Material Balances Without Chemical Reaction

Material Balances
without chemical
reactions
Objectives
Classify processes as batch, semibatch,
continuous, transient, and steady-state.
Draw and label process flowcharts.
Select a calculation basis.
Perform a degree of freedom analysis.
Define/solve equations to calculate process
variables.
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 manufacture.
Continuous process
Feeds and effluents continuously 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
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.
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).
The General Balance

Equation
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
The General Balance

Equation
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).

accumulation
input: 50,000 people/year

generation: 22,000 people/year
ouput: 75,000 people/year
consumption: 19,000 people/year
accumulation: unknown
The General Balance

Equation
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).

accumulation
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
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
0
accumulation
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
system
Benzene/Toluene distillation
continuous process
steady-state operation
no reactions occurring
General species balance

0

accumulation
input = output
system
input = output
Benzene balance
500 kg B/h = 450 kg B/h + m2

m2 = 50 kg B/h
Toluene balance
500 kg T/h = m1 + 475 kg T/h
m1 = 25 kg T/h
Total mass balance

1000 = 450 + m1 + m2 + 475 (all with units of
kg/h)
1000 kg/h = 1000 kg/h
Integral Balances on Batch

Processes
consider the reaction N2 + H2 NH3 in a
batch reactor
at t=0, there is n0 moles of NH3 in the reactor

at t=tf, there is nf moles of NH3 in the reactor
between 0 and tf, no NH3 crosses system
boundary
NH3 accumulation in system from 0 to tf is nf
n0 .
therefore, for a batch process,

accumulation = final output initial input
= generation consumption
initial input + generation = final output +
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
x g CH3OH
0.400 g CH3OH
0.700 g CH3OH
200g
150g
mg
g
g
g
g CH3OH
x 0.529
g
Water balance
200(0.6) + 150(0.3) = 350(1-0.529)
165 g H2O = 165 g H2O
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 m3
of liquid?
Processes
differential air balance
input output
0.100
kmol air 0.900 kmol air

kmol
n
min
kmol
min
kmol
n 0.111
min
Processes
integral hexane balance
accumulation input generation output consumption

accumulation output
0.659kg 103 L 1kmol

accumulation n 10.0m
3
L
86.2kg
m
accumulation n 76.45 kmol C6 H14
3
output 0.100nt1 0.100 0.111 kmol t1

t1 6880 min
min
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
400 mol/h
on the chart.
0.21 mol O2/mol
0.79 mol N2/mol
320C, 1.4 atm
2. Assign algebraic symbols to unknown

stream variables and write these variable
400 mol/h
.
names and
their associated
units
on the
n (mol/h)
y (mol
O /mol)
0.21 mol O /mol
(1-y) (mol N /mol)
chart.
2
0.79 mol N2/mol

320C, 1.4 atm
320C, 1.4 atm
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.

Unit Op
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

Unit Op
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 ndf = 0, write equations relating
unknowns.
7. Solve the equations in (6).
8. Calculate requested quantities.
9. Scale results if necessary.
Distillation
This operation is carried out for the

separation of the components of a mixture
by partial vaporization and condensation.
Overall Material balance:

Feed= distillate + Bottoms
F= D+W.
Where F is the Feed in kg/hr. D is the
Distillate in kg/hr W bottom product
kg/hr.
Material Balance of Component A:
FXF= DXD+WXW
Where XF, XD and XW are the weight
fractions of A in the Feed, Distillate
Evaporation
This operation used in the chemical

industry for the concentration of weak
liquor to produce a thick liquor by
evaporating a portion of the solvent by
means of condensing steam.

Weak Liquor=Water evaporated +
Crystallized Product + Thick Liquor
If crystallized Product is nil:
Weak Liquor=Water evaporated + Thick
Liquor
Material balance on solids:
Solids(solute) in weak liquor=
Solids(solute) in Thick
Liquor.
Material balance of water:
Water in weak Liquor= Water evaporated
+ Water in
Absorption
The operation is used in the chemical

industry for the recovery/removal of solute
gas component from its mixture with
another component gases with the help of
a suitable liquid solvent in which the
solute gas absorbed.
Material balance of inert gas:

Inert gas entering the tower= Inert gas
leaving the tower
Material balance of solute gas (for no
solute in solvent)
Solute gas removed by absorption=Solute
in inlet gas-Solute in lean gas
Extraction Liquid-Liquid
The operation used in the chemical

industry for the separation of the
components of a liquid mixture with the
help of a suitable liquid solvent wherein
the solute from the feed solution is
transferred in the solvent yielding the
raffinate phase (rich in the feed solvent)
and Extract Phase (rich in the solvent
Overall material balance:

Feed Solution + Solvent = Extract Phase +
Raffinate Phase.
If A is the Solute to be extracted, Then the
material balance of A for fresh solvent is:
A in Feed solution= A in Extract Phase +A in
Raffinate Phase.
Extraction operation is carried out for the

removal of a soluble constituent of solids
with the help of a suitable liquid solvent.
Material Balance of solids:

Solids in seeds= Solids in meal.
Material balance of oil.
Oil in seeds= Oil in meal+ Oil in Solvent.
Drying
The operation is carried out in the
chemical industry for the removal of
moisture or volatile liquid associated with
wet solids with the help of hot air, or inert
gas Nitrogen.
Material balance of moisture:

Moisture removed from solids= Moisture
added in air
Initial moisture in wet solids- moisture in
dried solids= Moisture in outlet airMoisture in inlet air.
Material balance of solids.
Solids in wet solids = Solids in dried
product.
Filtration
The operation is carried out in the industry
for the separation of solid from a
suspension in a liquid.
Centrifuge machines, Drum filters, Press

filters etc.
Overall Material Balance:

Feed Slurry = Wet Solids + Filtrate.
Material Balance of Solids:
Solids in Slurry =Solids in Wet Solids Product
+Solids in
Filtrate
Mixing / Blending
This operation is carried out in Chemical
Industry to obtain a product of the desired
quality by mixing weak and concentrated
streams.

