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 city’s (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 0 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
0.400 g CH3OH 0.700 g CH3OH 
x g CH3OH 
200g 
g
150g 
g

mg 
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
kmol air 0.900 kmol air kmol
0.100  n
min kmol min
kmol
n  0.111
min

Processes
• integral hexane balance
accumulation  input  generation  output  consumption
accumulation  output
30.659kg 103 L 1kmol
accumulation  n  10.0m   3 
L m 86.2kg
accumulation  n  76.45 kmol C6 H14

output  0.100nt1  0.100 0.111 kmol t1
min 
t1  6880 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
on the chart.
400 mol/h
0.21 mol O2/mol
0.79 mol N2/mol
320°C, 1.4 atm
2. Assign algebraic symbols to unknown

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

2 (1-y) (mol N /mol)
2
0.79 mol N2/mol 320°C, 1.4 atm
320°C, 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 air-
Moisture 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 
 2
n   n3  
 min   min  mol 
 molH2O   mol  0.15molH2O  mol
 1 .11   n
 3    n
 3  74.1
 min   min  mol  min
Oxygenation
total mole balance:

1 n
0.200n 1 n
2 n
3
1.200 1.11mol
min   1.11min   74.1min
mol mol
 1  60.8mol
n min
Oxygenation
nitrogen balance:
 n 1 mol
min  0 .79 molN
2
mol   n 3  0.985  y   mol 
molN
2
 60.8molmin   0.79 molN2

mol    74 .1 mol
min  0 . 985  y  mol 
molN
2
y  0.337mol
O2
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 h
Flowchart Scaling
1250lbmolh lbmolhr
100mol mol
• top: 50.0mol 12.5lbmolhr  625lbmol

mol h
Flowchart Scaling
1250lbmolh lbmolhr
100mol mol
• bottom:12.5molA 12.5lbmolAhr  156lbmolA

molA h
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 / ρH2O = 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/
= 250 kg 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 ρ)
 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 ρ)
 process specification: 95% of the water is
condensed
• ndf = 5 – (3 + 1 + 1) = 0 Solvable
• Density relationship n  
 2  225LH2hO(l) 1.00kgHL2O(l)  1molH2O
18.0103kg

• 95% condensation specification  2  0.95 0.100n
n  1
• O2 Balance  1 0.900 0.21  n
n 3
• N2 Balance  1 0.900 0.79  n
n 4
• H2O Balance  1 0.100  n
n 2 n 5
• outlet gas composition yO2  n  total; yN2  n
3 n  total; yH2O  n
4 n 5 n
 total
• total outlet gas flow rate  total  n
n 3 n
4 n
5
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
example 2d. confirm every component mass flow in every
• Ex. 4.3-5
process stream can be expressed in terms of
labeled quantities and variables.
2e. process specification

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

m  
 1   2000hL  0.872kg
L  1744h
kg
ii. benzene split fraction

 B3   0.08 0.45m
m  1  62.8 kghB
. benzene balance iv. toluene balance

 0.45m
 1 m
 2yB2  m
 B3  0.55m  2 1 yB2   m
 1 m  T3
 2  766kghB
m  T3  915kghT
m
Distillation Column
example
• Ex. 4.3-5
8. Calculate additional quantities
=766 kg/h
=0.94
2 =0.05
=1744 kg/h 8
yB3  m  3  62.8kghB
 B3 m h  0.064kg
978kg kgB
yT3  1 0.064 0.936kgT

kg
=62.8 kg B/h
 3  62.8 kghB  915kghT  978kg
m 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.
 0.983n4   0.983n5   0.983 100

 0.017n4   0.017n5   0.017 100
Balances on an Air
Conditioner
 Overall: n = 2 variables (n , n ) – 2 balances
df 1 3 =requested
To find 0
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=
 Splitter: ndf = 2 variables (n4, n5) – 1 balances is 1no need to solve
the cooler or splitter
balances.
Balances on an Air
Conditioner
• 0.960n1  0.983100 n1  102.4mol
overall dry air balance
• overall mole balancen1  n3  100 n3  2.4 mol H2O condensed

