B/h + m
2
m
2
= 50 kg B/h
Toluene balance
500 kg T/h = m
1
+ 475 kg T/h
m
1
= 25 kg T/h
Total mass balance
1000 = 450 + m
1
+ m
2
+ 475 (all with units of kg/h)
1000 kg/h = 1000 kg/h
Integral Balances on Batch Processes
consider the reaction N
2
+ H
2
NH
3
in a batch reactor
at t=0, there is n
0
moles of NH
3
in the reactor
at t=t
f
, there is n
f
moles of NH
3
in the reactor
between 0 and t
f
, no NH
3
crosses system boundary
NH
3
accumulation in system from 0 to t
f
is n
f
n
0
.
therefore, for a batch process,
accumulation = final output initial input
= generation consumption
initial input + generation = final output + consumption
Identical to continuous steady-state balance except in/out terms
denote discrete amounts instead of flow rates
Batch Mixing Process Balance
Two methanol-water
mixtures are contained
in flasks of amounts and
concentrations shown.
If the flasks are mixed, what is the mass and
concentration of the resulting product?
no reactions, generation = consumption = 0
input = output
Batch Mixing Process Balance
Total Mass Balance
200 g + 150 g = m = 350 g
Methanol balance

Water balance
200(0.6) + 150(0.3) = 350(1-0.529)
165 g H
2
O = 165 g H
2
O
( )
( )
g
OH CH g
529 . 0 x
g
OH CH g x
g m
g
OH CH g 700 . 0
g 150
g
OH CH g 400 . 0
g 200
3
3 3 3
=
= +
Integral Balances on
Semibatch and Continous Processes

Air is bubbled through a drum of liquid hexane.
Gas stream leaving contains air and hexane.
How long does it take to vaporize 10.0 m
3
of liquid?


differential air balance

min
kmol
111 . 0 n
min
kmol
n
kmol
ir a mol k 900 . 0
min
ir a mol k
100 . 0
output input
=
=
=

integral hexane balance

( )
min 6880 t
t 111 . 0 100 . 0 nt 100 . 0 output
H C kmol 45 . 76 n on accumulati
kg 2 . 86
kmol 1
m
L 10
L
kg 659 . 0
m 0 . 10 n on accumulati
output on accumulati
n consumptio output generation input on accumulati
1
1 min
kmol
1
14 6
3
3
3
=
= =
= A =
= A =
=
+ =
Process Flowcharts
A process flowchart is a method for organizing
information about a process in a format that permits
convenient and easy to understand.
A process flowchart uses boxes and lines with arrows
to represent inputs and outputs of a process.

Labeling Process Flowcharts
1. Write the values of all known stream variables on
the locations of the streams on the chart.

1. Assign algebraic symbols to unknown stream
variables and write these variable names and their
associated units on the chart.
400 mol/h
0.21 mol O
2
/mol
0.79 mol N
2
/mol
320C, 1.4 atm
n (mol/h)
0.21 mol O
2
/mol
0.79 mol N
2
/mol
320C, 1.4 atm
.
400 mol/h
y (mol O
2
/mol)
(1-y) (mol N
2
/mol)
320C, 1.4 atm
Air Humidification and Oxygenation
An experiment on the growth rate of certain
organisms requires an environment of humid air
enriched in oxygen. Three input streams are fed into
an evaporation chamber to produce an output
stream with the desired composition.

A. liquid water, fed at a rate of 20.0 cm
3
/min
B. air (21 mol% O
2
, 79 mol% N
2
)
C. pure O
2
with a molar flow rate 1/5 of that of Stream B
Output gas is found to contain 1.5 mol% water.
An experiment on the growth rate of certain
organisms requires an environment of humid air
enriched in oxygen. Three input streams are fed into
an evaporation chamber to produce an output
stream with the desired composition.

A. liquid water, fed at a rate of 20.0 cm
3
/min
B. air (21 mol% O
2
, 79 mol% N
2
)
C. pure O
2
with a molar flow rate 1/5 of that of Stream B
Output gas is found to contain 1.5 mol% water.
Calculate n
2
from volumetric flowrate and density:
min
O H mol
11 . 1
O gH 02 . 18
mol 1
cm
O gH 00 . 1
min
O H cm 0 . 20
n
2
2
3
2 2
3
2
= =

water balance:
min
mol
1 . 74 n
mol
O H mol 015 . 0
min
mol
n
min
O molH
11 . 1
mol
O H mol 015 . 0
min
mol
n
min
O molH
n
3
2
3
2
2
3
2
2
=
|
.
|
\
|
|
.
|
\
|
=
|
.
|
\
|
|
.
|
\
|
|
.
|
\
|
=
|
.
|
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|

total mole balance:
( ) ( ) ( )
min
mol
1
min
mol
min
mol
1
3 2 1 1
8 . 60 n
1 . 74 11 . 1 n 200 . 1
n n n n 200 . 0
=
= +
= + +

nitrogen balance:
( )( ) ( )( )
( )( ) ( )( )( )
mol
O mol
mol
N mol
min
mol
mol
N mol
min
mol
mol
N mol
3 mol
N mol
min
mol
1
2
2 2
2 2
337 . 0 y
y 985 . 0 1 . 74 79 . 0 8 . 60
y 985 . 0 n 79 . 0 n
=
=
=

Flowchart Scaling
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 C
n
H
m
/kg = 2 kg 0.5 kg C
n
H
m
/kg
Flowchart Scaling
Scaling the
flowchart involves
changing all values
of stream flows by a
proportional
amount.
Note that mass (or
mole) fractions are
not scaled, but
remain unchanged.
Flowchart Scaling
A 60/40 mixture (molar)
of A and B is separated
batchwise into 2 fractions.
Scale the flowchart to a
continuous 1250 lbmol/hr feed rate.

feed:
mol
hr lbmol
5 . 12
mol 100
h lbmol 1250
= factor scale =
h
lbmol
1250
mol
hr lbmol
5 . 12 mol 100 =
Flowchart Scaling

top:
h
lbmol
625
mol
hr lbmol
5 . 12 mol 50.0 =
mol
hr lbmol
5 . 12
mol 100
h lbmol 1250
= factor scale =
Flowchart Scaling

bottom:
h
lbmolA
156
molA
hr lbmolA
5 . 12 molA 12.5 =
mol
hr lbmol
5 . 12
mol 100
h lbmol 1250
= factor scale =
Flowchart Scaling

bottom:
h
lbmolB
469
molB
hr lbmolB
5 . 12 molB 37.5 =
mol
hr lbmol
5 . 12
mol 100
h lbmol 1250
= factor scale =
Flowchart Scaling
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.
Basis of calculation
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 1, preferrably 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/h) as the basis.
If mole fractions are known, chose a total number of
moles or molar flow rate.
Balancing a Process
Suppose 3.0 kg/min of benzene and 1.0 kg/min of
toluene are mixed.
There are 2 unknown
quantities in this
process, m
dot
and x, thus 2 equations are needed to
solve for these unknowns.
For non-reacting processes, the material balance
takes the form: INPUT = OUTPUT.
3 balances can be written: one for total mass, and
one for each component (benzene and toluene).
Balancing a Process

Balances:

total mass: 3.0 kg/min + 1.0 kg/min = m
dot

m
dot
= 4.0 kg/min

benzene: 3.0 kg C
6
H
6
/min = m
dot
(kg/min) + x (kg C
6
H
6
/kg)
3.0 kg C
6
H
6
/min = 4.0 kg/min + x (kg C
6
H
6
/kg)
x = 0.75 kg C
6
H
6
/kg
Balancing nonreactive processes
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.
In the benzene/toluene example, only two of the three
balance equations are independent, thus only two
unknowns can be found from these balances.

Write balances first that involve the fewest unknown
variables.

Balances on a mixing unit
An aqueous solution of sodium hydroxide contains
20.0% mass NaOH. It is desired to produce an 8.0%
mass NaOH solution by diluting with pure water.
Calculate the ratios (liters H
2
O /kg feed solution) and
(kg product solution/kg feed solution).