Feed 1+ Feed2 +Feed3 = Desired Product.
Material Balance of A
A in Feed1+ A in Feed2+ A in Feed 3=
desired product.
Crystallization
It is the formation of solids particles within
a homogeneous liquid phase.
Crystallization gives almost pure product
and crystallization from Solution is very
important industrially.
Equipments are Stirred tanks, Vacuum

crystallizer etc.
Overall material balance:

Feed solution=Saturated solution
+crystals
Material balance of crystal solute:
crystals in feed solution= crystals obtained
+ crystals in saturated Solution.
Crystallization of the dissolved solids from
a solution is based on the differences in
solubility at different temperatures. It
usually consists of concentration of
solution and cooling of solution until it
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 cm3/min
B. air (21 mol% O2, 79 mol% N2)
C. pure O2 with a molar flow rate 1/5 of that of
Stream B
Output gas is found to contain 1.5 mol% water.

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 cm3/min
B. air (21 mol% O2, 79 mol% N2)
C. pure O2 with a molar flow rate 1/5 of that of
Stream B
Output gas is found to contain 1.5 mol% water.

Oxygenation
Calculate n2 from volumetric flowrate and density:
20.0cm3H2O 1.00gH2O
1mol
molH2O
2
n
1
.
11
min
cm3
18.02gH2O
min

Oxygenation
water balance:
molH2O
mol 0.15molH2O
n3
mol
min
min
molH2O
mol
mol 0.15molH2O
1
.
11
74
.
1
3
3
min
min
mol
min
2
n

Oxygenation
total mole balance:
1 n
1 n
2 n
3
0.200n
mol
mol
1.200 1.11mol
min 1.11min 74.1min
1 60.8mol
n
min

Oxygenation
nitrogen balance:
molN
molN
n 1 mol
0
.
79
n
0
.
985
y
3
min
mol
mol
molN
molN
mol
60.8mol
0
.
79
74
.
1
0
.
985
y
min
mol
min
mol
2
O2
y 0.337mol
mol
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 CnHm/kg = 2 kg 0.5 kg CnHm/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
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.
1250lbmolh
lbmolhr
scalefactor=
12.5
100mol
mol
feed: 100mol 12.5lbmolhr 1250lbmol

mol
Flowchart Scaling
1250lbmolh
lbmolhr
scalefactor=
12.5
100mol
mol
top: 50.0mol 12.5lbmolhr 625lbmol

mol
Flowchart Scaling
1250lbmolh
lbmolhr
scalefactor=
12.5
100mol
mol
bottom:12.5molA 12.5lbmolAhr 156lbmolA

molA
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
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, mdot 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 = mdot
mdot = 4.0 kg/min
benzene: 3.0 kg C6H6/min = mdot (kg/min) + x
(kg C6H6/kg)
3.0 kg C6H6/min = 4.0 kg/min + x
(kg C6H6/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 H2O /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.
V1/100 (liters H2O/kg feed solution)
m2/100 (kg product solution/kg feed solution)

3. Count unknown variables and equations.
If these quantities are not equal, problem
cannot be solved.
3 unknowns: m1, m2, V1 (need 3 equations)
equations:
2 species 2 independent material balances

density relates V1 to m1.

4. Outline solution procedure:
balances have the form INPUT = OUTPUT
1.
NaOH balance contains 1 unknown: m2
2.
total mass balance contains 2 unknowns: m1 and m2
3.
water balance contains 2 unknowns: m1 and m2
4.
density relation contains 2 unknowns: V1 and m1
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)
(m2)
m2 = 250 kg
= 250 kg NaOH

6. Total mass balance (INPUT = OUTPUT):
100 kg + m1 = m2 =250 kg
m1 = 150 kg
= 250 kg
= 150 kg

7. Diluent water volume:
V1 = m1 / H2O = 150 kg / (1 kg/L)
V1 = 150 L
= 250 kg
= 150 kg
= 150 L

7. Ratios:
V1 /100 kg = 150 L / (100 kg) = 1.50 L H2O / kg
feed solution
m2 /100 kg = 250 kg / 100 kg = 2.50 kg product
solution/
kg
= 250 kg
feed solution
= 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)
ndf = nunknowns nindep_eqns

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

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

6 unknowns
3 material balances (1 each for O2, N2, H2O)
condensate volumetric to molar flow relation
(MW and )
process specification: 95% of the water is
condensed
ndf = 6 (3 + 1 + 1) = 1 Underspecified
cannot solve

5 unknowns
3 material balances (1 each for O2, N2, H2O)
condensate volumetric to molar flow relation
(MW and )
process specification: 95% of the water is
condensed
ndf = 5 (3 + 1 + 1) = 0
Solvable
Density relationship
95% condensation specification
O2 Balance
N2 Balance
H2O Balance
outlet gas composition
total outlet gas flow rate
2 225LH2hO(l) 1.00kgHL2O(l)
n
2 0.95 0.100n
1
n
1 0.900 0.21 n
3
n
1molH2O
18.0103kg
1 0.900 0.79 n
4
n
1 0.100 n
2 n
5
n
3 n
total; yN2 n
4 n
total; yH2O n
5 n
total
yO2 n
total n
3 n
4 n
5
n
Distillation Column
example
Ex. 4.3-5
2a. Flowchart drawn from description
1. basis is given as a
volumetric quantity
2b. Convert mole to mass fractions
2c. no stream information known