Balances on an Air
Conditioner n n n
• overall mole balance 1 5 2
• water balance  0.04n1   0.017n5   0.023n2
n2  392.5mol; n5  290mol
 solved simultaneously:
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
m  5
 4 m
Process
•Feed/recycle mixer:
 ndf = 3 unknowns (m6, m1, x1) – 2 balances = 1
 underspecified
 4  0.95 m
m  5
 4 m
Process
•Evaporator:
 ndf = 3 unknowns (m3, m1, x1) – 2 balances = 1
 underspecified
 4  0.95 m
m  5
 4 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
m  5
 4 m
Process
•Overall system:
solve simultaneously for m and m 4 5
 K2CrO4 balance  0.333 4500 kghK  m

 4   0.364 m
5
 water balance  0.667 4500 kghK  m
 2   0.636m5
 total mass balance 4500kgh  m2  m4  m5
  
 specification  4  0.95 m
m  4 m  5
 4  1470kgKcrystals
m h
 5  77.5kgsolution
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Process
•Overall system:
solve for m with knowns m and m 2 4 5

 4   0.364m
5
 2   0.636m
5
  
 specification m  2950
2
kgH2O
h
 4  0.95 m
m  4 m  5
m h
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Process
•Overall system:
only 3 equations are independent
 4   0.364m
5
 2   0.636m
5
  
 specification m  2950
2
kgH2O
h
 4  0.95 m
m  4 m  5
m h
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Process
•Crystallizer:
solve simultaneously for m and m 3 6
 total mass balance  3 m

m  4 m
 5 m
6
m 3   1470 77.5 kgh  m6

 water balance  0.506m  3   0.636m
 5   0.636m
6
 2  2950kgHh2O
m
 3  97.4 kg
m h  1.257
m6
 3  7200kg
m  4  1470kgKcrystals
m h
h
m h
0.364kgK/kgsolu
 6  5650kg
m h
0.636kgW/kgsolu
Process
•feed/recycle mixer:
 total mass balance 4500kg
h  m
 6  m
 1  m
 1  kg
10150
h
 water or K2CRO4 balance could be used tp find

x1 if desired
 2  2950kgHh2O
m
 1  10150
m kg
h  3  7200kg
m  4  1470kgKcrystals
m h
h
m h
0.364kgK/kgsolu
 6  5650kg
m h
0.636kgW/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.
2S→2S
4O+2O→6O
• 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
what rate min  0.50
is water formed?  200
1lbmolC H
4 8 min
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
to the stoichiometric proportion.f XS 
n A   n A 
feed stoich
n A stoich
5 4
A + 2B → 2C 
4
 0.25

Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
 
nA
reacted
 
nA
fed
A + 2B → 2C

0 0
fA   0.0 f B   0.0
5 8
Limiting and Excess
Reactants
amount fed. f
 
nA
reacted
 
nA
fed
A + 2B → 2C

1 4
fA   0.2 f B   0.25
5 8
Limiting and Excess
Reactants
amount fed. f
 
nA
reacted
 
nA
fed
A + 2B → 2C

2 4
fA   0.4 f B   0.5
5 8
Limiting and Excess
Reactants
amount fed. f
 
nA
reacted
 
nA
fed
A + 2B → 2C

3 6
fA   0.6 f B   0.75
5 8
Limiting and Excess
Reactants
amount fed. f
 
nA
reacted
 
nA
fed
A + 2B → 2C

4 8
fA   0.8 f B   1.0
5 8
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
  i coefficients: νA= -1,
0 νB = -2, νC =
2
A + 2B → 2C
 
n A  n A0   n B  n B0  2 nC  nC0  2
Extent of Reaction
chemical reaction .
0 νB = -2, νC =
2
A + 2B → 2C
 
nA  5    5 n B  8  2  8 nC  0  2  0
Extent of Reaction
chemical reaction .
  i coefficients: νA =-1,
1 νB = -2, νC =
2
A + 2B → 2C
 
nA  5    4 n B  8  2  6 nC  0  2  2
Extent of Reaction
chemical reaction .
2 νB = -2, νC =
2
A + 2B → 2C
 
nA  5    3 n B  8  2  4 nC  0  2  4
Extent of Reaction
chemical reaction .
3 νB = -2, νC =
2
A + 2B → 2C
 
nA  5    2 n B  8  2  2 nC  0  2  6
Extent of Reaction
chemical reaction .
4 νB = -2, νC =
2
A + 2B → 2C
 