1. Chose basis of calculation and draw/label flowchart.
2. Express what the problem asks you to determine in
terms of the labeled variables on the flowchart.
V
1
/100 (liters H
2
O/kg feed solution)
m
2
/100 (kg product solution/kg feed solution)
3. Count unknown variables and equations. If these
quantities are not equal, problem cannot be solved.
3 unknowns: m
1
, m
2
, V
1
(need 3 equations)

equations:
2 species 2 independent material balances
density relates V
1
to m
1
.
4. Outline solution procedure:
balances have the form INPUT = OUTPUT
1. NaOH balance contains 1 unknown: m
2
2. total mass balance contains 2 unknowns: m
1
and m
2
3. water balance contains 2 unknowns: m
1
and m
2
4. density relation contains 2 unknowns: V
1
and m
1

only need 1 of Equations 2 and 3 above
5. NaOH balance (INPUT = OUTPUT):

(0.20 kg NaOH/kg)(100 kg) = (0.80 kg NaOH/kg)(m
2
)

m
2
= 250 kg
= 250 kg NaOH
6. Total mass balance (INPUT = OUTPUT):

100 kg + m
1
= m
2
=250 kg

m
1
= 150 kg
= 250 kg
= 150 kg
7. Diluent water volume:

V
1
= m
1
/
H2O
= 150 kg / (1 kg/L)

V
1
= 150 L
= 250 kg
= 150 kg
= 150 L
7. Ratios:

V
1
/100 kg = 150 L / (100 kg) = 1.50 L H
2
O / kg feed solution

m
2
/100 kg = 250 kg / 100 kg = 2.50 kg product solution/
kg feed solution
= 250 kg
= 150 kg
= 150 L
Degree of Freedom Analysis
Process used to determine if a material balance
problems has sufficient specifications to be solved.
a) draw and completely label the flowchart
b) count the unknown variables on the chart
c) count the independent equations relating these variables
d) calculate degrees of freedom by subtracting (b) from (c)

n
df
= n
unknowns
n
indep_eqns

n
df
= n
unknowns
n
indep_eqns

If ndf = 0, problem can be solved (in principle).
if ndf > 0, problem is underspecified and at least n
df

additional variables must be specified before the
remaining variable values can be determined.
if ndf < 0, the problem is overspecified with
redundant and possibly inconsistent relations.
Sources of equations relating unknown process
stream variables include:
Material balances. For a nonreactive process, no more
than n
ms
(number of molecular species) independent
material balances may be written.
Energy balance. An energy balance provides a relationship
between inlet and outlet material flows and temperatures.
Process specifications.
Physical properties and laws.
Physical constraints.
Stoichiometric relations. (for reacting systems)
A stream of humid air enters a condenser in which
95% of the water vapor in the air is condensed.
The flow rate of the condensate (liquid leaving the
condenser) is measured and found to be 225 L/h.
Calculate the flow
rate of the gas
stream leaving the
condenser and the
mole fractions of
O
2
, N
2
, and H
2
O.
6 unknowns
3 material balances (1 each for O
2
, N
2
, H
2
O)
condensate volumetric to molar flow relation (MW and )
process specification: 95% of the water is condensed
n
df
= 6 (3 + 1 + 1) = 1
Underspecified
cannot solve
5 unknowns
3 material balances (1 each for O
2
, N
2
, H
2
O)
condensate volumetric to molar flow relation (MW and )
process specification: 95% of the water is condensed
n
df
= 5 (3 + 1 + 1) = 0
Solvable
Density relationship
95% condensation specification
O
2
Balance
N
2
Balance
H
2
O Balance
outlet gas composition
total outlet gas flow rate
( )( )( )
( )
( )( )
( )( )
( )
5 4 3 total
total 5 O H total 4 N total 3 O
5 2 1
4 1
3 1
1 2
kg 10 0 . 18
O H ol m 1
L
O H kg
h
O H L
2
n n n n
n n y ; n n y ; n n y
n n 100 . 0 n
n 79 . 0 900 . 0 n
n 21 . 0 900 . 0 n
n 100 . 0 95 . 0 n
00 . 1 225 n
2 2 2
3
2
) l ( 2 ) l ( 2

+ + =
= = =
+ =
=
=
=
=

General Procedure Single Unit Op

1. Choose as a basis of calculation an amount or flow
rate of one of the process streams.
If an amount or flow of a stream is given, it is usually
convenient to use it as the basis of calculation.
Subsequently calculated quantities will be correctly scaled.
If several stream amounts or flows are given, always use
them collectively as the basis.
If no stream amount or flow rate is specified, take as a
basis an arbitrariy amount or flow rate of a stream with a
known composition.
2. Draw flowchart and fill in all variable values,
including the basis. Label unknown stream variables.
Flowchart is completely labeled if you can express the
mass / mass flow rate (moles / molar flow rate) of each
component of each stream in terms of labeled quantities.
Labeled variables for each stream should include 1 of:
a. total mass (or flow), and mass fractions of all stream components
b. total moles (or flow), and mole fractions of all stream components
c. mass, moles (or flow) of each component in each stream
use (c) if no steam information is known
incorporate given relationships into flowchart
label volumetric quantities only if necessary
3. Express what the problem statement ask you to do
in terms of the labeled variables.
4. If given mixed mass and mole units, convert.
5. Do a degree-of-freedom analysis.
6. If n
df
= 0, write equations relating unknowns.
7. Solve the equations in (6).
8. Calculate requested quantities.
9. Scale results if necessary.
Distillation Column example
Ex. 4.3-5
1. basis is given as a
volumetric quantity
2a. Flowchart drawn from description
2b. Convert mole to mass fractions
2c. no stream information known
write in terms of species flows
Ex. 4.3-5
2d. confirm every component mass flow in every process stream
can be expressed in terms of labeled quantities and variables.
2e. process specification
Ex. 4.3-5
3. write expressions for quantities requested in problem statement
B T 3 3 B B
x 1 x ; m m x = =

3 T 3 B 3
m m m

+ =
3 1 2
m m m

=
Ex. 4.3-5
4. Convert mixed units in overhead product stream
( )( )
( )( )
( ) ( )
( ) ( )
kg
T kg
2 T
kg
B kg
2 B
T kmol
T kg
B kmol
B kg
058 . 0 942 . 0 1 y
942 . 0 mixture kg 7881 B kg 7420 y
mixture kg 7881 T kg 461 B kg 7420
T kg 461 13 . 92 T kmol 0 . 5
B kg 7420 11 . 78 B kmol 0 . 95
= =
= =
= +
=
=
Ex. 4.3-5
5. Perform degree of freedom analysis
=0.942
=0.058
4 unknowns
-2 material balances
-1 density relationship
-1 process specification
0 degrees of freedom
Ex. 4.3-5
6. Write system equations
7. Solve
( )( )
h
kg
L
kg
h
L
1
1744 872 . 0 2000 m = =
i. volumetric flow conversion
( )( )
h
B kg
1 3 B
8 . 62 m 45 . 0 08 . 0 m = =
ii. benzene split fraction
( )
h
B kg
2
3 B 2 B 2 1
766 m
m y m m 45 . 0
=
+ =

iii. benzene balance
( ) ( )
h
T kg
3 T
3 T 2 B 2 1
915 m
m y 1 m m 55 . 0
=
+ =

iv. toluene balance
h
kg
h
kg
3 T 3 B 2 1
1744 1744
m m m m
=
+ + =
iv. total mass balance (check)
Ex. 4.3-5
8. Calculate additional quantities
=0.942
=0.058
=1744 kg/h
=915 kg T/h
=62.8 kg B/h
=766 kg/h
h
kg
h
T kg
h
B kg
3
978 915 8 . 62 m = + =
kg
T kg
3 T
kg
B kg
h
kg
h
B kg
3 3 B 3 B
936 . 0 064 . 0 1 y
064 . 0 978 8 . 62 m m y
= =
= = =

Balances on Multiple Unit Ops
A system is any portion of a process that can be
enclosed within a hypothetical box (boundary). It
may be the entire process, a single unit, or a point
where streams converge or combine.
Boundary A encloses the entire process.
inputs: Streams 1, 2, and 3
products: 1, 2, and 3
Balances on A would be considered overall balances
internal streams would not be included in balances
B: an internal mixing point (2 inputs, 1 product)
C: Unit 1 (1 input, 2 products)
D: an internal splitting point (1 input, 2 products)
E: Unit 2 (2 inputs, 1 product)
The procedure for solving material balances on
multi-unit processes is the same as for a single unit;
though, it may be necessary to perform balances on
several process subsystems to get enough equations
to determine all unknown stream variables.
Two-Unit Process Example
Variables for Streams 1, 2, and 3 are unknown
Variables for Streams 1, 2, and 3 are unknown
Label unknown stream variables
Degree-of-freedom analysis
overall system: 2 unknowns 2 balances = 0 (find m
3
, x
3
)
mixer: 4 unknowns 2 balances = 2
Unit 1: 2 unknowns 2 balances = 0 (find m
1
, x
1
)
mixer: 2 unknowns 2 balances = 0 (find m
2
, x
2
)
Extraction-Distillation Process
Simultaneously solve total
mass and acetone balances to
determine m
1
and m
3
.