write in terms of species flows
Distillation Column
2d. confirm every component mass flow in every
example
process stream can be expressed in terms of
Ex. 4.3-5
labeled quantities and variables.
2e. process specification
Distillation Column
example
3. write expressions for quantities requested in
Ex. 4.3-5
problem statement
2 m
1 m
3
m
3 m
B3 m
T3
m
B3 m
3 ; xT 1 xB
xB m
Distillation Column
example
4. Convert mixed units in overhead product stream
Ex. 4.3-5
kgB
95.0kmolB 78.11kmol
kgB
B 7420
kgT
5.0kmolT 92.13kmol
kgT
T 461
7420kgB 461kgT 7881kgmixture
0.942kgkgB
yB2 7420kgB 7881kgmixture
T
yT2 1 0.942 0.058kg
kg
Distillation Column
example
5. Perform degree of freedom analysis
Ex. 4.3-5
=0.94
2 =0.05
8
4 unknowns
-2 material balances
-1 density relationship
-1 process specification
0 degrees of freedom
Distillation Column
6. Write system equations
example
iv. total mass balance (check)
Ex. 4.3-57. Solve
kg
1744kg
h 1744h
i. volumetric flow conversion

kg
1 2000hL 0.872kg
m
L 1744h
1 m
2 m
B3 m
T3
m
ii. benzene split fraction

B3 0.08 0.45m
1 62.8 kghB
m
. benzene balance iv. toluene balance
1 m
2yB2 m
B3
0.45m
1 m
2 1 yB2 m
T3
0.55m
2 766kghB
m
T3 915kghT
m
Distillation Column
example
8. Calculate additional quantities
Ex. 4.3-5
=766 kg/h
=1744 kg/h
B3 m
3 62.8kghB
yB3 m
=0.94
2 =0.05
8
kgB
978kg
h 0.064kg
T
yT3 1 0.064 0.936kg
kg
3 62.8 kghB 915kghT 978kg

m
h
=62.8 kg B/h
=915 kg T/h
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.

Ops
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

Ops
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)

Ops
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, x1)
mixer: 2 unknowns 2 balances = 0 (find m2, x2)
Extraction-Distillation
Process
Process
Simultaneously solve
total mass and acetone
balances to determine m1
and m3.
Solve MIBK balance to
determine xM1.
Process
Solve acetone, MIBK, and

water balances to
determine mA4, mM4, and
mW4.
Process
For either (just 1)

extractor unit, solve
acetone, MIBK, and water
balances to determine
mA2, mM2, and mW2.
Process
ndf = 4 unknowns (mA6,

mM6, mW6, and m5) 3
balances = 1
underspecified
Process
ndf = 4 unknowns (mA6,

mM6, mW6, and m5) 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: n1, n2, n3, n4, n5 (requested by
problem)
degree-of-freedom analysis critical to
solution
basis
Balances on an Air
Conditioner
Overall system
ndf = 2 variables (n1, n3) 2 balances = 0
Balances on an Air
Conditioner
Mixer
Balances on an Air
Conditioner
Cooler
Balances on an Air
Conditioner
Splitter

only 1 independent balance can be written on the
splitter because the streams entering/leaving have
the same composition.
0.983n4 0.983n5 0.983 100

0.017n4 0.017n5 0.017 100
Balances on an Air
Conditioner
Overall: n = 2 variables (n , n ) 2 balances
=requested
0
To find
df
unknowns, solve overall

Mixer: ndf = 2 variables (n2, n5) 2 balances
=0
balances followed by
Cooler: ndf = 2 variables (n2, n4) 2 balances
=0
mixing
balances.
There=
is 1no need to solve
Splitter: ndf = 2 variables (n4, n5) 1 balances
the cooler or splitter
balances.
Balances on an Air
Conditioner
overall dry air balance

0.960n1 0.983100 n1 102.4mol
overall mole balance
n1 n3 100 n3 2.4 mol H2O condensed
Balances on an Air
Conditioner
n n n
overall mole balance 1 5 2

0.04n1 0.017n5 0.023n2
water balance
solved simultaneously:
n2 392.5mol; n5 290mol
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 K2CrO4
feed rates to evaporator and crystallizer
recycle ratio (mass or recycle/mass of fresh
feed)
Process
Overall system:
ndf = 3 unknowns (m2, m4, m5) 2 balances 1

spec = 0
specification: m4 is 95% of total filter cake
mass
4 0.95 m
4 m
5
m
Process
Feed/recycle mixer:
ndf = 3 unknowns (m6, m1, x1) 2 balances = 1

underspecified
4 0.95 m
4 m
5
m
Process
Evaporator:
ndf = 3 unknowns (m3, m1, x1) 2 balances = 1

underspecified
4 0.95 m
4 m
5
m
Process
Crystallizer:
ndf = 2 unknowns (m3, m6) 2 balances = 0

solvable
Once m3, m6 are known, mixer or evaporator
balances can be solved.
4 0.95 m
4 m
5
m
Process
solve simultaneously for m and m

Overall system:
K2CrO4 balance
water balance
total mass balance
specification
4 0.364 m
5
0.333 4500 kghK m
2 0.636m
5
0.667 4500 kghK m
4500kg
h m2 m4 m5
4 0.95 m
4 m
5
m
4 1470kgKcrystals
m
h
5 77.5kgsolution
m
h
0.364kgK/kgsolu
0.636
kgW/kgsolu
Process
solve for m with knowns m and m

Overall system:
K2CrO4 balance
water balance
total mass balance
specification m 2950
2
kgH2O
h
4 0.364m
5
0.333 4500 kghK m
2 0.636m
5
0.667 4500 kghK m
4500kg
h m2 m4 m5
4 0.95 m
4 m
5
m
4 1470kgKcrystals
m
h
5 77.5kgsolution
m
h
0.364kgK/kgsolu
0.636
kgW/kgsolu
Process
only 3 equations are independent

Overall system:
K2CrO4 balance
water balance
total mass balance
specification m 2950
2
kgH2O
h
4 0.364m
5
0.333 4500 kghK m
2 0.636m
5
0.667 4500 kghK m
4500kg
h m2 m4 m5
4 0.95 m
4 m
5
m
4 1470kgKcrystals
m
h
5 77.5kgsolution
m
h
0.364kgK/kgsolu
0.636
kgW/kgsolu
Process
solve simultaneously for m and m