nA  5    1 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 ξ?
 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
C H  NH of 3 limiting reactant:
O  C H N  3H O
3 6 3 2 3 3 3 2
determine limiting reactant
nNH 3 0  0.120  100 0.100 100 1.20

nC 3 H 6
nNH 3
nC H  3
stoich
 1 1 1
6
nO 2
nC H   0.780  0.21 100 0.100  100 1.64
3 0 6
nO 2
nC H 
3 stoich6
 1.5 1 1.5
limiting f  0.20 f  0.093
conversion
C H  NH of
XS
3 limiting reactant:
XS
O  C H N  3H O
3 6 3 2 3 3 3 2
 
determine fractional excesses
 1 mol NH 3 
 stoich
n NH 3  10.0 mol C3 H6 
 1 mol C 3 H 6 
 10.0 mol NH 3
NH  NH 
f XS NH  NH 3
3 0 3 stoich
 12.010.0  0.20
10.0
3 stoich
 1.5 mol O 

 O stoich
n 2
 10.0 mol C 3 6  1 mol C H   15.0 mol O2
H
3
2
O  O 
 XS O
f 
2  
O
2 0

2 stoich
16.415.0
15.0
2 stoich
 0.093
limiting f  0.20 f  0.093
conversion
C H  NH of
XS
XS
O  C H N  3H O
3 6 3 2 3 3 3 2
 
 
nC 3 H 6  1 f nC 3 H 6 0  1  0.3010.0 mol C3H6  7.0 mol C3 H6
use fractional
conversion to
 determine amount of
propylene that leaves
the reactor
limiting f  0.20 f  0.093
conversion
C3 H6  NH3 of
XS
XS
O  C3 H3 N  3H2O n i  n i0   i 
2 3
 
determine extent of
nC 3 H 6  7.0 mol C3 H 6   3 mol 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

limiting f  0.20 what use are these calculated values?
f  0.093
conversion 3of limiting reactant:
XS XS
C H  NH  O  C H N  3H O n i  n i0   i 
3 6 3 2 2 3 3 2
 
nC 3 H 6  7.0 mol C3 H 6   3 mol apply mole balance

to all remaining
nNH 3   0.12 100
    1species
 3  9
 nO2   0.21 0.78100     32   3  11.9
nC3 H 3 N   0     1 3.0   3
nN 2   0.79  0.78100    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
 ii 
where yi is the mole fraction of species y
ntotal
ni  ni0   i
CO g  H2O g  CO2 g  H2 g

• Water-gas shift reaction:
 Assume 1 mole CO and 2 mole H2O
 K(1105 K) = 1.00
nCO   nCO 0    1    1   y y
  K T 
CO2 H2
nH2O  nH2O 0    1    2   yCOyH2O
nCO2  n     1    ni
CO2 0 yi 
nH2  n     1   
H2 0
ntotal
ni  ni0   i
ntotal  nCO  nH2O  nCO2  nH2  3
CO g  H2O g  CO2 g  H2 g

 K(1105 K) = 1.00
nCO  1   0.333
     yCO yH
nH2O  2   1.333  1  K T  2 2
 1   2  yCOyH O
nCO2    0.667 ni
2
yi 
nH2    0.667 2   1   2   ntotal
ntotal  3 2  2 2    2 ni  ni0   i
  0.667mol
CO g  H2O g  CO2 g  H2 g

 K(1105 K) = 1.00
yCO  0.333/ 3  0.111
     yCO yH
yH2O  1.333/ 3  0.444  1  K T  2 2
 1   2  yCOyH O
yCO2  0.667/ 3  0.222 ni
2
yi 
yH2  0.667/ 3  0.222 2   1   2   ntotal
ntotal  3 2  2 2    2 ni  ni0   i
  0.667mol
CO g  H2O g  CO2 g  H2 g

 K(1105 K) = 1.00
yCO  0.333/ 3  0.111
limiting reactant is CO
yH2O  1.333/ 3  0.444
at equilibrium, ni  ni0   i
yCO2  0.667/ 3  0.222   0.667mol
nCO  1   1 0.667
yH2  0.667/ 3  0.222  0.333mol

ntotal  3 fractional conversion at equilibrium
f  1.001.00
0.333
 0.667
CO g  H2O g  CO2 g  H2 g