Solve MIBK balance to
determine x
M1
.
Solve acetone, MIBK, and
water balances to determine
m
A4
, m
M4
, and m
W4
.
For either (just 1) extractor
unit, solve acetone, MIBK, and
water balances to determine
m
A2
, m
M2
, and m
W2
.
n
df
= 4 unknowns (m
A6
, m
M6
,
m
W6
, and m
5
) 3 balances = 1

underspecified
n
df
= 4 unknowns (m
A6
, m
M6
,
m
W6
, and m
5
) 3 balances = 1

underspecified
Recycle
It is seldom cost effective to waste reactant fed that
does not react to product. More often, this material
is separated (recovered), and recycled (returned to
its point of origin for reuse).
Balances on an Air Conditioner
process cools and dehumidifies feed air
unknowns: n
1
, n
2
, n
3
, n
4
, n
5
(requested by problem)
degree-of-freedom analysis critical to solution
basis
Overall system
n
df
= 2 variables (n
1
, n
3
) 2 balances = 0
Mixer
n
df
= 2 variables (n
2
, n
5
) 2 balances = 0
Cooler
n
df
= 2 variables (n
2
, n
4
) 2 balances = 0
Splitter
n
df
= 2 variables (n
4
, n
5
) 1 balances = 1
only 1 independent balance can be written on the splitter because
the streams entering/leaving have the same composition.
( ) ( ) ( )( )
( ) ( ) ( )( ) 100 017 . 0 n 017 . 0 n 017 . 0
100 983 . 0 n 983 . 0 n 983 . 0
5 4
5 4
+ =
+ =
Overall: n
df
= 2 variables (n
1
, n
3
) 2 balances = 0
Mixer: n
df
= 2 variables (n
2
, n
5
) 2 balances = 0
Cooler: n
df
= 2 variables (n
2
, n
4
) 2 balances = 0
Splitter: n
df
= 2 variables (n
4
, n
5
) 1 balances = 1
To find requested unknowns,
solve overall balances
followed by mixing balances.
There is no need to solve the
cooler or splitter balances.
overall dry air balance
overall mole balance

0.960
( )
n
1
= 0.983
( )
100
( )
n
1
=102.4mol
n
1
= n
3
+ 100
( )
n
3
= 2.4 mol H
2
O condensed
overall mole balance
water balance
solved simultaneously:
( ) ( ) ( )
mol 290 n ; mol 5 . 392 n
n 023 . 0 n 017 . 0 n 04 . 0
n n n
5 2
2 5 1
2 5 1
= =
= +
= +
Reasons to recycle
recover catalyst
typically most expensive chemical constituent
dilute a process stream
reduce slurry concentration
control a process variable
control heat produced by highly exothermic reaction
circulation of a working fluid
refrigerant
Evaporative Crystallization Process
Calculate:
rate of evaporation
rate of production of crystalline K
2
CrO
4
feed rates to evaporator and crystallizer
recycle ratio (mass or recycle/mass of fresh feed)
Overall system:
n
df
= 3 unknowns (m
2
, m
4
, m
5
) 2 balances 1 spec = 0
specification: m
4
is 95% of total filter cake mass
( )
5 4 4
m m 95 . 0 m + =
Feed/recycle mixer:
n
df
= 3 unknowns (m
6
, m
1
, x
1
) 2 balances = 1
underspecified
( )
5 4 4
m m 95 . 0 m + =
Evaporator:
n
df
= 3 unknowns (m
3
, m
1
, x
1
) 2 balances = 1
underspecified
( )
5 4 4
m m 95 . 0 m + =
Crystallizer:
n
df
= 2 unknowns (m
3
, m
6
) 2 balances = 0
solvable
Once m
3
, m
6
are known, mixer or evaporator balances can
be solved.
( )
5 4 4
m m 95 . 0 m + =
Overall system:
K
2
CrO
4
balance
water balance
total mass balance
specification
( )( ) ( )
( )( ) ( )
( )
5 4 4
5 4 2 h
kg
5 2 h
K kg
5 4 h
K kg
m m 95 . 0 m
m m m 4500
m 636 . 0 m 4500 667 . 0
m 364 . 0 m 4500 333 . 0

+ =
+ + =
+ =
+ =
solve simultaneously for m
4
and m
5
h
crystals K kg
4
1470 m =
solu W/kg kg 0.636

solu K/kg kg 364 . 0
5 . 77 m
h
solution kg
5
=
Overall system:
K
2
CrO
4
balance
water balance
total mass balance
specification
solve for m
2
with knowns m
4
and m
5
h
O H kg
2
2
2950 m =
h
crystals K kg
4
1470 m =
solu W/kg kg 0.636

5 . 77 m
h
solution kg
5
=
( )( ) ( )
( )( ) ( )
( )
5 4 4
5 4 2 h
kg
5 2 h
K kg
5 4 h
K kg
m m 95 . 0 m
m m m 4500
m 636 . 0 m 4500 667 . 0
m 364 . 0 m 4500 333 . 0

+ =
+ + =
+ =
+ =
Overall system:
K
2
CrO
4
balance
water balance
total mass balance
specification
only 3 equations are independent

h
O H kg
2
2
2950 m =
h
crystals K kg
4
1470 m =
solu W/kg kg 0.636

5 . 77 m
h
solution kg
5
=
( )( ) ( )
( )( ) ( )
( )
5 4 4
5 4 2 h
kg
5 2 h
K kg
5 4 h
K kg
m m 95 . 0 m
m m m 4500
m 636 . 0 m 4500 667 . 0
m 364 . 0 m 4500 333 . 0

+ =
+ + =
+ =
+ =
Crystallizer:
total mass balance

water balance
( )
( ) ( ) ( )
6 h
kg
3
6 5 3
6 h
kg
3
6 5 4 3
m 257 . 1 4 . 97 m
m 636 . 0 m 636 . 0 m 506 . 0
m 5 . 77 1470 m
m m m m

+ =
+ =
+ + =
+ + =
h
O H kg
2
2
2950 m =
solve simultaneously for m
3
and m
6
h
kg
3
7200 m = h
crystals K kg
4
1470 m =
solu W/kg kg 0.636

5 . 77 m
h
solution kg
5
=
h
kg
6
5650 m =
feed/recycle mixer:
total mass balance
water or K
2
CRO
4
balance could be used tp find x
1
if desired
h
kg
1 1 6 h
kg
10150 m m m 4500 = = +

h
kg
1
10150 m =
h
O H kg
2
2
2950 m =
h
kg
3
7200 m =
h
kg
6
5650 m =
h
crystals K kg
4
1470 m =
solu W/kg kg 0.636

5 . 77 m
h
solution kg
5
=
If recycle is not used,
crystal production is 622 kg/h vs 1470 kg/h (w/ recycle)
discarded filtrate (m
4
) is 2380 kg/h, representing 866 kg/h
of potassium chromate
What are cost consequences of using recycle vs not?