Crystallizer:
total mass balance
3 m
4 m
5 m
6
m
3 1470 77.5 kg
m
h m6
3 0.636m
5 0.636m
6
0.506m
water balance
2 2950kgHh2O
m
3 97.4 kg
6
m
m
h 1.257
3 7200kg
m
h
4 1470kgKcrystals
m
h
5 77.5kgsolution
m
h
6 5650kg
m
h
0.364kgK/kgsolu
0.636
kgW/kgsolu
Process
feed/recycle mixer:
kg
total mass balance 4500kg
10150
6
1
1
h
h
water or K2CRO4 balance could be used tp find
x1 if desired
2 2950kgHh2O
m
kg
1 10150
m
h
3 7200kg
m
h
4 1470kgKcrystals
m
h
5 77.5kgsolution
m
h
6 5650kg
m
h
0.364kgK/kgsolu
0.636
kgW/kgsolu
Process
If recycle is not used,
crystal production is 622 kg/h vs 1470 kg/h (w/

recycle)
discarded filtrate (m4) 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 SO2 + O2 2 SO3
A stoichiometric equation is valid only if
the number of atoms of each atomic
species is balanced.
2S2S
4O+2O6O
The stoichiometric equation of a chemical
reaction is a statement of the relative
amounts of reactants and products that
participate in the reaction.
2 SO2 + O2 2 SO3
A stoichiometric rato of two molecular
species participating in a reaction is the
ratio of their stoichiometric coefficients:
2 mol SO3 generated / 1 mol O2 consumed
2 mol SO3 generated / 2 mol SO2 consumed
C4H8 + 6 O2 4 CO2 + 4 H2O
Is this stoichiometric equation balanced?
What is the stoichiometric coefficient of CO2?
What is the stoichiometric ratio of H2O to O2?
How many lb-mol O2 react to form 400 lb-mol
CO2? 400lbmolCO2 6lbmolO2 600lbmolO2
4lbmolCO2
100 lbmol/min C4H8 if fed and 50% reacts. At

lbmolC4H8
4lbmolH2O
lbmolH2O
100
0
.
50
200
what rate min
is water formed?
1lbmolC H
min
4 8
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 SO2 + O2 2 SO3
the feed ratio that would represent
stoichiometric proportion is nSO2/nO2 = 2:1
If reactants are fed in stoichometric
proportion, and the reaction proceeds to
completion, all reactants are consumed.
Limiting and Excess

Reactants
Stoichiometric Proportion Reactants are

present in a ratio equivalent to the ratio of
the stoichiometric coefficients.
A + 2B 2C
Limiting and Excess

Reactants
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.
Limiting and Excess

Reactants
fractional excess (fXS) ratio of the excess

n A n A
to the stoichiometric proportion.
feed
stoich
f XS
n A stoich
A + 2B 2C
5 4
0.25
4
Limiting and Excess

Reactants
fractional conversion (f) ratio of the

amount of a reactant reacted, to the
nA
reacted
amount fed.
f
nA
fed
A + 2B 2C
fA
0
0.0
5
0
f B 0.0
8
Limiting and Excess

Reactants

nA
reacted
amount fed.
f
nA
fed
A + 2B 2C
fA
1
0.2
5
4
f B 0.25
8
Limiting and Excess

Reactants

nA
reacted
amount fed.
f
nA
fed
A + 2B 2C
fA
2
0.4
5
4
f B 0.5
8
Limiting and Excess

Reactants

nA
reacted
amount fed.
f
nA
fed
A + 2B 2C
fA
3
0.6
5
6
f B 0.75
8
Limiting and Excess

Reactants

nA
reacted
amount fed.
f
nA
fed
A + 2B 2C
fA
4
0.8
5
8
f B 1.0
8
Extent of Reaction
extent of reaction () an extensive
quantity describing the progress of a
chemical reaction .
coefficients: A= -1,
n i n i0stoichiometric
i
0 B = -2, C =
2
n A n A0
A + 2B 2C
n B n B0 2
nC nC0 2
Extent of Reaction
chemical reaction .
i
0 B = -2, C =
2
nA 5 5
A + 2B 2C
n B 8 2 8
nC 0 2 0
Extent of Reaction
chemical reaction .
coefficients: A =-1,
i
1 B = -2, C =
2
nA 5 4
A + 2B 2C
n B 8 2 6
nC 0 2 2
Extent of Reaction
chemical reaction .
i
2 B = -2, C =
2
nA 5 3
A + 2B 2C
n B 8 2 4
nC 0 2 4
Extent of Reaction
chemical reaction .
i
3 B = -2, C =
2
nA 5 2
A + 2B 2C
n B 8 2 2
nC 0 2 6
Extent of Reaction
chemical reaction .
i
4 B = -2, C =
2
nA 5 1
A + 2B 2C
n B 8 2 0
nC 0 2 8
2C2 H 4 O2 2C2 H 4O
Assume an equimolar reactant feed of 100
kmol:
What is the limiting reactant?
What is the percentage excess of each reactant?
If the reaction proceeds to completion: (a) how
much of the excess reactant will be left? (b) How
much C2H4O will be formed? (c) What is the
extent of reaction?
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 ?
If the reaction proceeds to a point where 60 mol
Reaction Stoichiometry
Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting
conversion
3 limiting reactant:
C H NH of
O C H N 3H O
3
determine limiting reactant
nNH
nNH
nO
nO
2
0 0.120 100 0.100 100 1.20