 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   ni  0    ij j
mole balance becomes
j

 
nC2H4  nC2H4 0    1 1    1 2
   
nO2  nO2 0    12  1    3 2 nCO2  nCO2 0    2 2
 
nC H O  nC H O    1 1
2 4 2 4 0
 
nH2O  nH2O 0    2 2
Multiple Reactions
C2 H 4  12 O2  C2 H 4O
C2 H 4  3O2  2CO2  2H2O
for j reactions of i species,n
i   ni  0    ij j
mole balance becomes
j
 molesdesired
productformed
yield
molesformedat100%
conversion
withnosidereactions
molesdesired
productformed
y
selectivit
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 A C
1. fA?
100 10
2. YB? fA   0.9
3. SB/C? 100
4. ξ1, ξ2
Multiple Reactions
C A  2B
What is A C
1. fA?
160
2. YB? YB   0.889
3. SB/C?  100 10  21 
4. ξ1, ξ2
Multiple Reactions
C A  2B
What is A C
1. fA?
160
2. YB? SB/ C   16
3. SB/C? 10
4. ξ1, ξ2
Multiple Reactions
C A  2B
What is A C
1. fA? nB  nBo  B11 nA  nAo   A11   A22
2. YB? 160 0  21 10 100 1  2
3. SB/C? 1  80 2  90 1  10
4. ξ1, ξ2
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
6  C2H4  H2
2H2
Processes
of ethane
C2H6 balance: input = output +

consumption
100 kmol C2H6H/min = n1 + (C2H6
C2H6  C2H4 2
consumed)
Processes
of ethane
C2H4 balance: generation = output

(C2H4 generated) = n2
C2H6  C2H4  H2
Processes
of ethane
Atomic Cmol
100 balance: 
C H 2molCinput
n =2mol 
output
2 6 1molC2H6
C
n
 2molC
1 1molC2H6  
2 1molC2H4 
Atomic
100molC2H 
H6balance:
6molH
1molC2H6  
input
40 
1molH2  n 
2molH = output

1 1molC2H6  n2
6molH    4molH
1molC2H4 
C2H6  C2H4  H2
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]
x  2y  4 [1] multiples of the others.
adding/subtracting
2x  z  2 [4]
3x  6y  12 [2]
4y  z  6 [5]
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
3 4  2yof the
x  2y  4 [1] multiples
adding/subtracting  12
6y others.
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
n 3
 1  3.76n
3.76n 3
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
1000 kmolC2H6
min n
 1  40 kmolH2
min  1kmolC2H6
1kmolH2 
kmolC2H6
 1  60
n min
C2H6  C2H4  H2
at steady state
C2H4 Balance: generation = output

 2  40
n kmolH2
min  1kmolC2H4
1kmolH2 
kmolC2H4
 2  40
n min
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
100kmolC2H4
min  2kmolC
1kmolC2H6   n 2kmolC
1 1kmolC2H6   n 2kmolC
2 1kmolC2H4 
100kmol n
1 n
2
C2H6  C2H4  H2
H Balance: input = output
100kmolC2H4
min  6kmolH
1kmolC2H6   40kmolH2
min  2kmolH
1kmolH2 
n  6kmolH
1 1kmolC2H6   n 4kmolH
2 1kmolC2H4 
600kmol 80kmol+6n
 1  4n
2
C2H6  C2H4  H2
Solve simultaneously
C: 100kmol n
1 n
2
H: 600kmol 80kmol+6n  1  4n
2
 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
ni   ni  0    ij j
terms of extents of reaction (ξ).
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  CO2 H2O

2
CH4 2 O2  CO2  2 H2O
ndf = 5 unknowns

+ 2 independent reactions
- 5 expressions for ξ (CH4, O2, CO, CO2,
H2O)
- 1 nonreactive species balance (N2)
- 1 specified methane conversion
=0
CH4
CH4  3 O2  CO2 H2O