Bypass Stream
Similar to a recycle, but a fraction of a stream is
diverted around a process unit, rather than being
returned to it.
Calculation approach is identical.
Balances on Reactive Systems
Material balance no longer takes the form
INPUT = OUTPUT

Must account for the disappearance of reactants and
appearance of products through stoichiometry.
Stoichiometric Equations
The stoichiometric equation of a chemical reaction is
a statement of the relative amounts of reactants and
products that participate in the reaction.
2 SO
2
+ O
2
2 SO
3
A stoichiometric equation is valid only if the number
of atoms of each atomic species is balanced.
2 S 2 S

4 O + 2 O 6 O

The stoichiometric equation of a chemical reaction is
a statement of the relative amounts of reactants and
products that participate in the reaction.
2 SO
2
+ O
2
2 SO
3
A stoichiometric rato of two molecular species
participating in a reaction is the ratio of their
stoichiometric coefficients:
2 mol SO
3
generated / 1 mol O
2
consumed
2 mol SO
3
generated / 2 mol SO
2
consumed

C
4
H
8
+ 6 O
2
4 CO
2
+ 4 H
2
O

Is this stoichiometric equation balanced?
What is the stoichiometric coefficient of CO
2
?
What is the stoichiometric ratio of H
2
O to O
2
?

How many lb-mol O
2
react to form 400 lb-mol CO
2
?

100 lbmol/min C
4
H
8
is fed and 50% reacts. At what rate is
water formed?
2
2
2
2
O lbmol 600
CO lbmol 4
O lbmol 6
CO lbmol 400 =
min
O H lbmol
200
H C lbmol 1
O H lbmol 4
50 . 0
min
H C lbmol
100
2
8 4
2 8 4
=
Limiting and Excess Reactants
Two reactants are said to be in stoichiometric
proportion if the ratio (moles A present/moles B
present) equals the stoichiometric ratio from the
balanced reaction equation.
2 SO
2
+ O
2
2 SO
3

the feed ratio that would represent stoichiometric
proportion is n
SO2
/n
O2
= 2:1
If reactants are fed in stoichometric proportion, and
the reaction proceeds to completion, all reactants
are consumed.
Stoichiometric Proportion Reactants are present in
a ratio equivalent to the ratio of the stoichiometric
coefficients.
A + 2B 2C
Limiting reactant A reactant is limiting if it is
present in less than stoichiometric proportion
relative to every other reactant.
A + 2B 2C

Excess reactant All other reactants besides the
limiting reactant.
fractional excess (f
XS
) ratio of the excess to the
stoichiometric proportion.

A + 2B 2C

( ) ( )
( )
25 . 0
4
4 5
n
n n
f
stoich A
stoich A feed A
XS
=
=
fractional conversion (f) ratio of the amount of a
reactant reacted, to the amount fed.

A + 2B 2C

( )
( )
fed
A
reacted
A
n
n
f =
0 . 0
5
0
f
A
= =
0 . 0
8
0
f
B
= =

A + 2B 2C

( )
( )
fed
A
reacted
A
n
n
f =
2 . 0
5
1
f
A
= =
25 . 0
8
2
f
B
= =

A + 2B 2C

( )
( )
fed
A
reacted
A
n
n
f =
4 . 0
5
2
f
A
= =
5 . 0
8
4
f
B
= =

A + 2B 2C

( )
( )
fed
A
reacted
A
n
n
f =
6 . 0
5
3
f
A
= =
75 . 0
8
6
f
B
= =

A + 2B 2C

( )
( )
fed
A
reacted
A
n
n
f =
8 . 0
5
4
f
A
= =
0 . 1
8
8
f
B
= =
Extent of Reaction
extent of reaction () an extensive quantity
describing the progress of a chemical reaction .
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

n
A
= n
A0

n
B
= n
B0
2

n
C
= n
C0
+2

= 0
Extent of Reaction
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

n
B
=82 =8

n
C
=0+2 =0

= 0

n
A
=5 =5
Extent of Reaction
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

= 1

n
B
=82 =6

n
C
=0+2 =2

n
A
=5 = 4
Extent of Reaction
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

= 2

n
B
=82 = 4

n
C
=0+2 = 4

n
A
=5 =3
Extent of Reaction
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

= 3

n
B
=82 =2

n
C
=0+2 =6

n
A
=5 =2
Extent of Reaction
A
= -1,
B
= -2,
C
= 2
A + 2B 2C

n
i
= n
i0
+v
i

= 4

n
B
=82 =0

n
C
=0+2 =8

n
A
=5 =1
Assume an equimolar reactant feed of 100 kmol:
What is the limiting reactant?

2C
2
H
4
+O
2
2C
2
H
4
O
ethylene
A reactant is limiting if it is present in less than stoichiometric proportion
relative to every other reactant.
1
1
n
n
1
2
n
n
feed
O
H C
stoich
O
H C
2
4 2
2
4 2
=
|
|
.
|
\
|
=
|
|
.
|
\
|
What is the percentage excess of each reactant?

2C
2
H
4
+O
2
2C
2
H
4
O
( ) ( )
( )
% 100 00 . 1
50
50 100
n
n n
f
stoich
O
stoich
O
feed
O
O , XS
2
2 2
2
= =
=
If the reaction proceeds to completion:
(a) how much of the excess
reactant will be left?

(b) How much C
2
H
4
O
will be formed?

(c) What is the extent of reaction?

2C
2
H
4
+O
2
2C
2
H
4
O
( )
50
2 100 0
n n
4 2 4 2 4 2
H C
o
H C H C
=
+ =
v + =
( )
50 n
50 1 100 n
n n
2
2
2 2 2
O
O
O
o
O O
=
+ =
v + =
( )
100 n
50 2 0 n
n n
O H C
O H C
O H C
o
O H C O H C
4 2
4 2
4 2 4 2 4 2
=
+ =
v + =
If the reaction proceeds to a point where the fractional
conversion of the limiting reactant is 50%, how much of
each reactant and product is present at the end? What is ?

2C
2
H
4
+O
2
2C
2
H
4
O
( )
( )
5 . 0
n
n
f
fed
H C
reacted
H C
4 2
4 2
= =
( )
25
2 100 50 100
n n
4 2 4 2 4 2
H C
o
H C H C
=
+ =
v + =
( )
75 n
25 1 100 n
n n
2
2
2 2 2
O
O
O
o
O O
=
+ =
v + =
( )
50 n
25 2 0 n
n n
O H C
O H C
O H C
o
O H C O H C
4 2
4 2
4 2 4 2 4 2
=
+ =
v + =
5 . 0
n
n n
f
o
H C
H C
o
H C
4 2
4 2 4 2
=
=
50 n
5 . 0
100
n 100
4 2
4 2
H C
H C
=
=

If the reaction proceeds to a point where 60 mol of O
2
is left,
what is the fractional conversion of C
2
H
4
? What is ?

2C
2
H
4
+O
2
2C
2
H
4
O
( )
( )
8 . 0
100
20 100
n
n
f
fed
H C
reacted
H C
4 2
4 2
=
= =
( )
20 n
40 2 100 n
n n
4 2
4 2
4 2 4 2 4 2
H C
H C
H C
o
H C H C
=
+ =
v + =
( )
40
1 100 60
n n
2 2 2
O
o
O O
=
+ =
v + =
Reaction Stoichiometry
Acrylonitrile produced by reaction of ammonia,
propylene, and O
2
at 30% conversion of limiting reactant:

C
3
H
6
+ NH
3
+
3
2
O
3
C
3
H
3
N+3H
2
O

n
NH
3
n
C
3
H
6
( )
0
= 0.120100 0.100100
( )
=1.20
n
NH
3
n
C
3
H
6
( )
stoich
= 1 1
( )
=1
n
O
2
n
C
3
H
6
( )
0
= 0.7800.21100 0.100100
( )
=1.64
n
O
2
n
C
3
H
6
( )
stoich
= 1.5 1
( )
=1.5
limiting
determine limiting reactant
propylene, and O
2