nC H
1 1 1
stoich
nC H 0.780 0.21 100 0.100 100 1.64
0
nC H
1.5 1 1.5
stoich
nC 3 H 6
3
f 0.093
limiting f 0.20
conversion
C H NH of
O C H N 3H O
XS
XS
determine fractional excesses
1 mol NH 3
10.0 mol C3 H6
10.0 mol NH 3
1 mol C 3 H 6
stoich
NH NH
12.010.0 0.20
f XS NH NH
10.0
1.5 mol O
n
10.0
mol
C
H
O stoich
3 6 1 mol C H 15.0 mol O2
O O
16.415.0
f
0.093
XS O
15.0
O

n NH 3
3 0
3 stoich
3 stoich
2 0
2 stoich
2 stoich
f 0.093
limiting f 0.20
conversion
C H NH of
O C H N 3H O
XS
XS
nC 3 H 6 1 f nC 3 H 6
0 1 0.3010.0 mol C3H6 7.0 mol C3 H6

use fractional
conversion to
determine amount of
propylene that leaves
the reactor
f 0.093
limiting f 0.20
conversion
C3 H6 NH3 of
O C3 H3 N 3H2O
n i n i0 i
2 3
XS
XS
nC 3 H 6 7.0 mol C3 H 6
3 mol
determine extent of
reaction by applying
mole balance to
propylene
nC 3 H 6 nC 3 H 6
0 1
7.0 mol 10.0 mol

3 mol
what use are these calculated values?
f 0.093
limiting f 0.20
conversion 3of limiting reactant:
C H NH O C H N 3H O n i n i0 i
XS
XS
apply mole balance

to all remaining
1species
3 9
0.12 100
3 mol
nC 3 H 6 7.0 mol C3 H 6
nNH 3
nO2 0.21 0.78100 32 3 11.9

nC3 H 3 N 0 1 3.0 3
nN 2 0.79 0.78100 0 3 61.6

nH 2O 0 3 3.0 9
units not included and sig fig rules not followed to permit fit of all calculations
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
yCO2 yH2
K T
to an extent at temperature T based
yCOyH2O
on the equilibrium constant, K(T).
ni
where yi is the mole fraction of species y
ii
ntotal
ni ni0 i
Water-gas shift reaction:

CO g H2O g CO2 g H2 g
Assume 1 mole CO and 2 mole H2O
K(1105 K) = 1.00
nCO nCO 0 1 1
y

n 1
n 1
nH2O nH2O 0 1 2
nCO2
nH2
K T
CO2 0
H2 0
ntotal nCO nH2O nCO2 nH2 3
CO2 H2
yCOyH2O
ni
yi
ntotal
ni ni0 i

K(1105 K) = 1.00
nCO 1 0.333
nH2O 2 1.333
nCO2
nH2
ntotal 3
0.667
0.667
yCO yH

1 K T
1 2
yCOyH O
2
2 1 2
2 2 2 2
0.667mol
ni
yi
ntotal
ni ni0 i

K(1105 K) = 1.00
yCO 0.333/ 3 0.111
yH2O 1.333/ 3 0.444
yCO yH

1 K T
1 2
yCOyH O
2
yCO2 0.667/ 3 0.222
yH2 0.667/ 3 0.222 2 1 2

ntotal 3
2 2 2 2
ni
yi
ntotal
ni ni0 i
0.667mol
K(1105 K) = 1.00
yCO 0.333/ 3 0.111
yH2O 1.333/ 3 0.444
limiting reactant is CO
yCO2 0.667/ 3 0.222

yH2 0.667/ 3 0.222
ntotal 3
at equilibrium,
0.667mol
ni ni0 i
nCO 1 1 0.667
0.333mol
fractional conversion at equilibrium

0.333
f 1.001.00
0.667

K(1105 K) = 1.00
Multiple Reactions
C2 H 4 12 O2 C2 H 4O
C2 H 4 3O2 2CO2 2H2O
for j reactions of i species,n

i
mole balance becomes
ni 0 ij j
nC2H4 nC2H4 0 1 1 1 2
nO2 nO2 0 12 1 3 2 nCO2 nCO2 0 2 2

nH2O nH2O 0 2 2
nC H O nC H O 1 1
2 4
2 4
Multiple Reactions
C2 H 4 12 O2 C2 H 4O
C2 H 4 3O2 2CO2 2H2O
for j reactions of i species,n

i
mole balance becomes
ni 0 ij j
molesdesired
productformed
yield
molesformedat100%
conversion
withnosidereactions
molesdesired
productformed
selectivit
y
molesundesired
productformed
Multiple Reactions
100 moles A fed to a batch reactor
product composition: 10 mol A, 160 B, 10
C
A 2B
What is
1. fA?
2. YB?
3. SB/C?
4. 1, 2
A C
100 10
fA
0.9
100
Multiple Reactions
C
A 2B
What is
1. fA?
2. YB?
3. SB/C?
4. 1, 2
A C
160
YB
0
.
889
100 10 21
Multiple Reactions
C
A 2B
What is
1. fA?
2. YB?
3. SB/C?
4. 1, 2
A C
160
SB/ C
16
10
Multiple Reactions
C
A 2B
What is
1. fA?
2. YB?
3. SB/C?
4. 1, 2
A C
nB nBo B11
160 0 21
1 80
nA nAo A11 A22

10 100 1 2
2 90 1 10
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
C2H6 C2H4 H2
simple
form
Processes

of ethane
First consider molecular balances:
Molecular H2 balance: generation = output
generation H2 = 40
kmol CH
/min
2H2
6 C2H4 H2
Processes

of ethane
C2H6 balance: input = output +
consumption
100 kmol
C2H6H/min = n1 + (C2H6
C2H6 C2H
4
2
consumed)
Processes

of ethane
C2H4 balance: generation = output
(C2H4 generated) = n2
C2H6 C2H4 H2
Processes

of ethane
C
Atomic
Cmol
balance:
output
=2mol
2molC
100
C H 2molCinput
n
n
2 6 1molC2H6
1 1molC2H6
2 1molC2H4
Atomic
input
6molH
2molH = output
6molH
100
molC2H
H6balance:
40
n
1 1molC2H6 n2
1molC2H6
1molH2
C2H6 C2H4 H2
4molH
1molC2H4
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
x 2by
y 4 [3]
adding/subtracting
x 2y 4 [1] multiples of the others.
3x 6y 12 [2]
3[1] = [2]
2x z 2 [4]
4y z 6 [5]
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
3 4 2yof the
6y others.
12
adding/subtracting
x 2y 4 [1] multiples
3x 6y 12 [2]
12 6y 6y 12
12 12
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.
1 n
3
n
1 3.76n
3
3.76n
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.
A 2B [1]
B C
[2]
A 2C [3]
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