2
CH4 2 O2  CO2  2 H2O
N2 balance: nonreactive species, INPUT =

nN  0.728 mol  100mol  72.8molN2
OUTPUT molN2

2
CH
CH4  1 0.900  0.0780
n 4 conversion molCH
mol  100mol  0.780molCH
specification:
4
4
CH4
CH4  3 O2  CO2 H2O

2
CH4 2 O2  CO2  2 H2O
Extent of reaction balances:

nCH  nCH  0    1 1    1 2
4 4
0.78 7.80 1  2
nCO   nCO 0    1 1 nCO  1
nCO  nCO  0    1 2
nCO  8nCO  2
2
2 2
nH O  21 22
nH O  nH O  0    2 1    2 2
2
2 2 nO  19.4 3 1  22
nO  nO  0    2  1    2 2
2 2
3
2 2

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 95% overall
conversion
C3H8  C3H6 H2

Catalytic Propane
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
Mixing

point
ndf = 4 unknowns (n9, n10, n1, n2)
– 2 balances (C3H8 and C3H6)
=2
Catalytic Propane
Dehydrogenation
ndf = 2
ndf = 3
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 = 2
ndf = 3 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
conversion
C3H8  C3H6 H2
overall
 conversion
relationship
n6   1 0.95 100mol  5molC3H8

Catalytic Propane
conversion
n6  5 molC3H8
C3H8  C3H6 H2
overall
 C atomic balance
 100mol  1mol
3molC
CH
3 8
   5mol
C H   3molC
3 8 1molC H 
3 8
 n7 1molC H 
 3molC
3 6
n7  95molC3H6
Catalytic Propane
conversion
n6  5 molC3H8
n7  95molC3H6
C3H8  C3H6 H2
overall
 H atomic balance
 100mol  1mol
8molH
CH    5mol C3 8 1molC H 
H   8molH
  95molC3H6   1mol  8 1molH 


3 8 3 8
6molH
CH 
3 6
n 2molH
2
n8  95molH2
Catalytic Propane
conversion
n6  5 molC3H8
n7  95molC3H6
n8  95molH2
C3H8  C3H6 H2
separator
 given relations
n6   0.00555 n3  n3  900molC3H8

n10   0.0500n7  n10  4.75molC3H6
Catalytic Propane
conversion
n3  900molC3H8 n6  5 molC3H8
n7  95molC3H6
n8  95molH2
C3H8  C3H6 H2
separator
 propane balance
n10  4.75 mol C
3H6

n3  n6 n9  n9  895mol C
3H8

Catalytic Propane
conversion
n3  900molC3H8 n6  5 molC3H8
n7  95molC3H6
n8  95molH2
C3H8  C3H6 H2
mixer
n9  895mol C3H8 propane balance
 n10  4.75 mol C
3H6


100n9 n1  n1  995mol C

3H8

Catalytic Propane
conversion
n1  995mol C n3  900molC3H8 n6  5 molC3H8

3H8
n7  95molC3H6
n8  95molH2
 C3H8  C3H6 H2
mixer
n9  895mol C3H8 propylene balance
 n10  4.75 mol C
3H6


n10  n2  n2  4.75 mol C

3H6

Catalytic Propane
conversion

3H8
n7  95molC3H6
n2  4.75 mol C
3H6
n8  95molH2
 C3H8  C3H6 H2

reactor
n9  895mol C3H8 C atomic balance
 n10  4.75 mol C
3H6
 995molC3H8   1mol   3 6 1molC H 

 

 3molC
CH  4 .75 mol C H 3molC
  900molC3H8   1mol  4 1molC H 


3 8 3 6
3molC
CH   n  3molC
3 8 3 6
n4  99.75molC3H6
Catalytic Propane
conversion

3H8
n4  99.75molC3H6 n7  95molC3H6
n2  4.75 mol C
3H6
n8  95molH2
 C3H8  C3H6 H2

reactor
n9  895mol C3H8 H atomic balance
 n10  4.75 mol C
3H6
 995molC3H8   1mol  3 6 1molC H 




8molH
CH   4 .75 molC H  6molH
  900molC3H8   1mol    5 1molH 


3 8 3 6
8molH
CH   99.75
3 8
mol C H  6molH
3 6 1molC H  n 2molH
3 6 2
n5  95molH2
Catalytic Propane
conversion