C
3
H
6
+ NH
3
+
3
2
O
3
C
3
H
3
N+3H
2
O

n
NH
3
( )
stoich
=10.0 mol C
3
H
6
1 mol NH
3
1 mol C
3
H
6
|
\

|
.
|
=10.0 mol NH
3
f
XS
( )
NH
3
=
NH
3 ( )
0
NH
3 ( )
stoich
NH
3 ( )
stoich
=
12.010.0
10.0
= 0.20
n
O
2
( )
stoich
=10.0 mol C
3
H
6
1.5 mol O
2
1 mol C
3
H
6
|
\

|
.
|
=15.0 mol O
2
f
XS
( )
O
2
=
O
2 ( )
0
O
2 ( )
stoich
O
2 ( )
stoich
=
16.415.0
15.0
= 0.093

f
XS
=0.20

f
XS
=0.093
determine fractional excesses
limiting
propylene, and O
2

C
3
H
6
+ NH
3
+
3
2
O
3
C
3
H
3
N+3H
2
O

n
C
3
H
6
= 1f
( )
n
C
3
H
6
( )
0
= 10.30
( )
10.0 mol C
3
H
6
( )
=7.0 mol C
3
H
6

f
XS
=0.093

f
XS
=0.20
use fractional conversion to
determine amount of
propylene that leaves the
reactor
limiting

n
i
= n
i0
+v
i
propylene, and O
2

C
3
H
6
+ NH
3
+
3
2
O
3
C
3
H
3
N+3H
2
O

n
C
3
H
6
= 7.0 mol C
3
H
6

f
XS
=0.093

f
XS
=0.20

n
C
3
H
6
= n
C
3
H
6
( )
0
+ 1
( )
7.0 mol =10.0 mol

= 3 mol

= 3 mol
determine extent of
reaction by applying mole
balance to propylene
limiting
propylene, and O
2
O H N H C O NH H C
2 3 3 2 2
3
3 6 3
3 + + +
( )( ) ( )( )
( )( )( ) ( )( )
( ) ( )( )
( )( )( ) ( )( )
( ) ( )( ) 9 0 . 3 3 0
6 . 61 3 0 100 78 . 0 79 . 0
3 0 . 3 1 0
9 . 11 3 100 78 . 0 21 . 0
9 3 1 100 12 . 0
2
2
3 3
2
3
2
3
= + =
= + =
= + + =
= + =
= + =
O H
N
N H C
O
NH
n
n
n
n
n

f
XS
=0.093

f
XS
=0.20 limiting

n
C
3
H
6
= 7.0 mol C
3
H
6

= 3 mol

n
i
= n
i0
+v
i
units not included and sig fig rules not followed to permit fit of all calculations
apply mole balance to
all remaining species
Chemical Equilibrium
Given
a set of reactive species, and
reaction conditions
Determine
1. the final (equilibrium) composition of the reaction
mixture
2. how long the system takes to reach a specified state
short of equilibrium

This course will cover #1 (Ch E 441 will cover #2)
Irreversible reaction
reaction proceeds only in a single direction A B
concentration of the limiting reactant eventually
approaches zero (time duration can vary widely)

Equilibrium composition of an irreversible reaction is
that which corresponds to complete conversion.
Reversible reaction
reaction proceeds in both directions A B
net rate (forward backward) eventually approaches zero
(again, time can vary widely)

Equilibrium composition of a reversible reaction is that
which corresponds to the equilibrium conversion.
Equilibrium Composition
An equilibrium reaction proceeds
to an extent at temperature T based
on the equilibrium constant, K(T).
where y
i
is the mole fraction of species i

Water-gas shift reaction:
Assume 1 mole CO and 2 mole H
2
O
K(1105 K) = 1.00
( ) ( )
( ) ( ) g
2
g
2 g 2 g
H CO O H CO + +
( )
O H CO
H CO
2
2 2
y y
y y
T K =
v + =
i 0 i i
n n
total
i
i
n
n
y =

2
O
K(1105 K) = 1.00
( )
O H CO
H CO
2
2 2
y y
y y
T K =
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
( ) ( )
3 n n n n n
1 n n
1 n n
2 1 n n
1 1 n n
2 2 2
2 2
2 2
2 2
H CO O H CO total
0
H H
0
CO CO
0
O H O H
0
CO CO
= + + + =
= + + =
= + + =
= + =
= + =
v + =
i 0 i i
n n
total
i
i
n
n
y =
( ) ( )
( ) ( ) g
2
g
2 g 2 g
H CO O H CO + +

2
O
K(1105 K) = 1.00
( )
O H CO
H CO
2
2 2
y y
y y
T K =
v + =
i 0 i i
n n
total
i
i
n
n
y =
3 n
n
n
2 n
1 n
total
H
CO
O H
CO
2
2
2
=
=
=
=
=
( )( )
( )( )
= =

1
2 1
( )( )
mol 667 . 0
2 2
2 1
2 2
2
=
+ =
=
667 . 0
667 . 0
333 . 1
333 . 0
=
=
=
=
( ) ( )
( ) ( ) g
2
g
2 g 2 g
H CO O H CO + +

2
O
K(1105 K) = 1.00
3 n
222 . 0 3 / 667 . 0 y
222 . 0 3 / 667 . 0 y
444 . 0 3 / 333 . 1 y
111 . 0 3 / 333 . 0 y
total
H
CO
O H
CO
2
2
2
=
= =
= =
= =
= =
( )( )
( )( )
= =

1
2 1
( )( )
mol 667 . 0
2 2
2 1
2 2
2
=
+ =
=
( )
O H CO
H CO
2
2 2
y y
y y
T K =
v + =
i 0 i i
n n
total
i
i
n
n
y =
( ) ( )
( ) ( ) g
2
g
2 g 2 g
H CO O H CO + +

2
O
K(1105 K) = 1.00
limiting reactant is CO
v + =
i 0 i i
n n

= 0.667mol
( )( )
mol 333 . 0
667 . 0 1 1 n
CO
=
+ =
at equilibrium,
fractional conversion at equilibrium
667 . 0 f
00 . 1
333 . 0 00 . 1
= =

( ) ( )
( ) ( ) g
2
g
2 g 2 g
H CO O H CO + +
3 n
222 . 0 3 / 667 . 0 y
222 . 0 3 / 667 . 0 y
444 . 0 3 / 333 . 1 y
111 . 0 3 / 333 . 0 y
total
H
CO
O H
CO
2
2
2
=
= =
= =
= =
= =
Multiple Reactions

C
2
H
4
+
1
2
O
2
C
2
H
4
O
C
2
H
4
+3O
2
2CO
2
+2H
2
O
( )

v + =
j
j ij
0
i i
n n
for j reactions of i species,
mole balance becomes
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
1
0
O H C O H C
2 1 2
1
0
O O
2 1
0
H C H C
1 n n
3 n n
1 1 n n
4 2 4 2
2 2
4 2 4 2
+ + =
+ + =
+ + =
( ) ( )
( ) ( )
2
0
O H O H
2
0
CO CO
2 n n
2 n n
2 2
2 2
+ + =
+ + =
Multiple Reactions

C
2
H
4
+
1
2
O
2
C
2
H
4
O
C
2
H
4
+3O
2
2CO
2
+2H
2
O
reactions side no with conversion 100% at formed moles
formed product desired moles
yield =
formed product undesired moles
formed product desired moles
y selectivit =
( )

v + =
j
j ij
0
i i
n n
for j reactions of i species,
mole balance becomes
Multiple Reactions
100 moles A fed to a batch reactor
product composition: 10 mol A, 160 B, 10 C

What is
1. f
A
?
2. Y
B
?
3. S
B/C
?
4.
1
,
2

C A
B 2 A
9 . 0
100
10 100
f
A
=
=
Multiple Reactions

What is
1. f
A
?
2. Y
B
?
3. S
B/C
?
4.
1
,
2

( )( )
889 . 0
10 100
160
Y
1
2
B
=
=
C A
B 2 A
Multiple Reactions

What is
1. f
A
?
2. Y
B
?
3. S
B/C
?
4.
1
,
2

16
10
160
S
C / B
= =
C A
B 2 A
Multiple Reactions

What is
1. f
A
?
2. Y
B
?
3. S
B/C
?
4.
1
,
2

10 90
100 10
n n
1 2
2 1
2 2 A 1 1 A Ao A
= =
=
v + v + =
80
2 0 160
n n
1
1
1 1 B Bo B
=
+ =
v + =
C A
B 2 A
Balances on Reactive Processes