C2H6 C2H4 H2
at steady state
2 unknown labeled variables

+ 1 independent chemical reactions
- 3 independent molecular species balances
- 0 other equations relating unknown variables
0 degrees of freedom

C2H6 C2H4 H2
at steady state
H2 Balance: generation = output
genH2 40kmolH2

C2H6 C2H4 H2
at steady state
C2H6 Balance: input = output + consumption

kmolC2H6
min
1000
kmolH2
min
1 40
n
kmolC2H6
min
1 60
n
1kmolC2H6
1kmolH2

C2H6 C2H4 H2
at steady state
C2H4 Balance: generation = output
kmolH2
min
2 40
n
kmolC2H4
min
2 40
n
1kmolC2H4
1kmolH2
Atomic Species Balance

C2H6 C2H4 H2
All atomic species balances take the form

INPUT = OUTPUT
Degree-of-freedom analysis, ndf =

# unknown labeled variables
- # independent atomic species balances
- # molecular balances on independent nonreactive
species
- # other equations relating unknown variables

C2H6 C2H4 H2
All atomic species balances take the form

INPUT = OUTPUT
Degree-of-freedom analysis, ndf = 0 =

2 unknown labeled variables
- 2 independent atomic species balances
- 0 molecular balances on independent nonreactive
species
- 0 other equations relating unknown variables

C2H6 C2H4 H2
C Balance: input = output
100
kmolC2H4
min
2kmolC
1kmolC2H6
2kmolC
1 1kmolC2H6
1 n
2
100kmol n
2kmolC
2 1kmolC2H4

C2H6 C2H4 H2
H Balance: input = output
100
kmolC2H4
min
6kmolH
1kmolC2H6
40

n
kmolH2
min
2kmolH
1kmolH2
6kmolH
1 1kmolC2H6
4kmolH
2 1kmolC2H4
1 4n
2
600kmol 80kmol+6n

C2H6 C2H4 H2
Solve simultaneously
1 n
2
C: 100kmol n
1 4n
2
H: 600kmol 80kmol+6n
1 60kmolC2H6 / min
n
2 40kmolC2H4 / min
n
Extent of Reaction
The 3rd 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 ().
ni ni 0 ij j
j
Degree-of-freedom analysis for such an

approach:
ndf = # of unknown labeled variables
+ # independent reactions
- # independent nonreactive species
- # other relationships or specifications
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.
CH4 3 O2 CO 2 H2O
2
CH4 2 O2 CO2 2 H2O
The feed to the reactor contains 7.80 mol

% CH
4, 19.4 mol% O2, 72.8 mol% N2.
Methane undergoes 90.0% conversion,
and the effluent gas contains 8 mol CO2
per mole CO.
CH4
CH4 3 O2 CO 2 H2O
2
CH4 2 O2 CO2 2 H2O
The feed to the reactor contains 7.80 mol

% CH4, 19.4 mol% O2, 72.8 mol% N2.
Methane
undergoes 90.0% conversion,
and the effluent gas contains 8 mol CO2

per mole CO.
CH4
CH4 3 O2 CO2 H2O
2
CH4 2 O2 CO2 2 H2O
ndf = 5 unknowns
+ 2 independent reactions
- 5 expressions for (CH4, O2, CO, CO2,
H2O)
- 1 nonreactive species balance (N2)
- 1 specified methane conversion
=0
CH4
CH4 3 O2 CO2 H2O
2
CH4 2 O2 CO2 2 H2O
N2 balance: nonreactive species, INPUT =
molN
OUTPUT
nN 0.728 mol 100mol 72.8molN2
2
molCH
CH
specification:
100mol 0.780molCH
1 0.900 0.0780
n 4 conversion
CH4
mol
CH4
CH4 3 O2 CO2 H2O
2
CH4 2 O2 CO2 2 H2O
Extent of reaction balances:

nCH nCH 0 1 1 1 2
0.78 7.80 1 2
nCO 1
nCO nCO 0 1 1
nCO 8nCO 2
nCO nCO 0 1 2
nH O 21 22
nH O nH O 0 2 1 2 2
nO 19.4 3 1 22
2
3
nO nO 0 2 1 2 2
4
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.
overall
inputtoprocess
- outputfromprocess
reactant
conversion
inputtoprocess
singlepass
inputtoreactor- outputfromreactor
reactant
conversion
inputtoreactor

Recycle
overall
inputtoprocess
- outputfromprocess
reactant
conversion
inputtoprocess
singlepass
inputtoreactor- outputfromreactor
reactant
conversion
inputtoreactor

Recycle
overall
75molA/min- 0
100% 100%
conversion 75molA/min
singlepass 100molA/min- 25molA/min
100% 75%
conversion
100molA/min
Catalytic Propane
Dehydrogenation
C3H8 C3H6 H2
95% overall
conversion
Catalytic Propane
Dehydrogenation
95% overall
conversion
C3H8 C3H6 H2
Overall
Process
ndf = 3 unknowns (n6, n7, n8)

2 independent atomic balances (C and H)
1 relation (overall conversion)
=0
consider n6, n7, n8 known for further DOF analyses
Catalytic Propane
Dehydrogenation
ndf = 2
95% overall
conversion
C3H8 C3H6 H2
ndf = 4 unknowns (n9, n10, n1, n2)