3H8
n4  99.75molC3H6 n7  95molC3H6
n2  4.75 mol C
3H6
n5  95molH2 n8  95molH2
 C3H8  C3H6 H2

single-pass
n9  895mol C3H8
 n10  4.75 mol C
3H6 conversion


fsinglepass
 995molC3H8    900molC3H8 
 100% 9.55%
 995molC3H8 
Catalytic Propane
Dehydrogenation fsinglepass 9.55% 95% overall
conversion

3H8
n4  99.75molC3H6 n7  95molC3H6
n2  4.75 mol C
3H6
n5  95molH2 n8  95molH2
 C3H8  C3H6 H2

recycle
n9  895mol C3H8
 n10  4.75 mol C
3H6 ratio


n9  n10  895mol   4.75mol

R   9.0 mol
molrecycle
 100molfeed  100mol freshfeed

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 fsinglepass 60%
CO2 3H2  CH3OHH2O


Methanol Synthesis
• ndf = 7 unknowns (n0, x0C, np, x5C, x5H, n3,
n4) + 1 rxn
- 5 independent species balances =
3
fsinglepass 60%


Methanol Synthesis
• ndf = 4 unknowns (n1, n2, n3, n4) + 1 rxn
– 4 independent species balances
– 1 single pass conversion = 0


Methanol Synthesis
• ndf = 3 unknowns (n5, x5C, X5H)
=0


Methanol Synthesis
• ndf = 3 unknowns (n0, x0C, nr)
=0


Methanol Synthesis
investigate
• ndf = 1 unknowns (np) mole balances and
their solution in
– 1 independent species balance
the text
=0


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 world’s 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 1800°C)
• Air is used as the source of oxygen. DRY
usually safe to assume:
air analysis: 79 mol% N2
 78.03 mol% N2 21 mol% O2
 20.99 mol% O2
 0.94 mol% Ar
 0.03 mol% CO2
• 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 lbmoldry gas lbmolH2O
0.0700  0.9300  0.0753
 Wet basis analysis: lb wet gas lb wet gas lb dry gas
• assume 100 mole dry gas basis xH O  7.53  0.0700

2 107.5
 H2O
– 7.53 mole  65
xN2   0.605
107.5
– 65 mole N2
xCO2  14  0.130
– 14 mole CO2 107.5
– 10 mole O2 xO2  10  0.0930

107.5
– 11 mole CO xCO  11  0.102
107.5
– total = 107.5 mole

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
air. moles air fed
- moles air theoretical
% excess air
= 100%
moles air theoretical
C4H10  13O2  4CO2  5H2O
2
nC4H10 = 100 mol/hr; nair = 5000 mol/hr
 6.5molO2 
 

nO2 theoretica
 100molC4H10 
hr
    650
molO2
   molC4H10  hr
l
 650molO2   4.76molair molair

 nair theoretical       3094
 hr   molO2  hr
50003094

% 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  2CO3H2O
2
degree-of-freedom
analysis 
fC2H6 = 0.9
25% of the ethane burned forms CO
ndf = 7 unknowns
- 3 atomic balances
- 1 nitrogen balance
- 1 excess air specification
- 1 ethane conversion specification
- 1 CO/CO2 ratio specification
=0
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2
excess air
specification 
fC2H6 = 0.9
 100molC2H6   3.5molO2 
 
nO2 theoretica      350molO2
  molC2H6 
l

0.21n0  1.5 350molO2 
n0  2500molair
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2
ethane
conversion 
fC2H6 = 0.9
specification
n0  2500mol air


n1   1 0.90  100molC2H6   10.0molC2H6

C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1 10.0 mol C
2H6
CO/CO2 ratio
specification 
fC2H6 = 0.9

n0  2500mol air


 2molCOgen 
n4   0.25 0.9  100molC2H6     45.0molCO
 1molC2H6 react
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1  10.0 mol C
2H6
nitrogen
balance 
fC2H6 = 0.9
 n4  45.0 mol C
O
n0  2500mol air
ethane burned forms CO

25% of the

n3   0.79 2500molair  1975molN2

C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1  10.0 mol C
2H6
atomic C
n3  1975mol N
balance 
fC2H6 = 0.9
2
 n4  45.0 mol C
O
n0  2500mol air 