Continuous, steady-state dehydrogenation of ethane
Total mass balance still has INPUT = OUTPUT form
Molecular balances contain consumption/generation
Atomic balances (H and C) also have simple form
2 4 2 6 2
H H C H C +
First consider molecular balances:

Molecular H
2
balance: generation = output
generation H
2
= 40 kmol H
2
/min
2 4 2 6 2
H H C H C +

C
2
H
6
balance: input = output + consumption
100 kmol C
2
H
6
/min = n
1
+ (C
2
H
6
consumed)
2 4 2 6 2
H H C H C +

C
2
H
4
balance: generation = output
(C
2
H
4
generated) = n
2

2 4 2 6 2
H H C H C +
Atomic C balance: input = output

Atomic H balance: input = output

2 4 2 6 2
H H C H C +
( ) ( ) ( )
4 2 6 2 6 2
H C mol 1
C mol 2
2 H C mol 1
C mol 2
1 H C mol 1
C mol 2
6 2
n n H C mol 100

+ =
( ) ( ) ( ) ( )
4 2 6 2 2 6 2
H C mol 1
H mol 4
2 H C mol 1
H mol 6
1 H mol 1
H mol 2
H C mol 1
H mol 6
6 2
n n 40 H C mol 100

+ + =
Independent Equations
To understand the number of independent species
balances in a reacting system requires an
understanding of independent algebraic equations.
Algebraic equations are independent if you cannot
obtain any of them by adding/subtracting multiples
of the others.
2] [ 12 y 6 x 3
[1] 4 y 2 x
= +
= +
[5] 6 z y 4
[4] 2 z x 2
[3] 4 y 2 x
= +
=
= +
3[1] = [2] 2[3] [4] = [5]
Independent Equations
To understand the number of independent species
balances in a reacting system requires an
understanding of independent algebraic equations.
Algebraic equations are independent if you cannot
obtain any of them by adding/subtracting multiples
of the others.
2] [ 12 y 6 x 3
[1] 4 y 2 x
= +
= +
( )
( )
12 12
12 y 6 y 6 12
12 y 6 y 2 4 3
=
= +
= +
Independent Species
If two molecular or atomic species are in the same
ratio to each other where ever they appear in a
process and this ratio is incorporated in the
flowchart labeling, balances on those species will not
be independent equations.
3 1
3 1
n 76 . 3 n 76 . 3
n n

=
=
Independent Chemical Reactions
When using molecular species balances or extents of
reaction to analyze a reactive system, the degree of
freedom analysis must account for the number of
independent chemical reactions among the species
entering and leaving the system.
Independent Chemical Reactions
Chemical reactions are independent if the
stoichiometric equation of any one of them cannot
be obtained by adding and subtracting multiples of
the stoichiometric equations of the others.

[3] 2C A
[2] C B
[1] 2B A
2[2] + [1] = [3]

Solving Reactive Systems
There are 3 possible methods for solving balances
around a reactive system:
1. Molecular species balances require more complex
calculations than the other methods and should be
used only for simple (single reaction) systems.
2. Atomic species balances generally lead to the most
straightforward solution procedure, especially
when more than one reaction is involved
3. Extents of reaction are convenient for chemical
equilibrium problems.
Molecular Species Balances
To use molecular species balances to analyze a
reactive system, the balances must contain
generation and/or consumption terms.

The degree-of-freedom analysis is as follows:
# unknown labeled variables
+ # independent chemical reactions
- # independent molecular species balances
- # other equations relating unknown variables
# of degrees of freedom

2 unknown labeled variables
+ 1 independent chemical reactions
- 3 independent molecular species balances
- 0 other equations relating unknown variables
0 degrees of freedom
at steady state
2 4 2 6 2
H H C H C +
H
2
Balance: generation = output
2 H
H kmol 40 gen
2
=
at steady state
2 4 2 6 2
H H C H C +
C
2
H
6
Balance: input = output + consumption
( )( )
min
H C kmol
1
H kmol 1
H C kmol 1
min
H kmol
1 min
H C kmol
6 2
2
6 2 2 6 2
60 n
40 n 1000
=
+ =
at steady state
2 4 2 6 2
H H C H C +
2 4 2 6 2
H H C H C +
C
2
H
4
Balance: generation = output
( )( )
min
H C kmol
2
H kmol 1
H C kmol 1
min
H kmol
2
4 2
2
4 2 2
40 n
40 n
=
=
at steady state
Atomic Species Balance

All atomic species balances take the form
INPUT = OUTPUT
Degree-of-freedom analysis, n
df
=
# unknown labeled variables
- # independent atomic species balances
- # molecular balances on independent nonreactive species
- # other equations relating unknown variables

2 4 2 6 2
H H C H C +

All atomic species balances take the form
INPUT = OUTPUT
Degree-of-freedom analysis, n
df
= 0 =
2 unknown labeled variables
- 2 independent atomic species balances
- 0 molecular balances on independent nonreactive species
- 0 other equations relating unknown variables

2 4 2 6 2
H H C H C +
C Balance: input = output
( )( ) ( ) ( )
2 1
H C kmol 1
C kmol 2
2 H C kmol 1
C kmol 2
1 H C kmol 1
C kmol 2
min
H C kmol
n n mol k 100
n n 100
4 2 6 2 6 2
4 2

+ =
+ =
2 4 2 6 2
H H C H C +
H Balance: input = output
( )( ) ( )( )
( ) ( )
2 1
H C kmol 1
H kmol 4
2 H C kmol 1
H kmol 6
1
H kmol 1
H kmol 2
min
H kmol
H C kmol 1
H kmol 6
min
H C kmol
n 4 n 6 + mol k 80 mol k 600
n n
40 100
4 2 6 2
2
2
6 2
4 2

+ =
+ +
=
2 4 2 6 2
H H C H C +
Solve simultaneously
min / H C kmol 40 n
min / H C kmol 60 n
n 4 n 6 + mol k 80 mol k 600 : H
n n mol k 100 : C
4 2 2
6 2 1
2 1
2 1
=
=
+ =
+ =

2 4 2 6 2
H H C H C +
Extent of Reaction
The 3
rd
method by which to determine molar flows
in a reactive system is using expressions for each
species flow rate in terms of extents of reaction ().

Degree-of-freedom analysis for such an approach:
n
df
= # of unknown labeled variables
+ # independent reactions
- # independent nonreactive species
- # other relationships or specifications
( )

v + =
j
j ij
0
i i
n n
Incomplete Combustion of CH
4
Methane is burned with air in a continuous steady-
state reactor to yield a mixture of carbon monoxide,
carbon dioxide, and water.

The feed to the reactor contains 7.80 mol% CH
4
, 19.4
mol% O
2
, 72.8 mol% N
2
. Methane undergoes 90.0%
conversion, and the effluent gas contains 8 mol CO
2

per mole CO.

CH
4
+
3
2
O
2
CO+2 H
2
O
CH
4
+2 O
2
CO
2
+2 H
2
O
4

The feed to the reactor contains 7.80 mol% CH
4
, 19.4
mol% O
2
, 72.8 mol% N
2
. Methane undergoes 90.0%
conversion, and the effluent gas contains 8 mol CO
2

per mole CO.