2 balances (C3H8 and C3H6)
=2
Mixing
point
Catalytic Propane
Dehydrogenation
ndf = 3
ndf = 2
95% overall
conversion
C3H8 C3H6 H2
reactor
ndf = 5 unknowns (n3, n4, n5, n1, n2)

2 balances (C and H)
=3
Catalytic Propane
Dehydrogenation
ndf = 3
ndf = 2
ndf = 0
95% overall
conversion
C3H8 C3H6 H2
separator
ndf = 5 unknowns (n3, n4, n5, n9, n10)

3 balances (C3H8, C3H6, and H2)
2 relations (reactant and product recovery fractions)
=0
Catalytic Propane
Dehydrogenation
95% overall
conversion
C3H8 C3H6 H2
overall
n6 1 0.95 100mol 5molC3H8
conversion
relationship
Catalytic Propane
Dehydrogenation
95% overall
conversion
n6 5 molC3H8
C3H8 C3H6 H2
overall
C atomic balance
3molC
3molC
3molC
100mol 1mol
5
mol
C
H
n
3 8 1molC H
7 1molC H
CH
3 8
n7 95molC3H6
3 8
3 6
Catalytic Propane
Dehydrogenation
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
C3H8 C3H6 H2
overall
H atomic balance
8molH
8molH
100mol 1mol
5
mol
C
H
3 8 1molC H
CH
6molH
2molH
95molC3H6 1mol
n
8 1molH
CH
3 8
n8 95molH2
3 8
3 6
Catalytic Propane
Dehydrogenation
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
separator
given relations
n3 n3 900molC3H8
n6 0.00555
n10 0.0500n7 n10 4.75molC3H6
Catalytic Propane
Dehydrogenation
n3 900molC3H8
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
separator
n10 4.75 mol C

3H6
n3 n6 n9 n9 895mol C
3H8
propane balance
Catalytic Propane
Dehydrogenation
n3 900molC3H8
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
n9 895mol C
3H8
n10 4.75 mol C
3H6
100n9 n1 n1 995mol C
3H8
mixer
propane balance
Catalytic Propane
Dehydrogenation
n1 995mol C
3H8
n3 900molC3H8
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
n9 895mol C
3H8
n10 4.75 mol C
3H6
n10 n2 n2 4.75 mol C

3H6
95% overall
conversion
mixer
propylene balance
Catalytic Propane
Dehydrogenation
n1 995mol C
3H8
n3 900molC3H8
n2 4.75 mol C
3H6
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
reactor
n9 895mol C
3H8
n10 4.75 mol C
3H6
C atomic balance
3molC
3molC
995molC3H8 1mol
4
.75
mol
C
H
3 6 1molC H
CH
3molC
3molC
900molC3H8 1mol
n
4 1molC H
CH
3 8
3 6
3 8
n4 99.75molC3H6
3 6
Catalytic Propane
Dehydrogenation
n3 900molC3H8
n1 995mol C
3H8
n4 99.75molC3H6
n2 4.75 mol C
3H6
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
reactor
n9 895mol C
3H8
n10 4.75 mol C
3H6
H atomic balance
8molH
6molH
995molC3H8 1mol
4
.75
mol
C
H
3 6 1molC H
CH
8molH
6molH
2molH
900molC3H8 1mol
99
.
75
mol
C
H
n
3 6 1molC H
5 1molH
CH
3 8
3 6
3 8
n5 95molH2
3 6
Catalytic Propane
Dehydrogenation
n1 995mol C
3H8
n2 4.75 mol C
3H6
n3 900molC3H8
n4 99.75molC3H6
n5 95molH2
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
n9 895mol C
3H8
n10 4.75 mol C
3H6
single-pass
conversion
995molC3H8 900molC3H8
fsinglepass
100% 9.55%
995molC3H8
Catalytic Propane
Dehydrogenation
fsinglepass 9.55%
n1 995mol C
3H8
n2 4.75 mol C
3H6
n3 900molC3H8
n4 99.75molC3H6
n5 95molH2
95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
n9 895mol C
3H8
n10 4.75 mol C
3H6
recycle
ratio
895mol 4.75mol
n9 n10
molrecycle
R
9.0 mol
freshfeed
100molfeed
100mol
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.
mixed fresh feed
and recycle is a
convenient
basis selection
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
ndf = 7 unknowns (n0, x0C, np, x5C, x5H, n3,
n4) + 1 rxn
- 5 independent species balances =
3
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
ndf = 4 unknowns (n1, n2, n3, n4) + 1 rxn
4 independent species balances
1 single pass conversion = 0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
ndf = 3 unknowns (n5, x5C, X5H)
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
ndf = 3 unknowns (n0, x0C, nr)
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
ndf = 1 unknowns (np)
1 independent species
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
investigate
mole balances and
their solution in
balance
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
Combustion Chemistry
When a fuel is burned
C forms CO2 (complete) or CO (partial
combustion)
H forms H2O
S forms SO2
N forms NO2 (above 1800C)
Air is used as the source of oxygen. DRY

usually safe to assume:
air analysis:
79 mol% N2
78.03 mol% N2
20.99 mol% O2
0.94 mol% Ar
0.03 mol% CO2
21 mol% O2
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% N2, 15.0% CO2, 10.0% O2, 15.0% H2O
Dry basis analysis:
60/(60+15+10) = 0.706 mol N2/mol
15/(60+15+10) = 0.176 mol CO2/mol
10/(60+15+10) = 0.118 mol O2/mol
Stack gas contains (mol) on a dry basis:
65% N2, 14% CO2, 10% O2, 11% CO
xH2O = 0.0700 (humidity measurement)
lbmolH2O
0.0700
Wet basis analysis:
lbmoldry gas
0.9300
lb wet gas
lb wet gas
assume 100 mole dry gas basis xH O 7.53 0.0700