25% of the

 100molC2H6   1mol
2molC
CH  
2 6
n1  2molC
1molC H   n4 
2 6
1molC
1molCO   n5  1molCO 
1molC
2
n5  135molCO2
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1  10.0 mol C
2H6
atomic H
n3  1975mol N
balance 
fC2H6 = 0.9
2
 n4  45.0 mol C
O
n5  135mol CO2
n0  2500mol air 

25% of the


 100molC2H6   1mol
6molH
CH 
2 6
  10mol
C 2H6   6molH
1molC H   n6  1molH O 
2molH
2 6 2
n6  270molH2O
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1  10.0 mol C
2H6
atomic O
n3  1975mol N
balance 
fC2H6 = 0.9
2
 n4  45.0 mol C
O
n5  135mol CO2
n0  2500mol air  n6  270molH2O
25% of the



 525molO2   12mol
molO
O   n  2molO
2 1molO    45molCO   1molCO
1molO
  135molCO2   12molCO    270molH2O  1molH O 

2 2
molO 1molO
2 2
n2  232molO2
C2H6  7 O2  2CO2 3H2O
2
C2H6  5 O2  2CO3H2O
2 n1  10.0 mol C
2H6
n2  232mol O
stack gas 2
n3  1975mol N
composition 
fC2H6 = 0.9
2
 n4  45.0 mol C
O
(dry basis)  n5  135mol CO2
n0  2500mol air  n6  270molH2O
25% of the



sum102321974 45135 2396
270mol H2O
y1 10 2396 0.00417molC2H6 mol
2396mol dry stack gas
y2  2322396 0.0970molO2 mol
mol H2O
y3 19742396 0.824molN2 mol  0.113
mol dry stack gas
y4  45 2396 0.019molCOmol
y5 1352396 0.0563molCO2 mol


Material Balances Without Chemical Reaction

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Material Balances

• Maybe methane is…

input + generation – output – consumption =

 input: enters through system boundaries

 input: 50,000 people/year

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

 ∴ the city’s (system) population is decreasing

• If the balance substance is a nonreactive

• If a system is at steady state,

input + generation = output +

• If the balance is for a nonreactive species

• General species balance

2. Assign algebraic symbols to unknown

chart. 0.21 mol O /mol

• This operation is carried out for the

• Material Balance of Component A:

• This operation used in the chemical

• The operation is used in the chemical

• The operation used in the chemical

If A is the Solute to be extracted, Then the

A in Feed solution= A in Extract Phase +A in

• Material Balance of solids:

• Material balance of solids.

• Centrifuge machines, Drum filters, Press

• Material Balance of Solids:

• Equipments are Stirred tanks, Vacuum

• Material balance of crystal solute:

Crystallization of the dissolved solids from

A. liquid water, fed at a rate of 20.0 cm3/min

A. liquid water, fed at a rate of 20.0 cm3/min

Calculate n2 from volumetric flowrate and density:

20.0cm3H2O 1.00gH2O 1mol molH2O

total mole balance:

 60.8molmin   0.79 molN2

• The flowchart is balanced because

• feed: 100mol 12.5lbmolhr  1250lbmol

• top: 50.0mol 12.5lbmolhr  625lbmol

• bottom:12.5molA 12.5lbmolAhr  156lbmolA

 total mass: 3.0 kg/min + 1.0 kg/min = mdot

 benzene: 3.0 kg C6H6/min = mdot (kg/min) + x

• Write balances first that involve the fewest

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

V1 = m1 / ρH2O = 150 kg / (1 kg/L)

V1 /100 kg = 150 L / (100 kg) = 1.50 L H2O / kg

m2 /100 kg = 250 kg / 100 kg = 2.50 kg product

ndf = nunknowns – nindep_eqns

• If ndf = 0, problem can be solved (in

2b. Convert mole to mass fractions

2c. no stream information known

2e. process specification

i. volumetric flow conversion

ii. benzene split fraction

. benzene balance iv. toluene balance

yT3  1 0.064 0.936kgT

Solve MIBK balance to

Solve acetone, MIBK, and

For either (just 1)

ndf = 4 unknowns (mA6,

ndf = 4 unknowns (mA6,

 0.983n4   0.983n5   0.983 100

 K2CrO4 balance  0.333 4500 kghK  m

 K2CrO4 balance  0.333 4500 kghK  m