CH
4
+
3
2
O
2
CO+2 H
2
O
CH
4
+2 O
2
CO
2
+2 H
2
O
f
CH4
= 0.9
4

n
df
= 5 unknowns
+ 2 independent reactions
- 5 expressions for (CH
4
, O
2
, CO, CO
2
, H
2
O)
- 1 nonreactive species balance (N
2
)
- 1 specified methane conversion
=0

CH
4
+
3
2
O
2
CO+2 H
2
O
CH
4
+2 O
2
CO
2
+2 H
2
O
f
CH4
= 0.9
4

N
2
balance: nonreactive species, INPUT = OUTPUT

CH
4
conversion specification:

CH
4
+
3
2
O
2
CO+2 H
2
O
CH
4
+2 O
2
CO
2
+2 H
2
O
( )
2 mol
N mol
N
N mol 8 . 72 mol 100 728 . 0 n
2
2
= =
( )( )( )
4 mol
CH mol
CH
CH mol 780 . 0 mol 100 0780 . 0 900 . 0 1 n
4
4
= =
f
CH4
= 0.9
4

Extent of reaction mole balances:

CH
4
+
3
2
O
2
CO+2 H
2
O
CH
4
+2 O
2
CO
2
+2 H
2
O
( ) ( ) ( )
( ) ( )
( ) ( )
( ) ( ) ( )
( ) ( ) ( )
2 1 2
3
0
O O
2 1
0
O H O H
2
0
CO CO
1
0
CO CO
2 1
0
CH CH
2 n n
2 2 n n
1 n n
1 n n
1 1 n n
2 2
2 2
2 2
4 4
+ + =
+ + + + =
+ + =
+ + =
+ + =

0.78 =7.80
1
2
n
CO
=
1
n
CO
2
=8n
CO
=
2
n
H
2
O
=2
1
+2
2
n
O
2
=19.4
3
2

1
2
2
f
CH4
= 0.9
Product Separation and Recycle
Two definitions of reactant conversion are used in
the analysis of chemical reactors with product
separation and recycle of unconsumed reactants.
|
|
.
|
\
|
=
|
|
.
|
\
|
=
reactor to input
reactor from output - reactor to input
reactant
conversion
pass gle sin
process to input
process from output - process to input
reactant
conversion
overall
|
|
.
|
\
|
=
|
|
.
|
\
|
=
reactor to input
reactor from output - reactor to input
reactant
conversion
pass gle sin
process to input
process from output - process to input
reactant
conversion
overall
% 75 % 100
A/min mol 100
A/min mol 25 - A/min mol 100
conversion
pass gle sin
% 100 % 100
A/min mol 75
0 - A/min mol 75
conversion
overall
=
|
.
|
\
|
=
=
|
.
|
\
|
=
Catalytic Propane Dehydrogenation

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
Overall
Process
n
df
= 3 unknowns (n
6
, n
7
, n
8
)
2 independent atomic balances (C and H)
1 relation (overall conversion)
= 0
consider n
6
, n
7
, n
8
known for further DOF analyses

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
Mixing
point
n
df
= 4 unknowns (n
9
, n
10
, n
1
, n
2
)
2 balances (C
3
H
8
and C
3
H
6
)
= 2
n
df
= 2

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
reactor
n
df
= 5 unknowns (n
3
, n
4
, n
5
, n
1
, n
2
)
2 balances (C and H)
= 3
n
df
= 2
n
df
= 3

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
separator
n
df
= 5 unknowns (n
3
, n
4
, n
5
, n
9
, n
10
)
3 balances (C
3
H
8
, C
3
H
6
, and H
2
)
2 relations (reactant and product recovery fractions)
= 0
n
df
= 2
n
df
= 3 n
df
= 0

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
overall
( )( )
8 3 6
H C mol 5 mol 100 95 . 0 1 n = =
conversion
relationship

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
overall
( )( ) ( )( ) ( )
6 3 7
H C mol 1
C mol 3
7 H C mol 1
C mol 3
8 3 H C mol 1
C mol 3
H C mol 95 n
n H C mol 5 mol 100
6 3 8 3 8 3
=
+ =
C atomic balance
8 3 6
H C mol 5 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
overall
( )( ) ( )( )
( )( ) ( )
2 6 3
8 3 8 3
H mol 1
H mol 2
8 H C mol 1
H mol 6
6 3
H C mol 1
H mol 8
8 3 H C mol 1
H mol 8
n H C mol 95
H C mol 5 mol 100
+ +
=
H atomic balance
2 8
H mol 95 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
separator
( )
( )
6 3 10 7 10
8 3 3 3 6
H C mol 75 . 4 n n 0500 . 0 n
H C mol 900 n n 00555 . 0 n
= =
= =
given relations
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
separator

n
3
=n
6
+n
9
n
9
=895 mol C
3
H
8
propane balance

n
10
=4.75 mol C
3
H
6
8 3 3
H C mol 900 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
mixer

100+n
9
=n
1
n
1
=995 mol C
3
H
8
propane balance

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8
8 3 3
H C mol 900 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
mixer

n
10
=n
2
n
2
=4.75 mol C
3
H
6
propylene balance

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8

n
1
=995 mol C
3
H
8
8 3 3
H C mol 900 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
reactor
C atomic balance

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8

n
1
=995 mol C
3
H
8

n
2
=4.75 mol C
3
H
6
( )( ) ( )( )
( )( ) ( )( )
6 3 4
H C mol 1
C mol 3
4 H C mol 1
C mol 3
8 3
H C mol 1
C mol 3
6 3 H C mol 1
C mol 3
8 3
H C mol 75 . 99 n
n H C mol 0 0 9
H C mol .75 4 H C mol 95 9
6 3 8 3
6 3 8 3
=
+ =
+
8 3 3
H C mol 900 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
reactor
H atomic balance

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8

n
1
=995 mol C
3
H
8

n
2
=4.75 mol C
3
H
6
( )( ) ( )( )
( )( ) ( )( ) ( )
2 5
H mol 1
H mol 2
5 H C mol 1
H mol 6
6 3 H C mol 1
H mol 8
8 3
H C mol 1
H mol 6
6 3 H C mol 1
H mol 8
8 3
H mol 95 n
n H C mol 75 . 99 H C mol 0 0 9
H C mol .75 4 H C mol 95 9
2 6 3 8 3
6 3 8 3
=
+ + =
+
8 3 3
H C mol 900 n =
6 3 4
H C mol 75 . 99 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
single-pass
conversion

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8

n
1
=995 mol C
3
H
8

n
2
=4.75 mol C
3
H
6
( ) ( )
( )
% 55 . 9 % 100
H C mol 95 9
H C mol 0 0 9 H C mol 95 9
f
8 3
8 3 8 3
pass single
=
8 3 3
H C mol 900 n =
6 3 4
H C mol 75 . 99 n =
2 5
H mol 95 n =
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =

C
3
H
8
C
3
H
6
+H
2
95% overall
conversion
recycle
ratio
6 3 7
H C mol 95 n =
8 3 6
H C mol 5 n =
2 8
H mol 95 n =
8 3 3
H C mol 900 n =

n
10
=4.75 mol C
3
H
6

n
9
=895 mol C
3
H
8

n
1
=995 mol C
3
H
8

n
2
=4.75 mol C
3
H
6
( )
( ) ( )
( )
feed fresh mol
recycle mol
10 9
0 . 9
mol 00 1
mol .75 4 mol 95 8
feed mol 00 1
n n
R =
+
=
+
=
6 3 4
H C mol 75 . 99 n =
2 5
H mol 95 n =

f
singlepass
=9.55%
Purging
Necessary with recycle to prevent accumulation of a
species that is both present in the fresh feed and is
recycled rather than separated with the product.