2
107.5
65
xN2
0.605
H2O
7.53 mole
107.5
xCO2 14 0.130
107.5
xO2 10 0.0930
107.5
xCO 11 0.102
107.5
65 mole N2
14 mole CO2
10 mole O2
11 mole CO
total = 107.5 mole
lbmolH2O
0.0753
lb dry gas
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
O2 needed to completely combust the fuel
to CO2 and H2O.
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
moles air fed
- moles air theoretical
air.
% excess air
=
100%
moles air theoretical

C4H10 13O2 4CO2 5H2O
2
nC4H10 = 100 mol/hr;
100molC4H10
nO2 theoretica
l
hr
650molO2
nair theoretical
hr
nair = 5000 mol/hr

6.5molO2
molO2
650
hr
molC4H10
4.76molair
molair
3094
hr
molO2
50003094
% excess air
100% 61.6%
3094
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 O2 feed rate from the specifed

percent excess oxygen or air
3. If multiple reactions, use atomic balances
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
degree-of-freedom
analysis
fC2H6 = 0.9
25% of the ethane burned forms CO
ndf =
=0
7 unknowns
3 atomic balances
1 nitrogen balance
1 excess air specification
1 ethane conversion specification
1 CO/CO2 ratio specification
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
excess air
specification
fC2H6 = 0.9
100molC2H6 3.5molO2

350molO2
nO2 theoretica

l
molC2H6
0.21n0 1.5 350molO2

n0 2500molair
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
ethane
conversion
specification
fC2H6 = 0.9
n0 2500mol air
n1 1 0.90 100molC2H6 10.0molC2H6
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
CO/CO2 ratio
specification
n1 10.0 mol C
2H6
fC2H6 = 0.9
n0 2500mol air
2molCOgen
45.0molCO
n4 0.25 0.9 100molC2H6
1molC2H6 react
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
nitrogen
balance
fC2H6 = 0.9
n1 10.0 mol C
2H6
n4 45.0 mol C
O
n0 2500mol air
25% of the
ethane burned forms CO
n3 0.79 2500molair 1975molN2
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
atomic C
balance
fC2H6 = 0.9
n0 2500mol air
n1 10.0 mol C
2H6
n3 1975mol N
2
n4 45.0 mol C
O
25% of the
2molC
2molC
1molC
1molC
100molC2H6 1mol
n
1
4
5
CH
1molC H
1molCO
1molCO
2 6
n5 135molCO2
2 6
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
atomic H
balance
n0 2500mol air
fC2H6 = 0.9
n1 10.0 mol C
2H6
n3 1975mol N
2
n4 45.0 mol C
O
n5 135mol C
O2
25% of the
6molH
6molH
2molH
100molC2H6 1mol
10
mol
C
H
n
2
6
6
CH
1molC H
1molH O
2 6
n6 270molH2O
2 6
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
atomic O
balance
fC2H6 = 0.9
n0 2500mol air
n1 10.0 mol C
2H6
n3 1975mol N
2
n4 45.0 mol C
O
n5 135mol C
O2
n6 270molH2O
25% of the
molO
2molO
1molO
525molO2 12mol
4
5
mol
CO
2 1molO
O
1molCO
molO
1molO
135molCO2 12mol
CO 270molH2O 1molH O
2
n2 232molO2
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
stack gas
composition
(dry basis)
n0 2500mol air
sum102321974 45135 2396

y1 10 2396 0.00417molC2H6 mol
y2 2322396 0.0970molO2 mol
y3 19742396 0.824molN2 mol
y4 45 2396 0.019molCOmol
y5 1352396 0.0563molCO2 mol
fC2H6 = 0.9
n1 10.0 mol C
2H6
n2 232mol O
2
n3 1975mol N
2
n4 45.0 mol C
O
n5 135mol C
O2
n6 270molH2O
25% of the
270mol H
2O
2396mol dry stack gas
mol H
2O
0.113
mol dry stack gas

Material Balances Without Chemical Reaction

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Material Balances Without Chemical Reaction

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Material Balances

The General Balance

Consider the following continuous process

The General Balance

A balance of a conserved quantity (mass,

input + generation output consumption =

input: enters through system boundaries

The General Balance

Each year, 50,000 people move into a city;

input + generation output consumption =

input: 50,000 people/year

The General Balance

Each year, 50,000 people move into a city;

input + generation output consumption =

If the balance substance is a nonreactive

If a system is at steady state,

input + generation = output +

General species balance

input + generation output consumption =

500 kg B/h = 450 kg B/h + m2

Total mass balance

Integral Balances on Batch

at t=0, there is n0 moles of NH3 in the reactor

therefore, for a batch process,

Batch Mixing Process

Batch Mixing Process

Total Mass Balance

200 g + 150 g = m = 350 g

kmol air 0.900 kmol air

accumulation input generation output consumption

0.659kg 103 L 1kmol

output 0.100nt1 0.100 0.111 kmol t1

1. Write the values of all known stream

2. Assign algebraic symbols to unknown

0.79 mol N2/mol

320C, 1.4 atm

General Procedure Single

1. Choose as a basis of calculation an

General Procedure Single

2. Draw flowchart and fill in all variable

Flowchart is completely labeled if you can

General Procedure Single

3. Express what the problem statement ask

This operation is carried out for the

Overall Material balance:

This operation used in the chemical

Overall Material balance:

The operation is used in the chemical

Material balance of inert gas:

The operation used in the chemical

Overall material balance:

Extraction operation is carried out for the

Material Balance of solids:

Material balance of moisture:

Centrifuge machines, Drum filters, Press

Overall Material Balance:

Overall Material balance:

Equipments are Stirred tanks, Vacuum

Overall material balance:

Air Humidification and

An experiment on the growth rate of

Air Humidification and

An experiment on the growth rate of