CO
2
+3H
2
CH
3
OH+H
2
O
mixed fresh feed
and recycle is a
convenient
basis selection

f
singlepass
=60%
Methanol Synthesis
n
df
= 7 unknowns (n
0
, x
0C
, n
p
, x
5C
, x
5H
, n
3
, n
4
) + 1 rxn
- 5 independent species balances = 3

CO
2
+3H
2
CH
3
OH+H
2
O

f
singlepass
=60%
Methanol Synthesis
n
df
= 4 unknowns (n
1
, n
2
, n
3
, n
4
) + 1 rxn
4 independent species balances
1 single pass conversion = 0

CO
2
+3H
2
CH
3
OH+H
2
O

f
singlepass
=60%
Methanol Synthesis
n
df
= 3 unknowns (n
5
, x
5C
, X
5H
)
= 0

CO
2
+3H
2
CH
3
OH+H
2
O

f
singlepass
=60%
Methanol Synthesis
n
df
= 3 unknowns (n
0
, x
0C
, n
r
)
= 0

CO
2
+3H
2
CH
3
OH+H
2
O

f
singlepass
=60%
Methanol Synthesis
n
df
= 1 unknowns (n
p
)
1 independent species balance
= 0

CO
2
+3H
2
CH
3
OH+H
2
O

f
singlepass
=60%
investigate
mole balances and
their solution in
the text
Combustion Reactions
Combustion - rapid reaction of a fuel with oxygen.
Valuable class of reactions due to the tremendous
amount of heat liberated, subsequently used to
produce steam used to drive turbines which
generates most of the worlds electrical power.
Common fuels used in power plants:
coal
fuel oil (high MW hydrocarbons)
gaseous fuel (natural gas)
liquified petroleum gas (propane and/or butane)
Combustion Chemistry
When a fuel is burned
C forms CO
2
(complete) or CO (partial combustion)
H forms H
2
O
S forms SO
2

N forms NO
2
(above 1800C)
Air is used as the source of oxygen. DRY air analysis:
78.03 mol% N
2
20.99 mol% O
2
0.94 mol% Ar
0.03 mol% CO
2
0.01 mol% H
2
, He, Ne, Kr, Xe
usually safe to assume:
79 mol% N
2
21 mol% O
2
Stack (flue) gas product gas that leaves a furnace.
Composition analysis:
wet basis water is included in mole fractions
dry basis does not include water in mole fractions
Stack gas contains (mol) on a wet basis:
60.0% N
2
, 15.0% CO
2
, 10.0% O
2
, 15.0% H
2
O
Dry basis analysis:
60/(60+15+10) = 0.706 mol N
2
/mol
15/(60+15+10) = 0.176 mol CO
2
/mol
10/(60+15+10) = 0.118 mol O
2
/mol
Stack gas contains (mol) on a dry basis:
65% N
2
, 14% CO
2
, 10% O
2
, 11% CO
x
H2O
= 0.0700 (humidity measurement)

Wet basis analysis:

assume 100 mole dry gas basis
7.53 mole H
2
O
65 mole N
2
14 mole CO
2
10 mole O
2
11 mole CO
total = 107.5 mole
gas wet lbmol
gas ry d lbmol
gas wet lbmol
O H lbmol
9300 . 0 0700 . 0
2
gas dry lbmol

O H lbmol
2
0753 . 0

x
H
2
O
=
7.53
107.5
=0.0700
x
N
2
=
65
107.5
=0.605
x
CO
2
=
14
107.5
=0.130
x
O
2
=
10
107.5
=0.0930
x
CO
=
11
107.5
=0.102
Theoretical and Excess Air
The less expensive reactant is commonly fed in
excess of stoichiometric ratio relative to the more
valuable reactant, thereby increasing conversion of
the more expensive reactant at the expense of
increased use of excess reactant.
In a combustion reaction, the less expensive reactant
is oxygen, obtained from the air. Conseqently, air is
fed in excess to the fuel.
Theoretical oxygen is the exact amount of O
2
needed
to completely combust the fuel to CO
2
and H
2
O.
Theoretical air is that amount of air that contains the
amount of theoretical oxygen.
Excess air is the amount by which the air fed to the
reactor exceeds the theoretical air.

% excess air =
moles air fed - moles air theoretical
moles air theoretical
100%

n
C4H10
= 100 mol/hr; n
air
= 5000 mol/hr

C
4
H
10
+
13
2
O
2
4CO
2
+5H
2
O
( )
hr
O mol
650
H C mol
O mol 5 . 6
hr
H C mol 100
n
2
10 4
2 10 4
l theoretica
O
2
=
|
|
.
|
\
|
|
.
|
\
|
=
( )
hr
air mol
3094
O mol
air mol .76 4
hr
O mol 50 6
n
2
2
l theoretica
air
=
|
|
.
|
\
|
|
.
|
\
|
=

% excess air=
50003094
3094
100%=61.6%
Combustion Reactors
Procedure for writing/solving material balances for a
combustion reactor
1. When you draw and label the flowchart, be sure the
outlet stream (the stack gas) includes
a. unreacted fuel (unless the fuel is completely consumed)
b. unreacted oxygen
c. water and carbon dioxide (and CO if combustion is incomplete)
d. nitrogen (if air is used as the oxygen source)
2. Calculate the O
2
feed rate from the specifed percent
excess oxygen or air
3. If multiple reactions, use atomic balances
Combustion of Ethane

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
25% of the ethane burned forms CO
degree-of-freedom
analysis
n
df
= 7 unknowns
- 3 atomic balances
- 1 nitrogen balance
- 1 excess air specification
- 1 ethane conversion specification
- 1 CO/CO
2
ratio specification
= 0

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
excess air
specification
( )
2
6 2
2 6 2
l theoretica
O
O mol 350
H C mol
O mol 5 . 3 H C mol 100
n
2
=
|
|
.
|
\
|
|
|
.
|
\
|
=
( )
air mol 2500 n
O mol 350 5 . 1 n 21 . 0
0
2 0
=
=

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
ethane
conversion
specification
( )( )
6 2 6 2 1
H C mol 0 . 10 H C mol 100 90 . 0 1 n = =

n
0
=2500 mol air

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
CO/CO
2
ratio
specification
( )( )( ) O C mol 0 . 45
react H C mol 1
gen CO mol 2
H C mol 100 9 . 0 25 . 0 n
6 2
6 2 4
=
|
|
.
|
\
|
=

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
nitrogen
balance
( )( )
2 3
N mol 1975 ir a mol 2500 79 . 0 n = =

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

n
4
=45.0 mol CO

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
atomic C
balance
( )( ) ( ) ( ) ( )
2 5
CO mol 1
C mol 1
5 CO mol 1
C mol 1
4 H C mol 1
C mol 2
1 H C mol 1
C mol 2
6 2
CO mol 135 n
n n n H C mol 100
2 6 2 6 2
=
+ + =

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

n
4
=45.0 mol CO

n
3
=1975 mol N
2

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
atomic H
balance
( )( ) ( )( ) ( )
O H mol 270 n
n H C mol 10 H C mol 100
2 6
O H mol 1
H mol 2
6 H C mol 1
H mol 6
6 2 H C mol 1
H mol 6
6 2
2 6 2 6 2
=
+ =

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

n
4
=45.0 mol CO

n
3
=1975 mol N
2

n
5
=135 mol CO
2

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
atomic O
balance
( )( ) ( ) ( )( )
( )( ) ( )( )
2 2
O H mol 1
O mol 1
2 CO mol 1
O mol 2
2
CO mol 1
O mol 1
O mol 1
O mol 2
2 O mol 1
O mol 2
2
O mol 232 n
O H mol 70 2 CO mol 135
CO mol 5 4 n O mol 25 5
2 2
2 2
=
+ +
+ =

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

n
4
=45.0 mol CO

n
3
=1975 mol N
2

n
5
=135 mol CO
2

n
6
=270 mol H
2
O

C
2
H
6
+
7
2
O
2
2CO
2
+3H
2
O
C
2
H
6
+
5
2
O
2
2CO+3H
2
O
f
C2H6
= 0.9
stack gas
composition
(dry basis)

sum=10+232+1974+45+135=2396
y
1
=10 2396=0.00417 mol C
2
H
6
mol
y
2
=232 2396=0.0970 mol O
2
mol
y
3
=1974 2396=0.824 mol N
2
mol
y
4
=45 2396=0.019 mol CO mol
y
5
=135 2396=0.0563 mol CO
2
mol

n
0
=2500 mol air

n
1
=10.0 mol C
2
H
6

n
4
=45.0 mol CO

n
3
=1975 mol N
2

n
5
=135 mol CO
2

n
6
=270 mol H
2
O

n
2
=232 mol O
2

270 mol H
2
O
2396 mol dry stack gas
=0.113
mol H
2
O
mol dry stack gas

4 Material Balances

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4 Material Balances

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Fundamentals of

Air Humidification and Oxygenation

General Procedure Single Unit Op

solu W/kg kg 0.636

solu W/kg kg 0.636

solu W/kg kg 0.636

solu W/kg kg 0.636

solu W/kg kg 0.636

Assume an equimolar reactant feed of 100 kmol:

7.0 mol =10.0 mol

Balances on Reactive Processes

2[2] + [1] = [3]

gas dry lbmol

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