2/12/15

OBJECTIVES

Understand & convert units

Understand processes & process variables
Formulate material balance equation
Calculate material balances
Use ideal gas law
Use the compressibility charts

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SOME APPLICATIONS OF
MATERIAL (& ENERGY)
BALANCES
Process & Equipment Design
Process Monitoring
Process Troubleshooting
Process Improvement & Development

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Units & Dimensions

110 mg of sodium
5 litre of gasoline
6 metre
Value

Unit

Dimension

110

mg

mass

litre

volume

metre

length

Conversion of Units
To convert
terms
of one unit
to
2
Convert
23 Ibamquantity
.ft/min2 toinits
equivalent
in kg.cm/s
an equivalent in new units
1. Convert one unit to an equivalent new unit
Multiply by a conversion factor (a ratio of
2.
Multiply quantities)
by a conversion factor
equivalent
4. Units & values
raised
3.2808
ft to same power
1m
3. Old units cancel
out
1 min
23 Old
Ibm .ft
0.454
kg out
units
cancel
min2

1 Ibm

60 s

30.48 cm
1 ft

0.088 kg.cm
s2

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Systems of Units
SI (Systeme Internationale d Unites)
cgs
Engineering (American, English, fps)
Systems Base units
SI
cgs
Eng.

Multiples

kg,m,s,K,A powers of 10 - k,c,m

g,cm

same as SI

Derived
N,Pa,J,W
dyne, erg

Ibm,ft,s,R yds,inches,miles,tons Ibf,gal,psi,BTU

Mass, Force and Weight

Newton s 2nd law of Motion
Force = mass x acceleration

Weight
Units of force:

kg.m/s2 = Newton(N)
g.cm/s2 = 1 dyne
The force exerted on the
2 by
Ibobject
m.ft/s = 1 Ibf
gravitational attraction,g

mg
gc
2
2
lb .ft/s2
gc = a constant = 1 kg.m/s = 1 g.cm/s = 32.174 mlb
N
dyne
f
W=

g = acceleration of gravity
= 9.8066 m/s2 = 980.66 cm/s2 = 32.174 ft/s2

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Process
Any operation or series of operations that
causes a physical or chemical change in a
substance or mixture of substances
CO2

Glycol
product

C2H4

Diglycol
O2 & N2

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Process Unit
An apparatus in which one of the operation
that constitute a process is carried out. Each
process unit has a set of input and output
process stream

Input or
feed

Output or
product

Process Variables
Properties and conditions of the materials
that enter and leave each process unit
Examples:
Mass, volume and density
Flow rate
Chemical composition
Concentration
Pressure
Temperature

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Flow Rate
rate at which material is transported
through a process line
Mass flow rate = mass (kg)
time (s)
Volumetric flow rate = volume (m3)
time (s)

Mass and Volume

Density, = mass, m (kg)
volume, V (m3)
Specific volume = volume, V (m3)
mass, m (kg)
Specific
=
density of a substance
gravity, SG
density of a reference substance
= / ref

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Moles & Molecular Weight

Molecular weight, M
sum of all the atomic weights of its atoms
Mol
MO2 = 2(16) = 32
amount of a species whose mass (g) equivalent
to its molecular weight
Example
1 mol O2 = 32 g
For NH3, 1 mol
NHO32 contains
1 kmol
= 32 kg 17g (M=17)
Therefore,
34 kg NH3 = 34 kg NH3 1 kmol NH3
17 kg NH3
= 2 kmol NH3

Composition
Composition fractions :
Mass fraction, xA = mass of A (kg A)
total mass (kg total)
Mole fraction, yA = moles of A (moles A)
total moles (moles total)
x

= y

all
components

=1

all
components

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Conversion of Mass Fractions to

Mole Fractions (or vice versa)
1

Assume a basis of calculation

Calculate the mass of each

component in the basis quantity

Convert these masses to moles

Take the ratio of the moles of each

component to the total number of
moles

Conversion from % mass to %

mole
A mixture of gases has the following composition
by mass :
O2
CO
CO2
N2

16%
4.0%
17%
63%

What is the molar composition ?

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Solution:
Basis : 100 g of the mixture
For O2, amount of moles, nO2 =
100 g total 0.16 g O2 1 mol O2
g total
32 g O2
= 0.5 mol O2
nO2 = 0.5 mol

O2
CO

nCO =

(100)(0.04)
= 0.143 mol
28

CO2

nCO2 =

(100)(0.17)
= 0.386 mol
44

N2

nN2 =

(100)(0.63)
= 2.250 mol
28
Total moles = 3.279 mol

Step
Step 421 & 3
Molar fraction
Assume
Amount
of
a moles
basis of
calculation
each
components
component in
100g of the mixture
mol O2
=
mol total
mol CO
=
yCO =
mol total
mol CO2
=
yCO2 =
mol total
mol N2
=
yN2 =
mol total
yO2 =

0.5
= 0.15
3.279
0.143
= 0.044
3.279
0.386
= 0.12
3.279
2.25
= 0.69
3.279

Check : yi = 1.00

Average molecular weight of a

mixture
Mole fractions,
M = y 1M 1 + y 2M 2 +
Mass fractions,
1 / M = (x1 / M1) + (x2 / M2) +

10

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Average Molecular Weight of Air

Calculate the average molecular weight of
air from its approximate
1. molar composition of 79% N2, and 21% O2
2. mass composition of 76.7% N2, and 23.3%
O2

Solution:
Given :

Mole fraction:
yN2 = 0.79, yO2 = 0.21
Mass fraction: xN2 = 0.767, xO2 = 0.233

1. M = yN2MN2 + yO2MO2
=

0.79 kmol N2 28 kg N2 0.21 kmol O2 32 kg O2

kmol
kmol N2 +
kmol
kmol O2

= 29 kg / kmol

2. 1 / M = (x1 / M1) + (x2 / M2)

=

0.767 g N2 mol N2
0.233 g O2 mol O2
+
g
28 g N2
g
32 g O2

= 0.035 mol / g

11

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Concentration
Concentrations are based on volume
Mass concentration = mass kg
volume m3
Molar concentration = moles kmol
volume m3
Molarity - concentration calculated in terms of mol/liter

Can be used to convert mass or mass flow

rates (moles or molar flow rates) to total
volume or volumetric flow rates

Pressure
Atmospheric
Pressure =pressure,
force,
Patm.F
N
the hydrostatic
areapressure
the forceon
acts,
theAsurface
m2
of the earth at sea level = 1 atm =
Po (N/m
14.696
psi2) = 760mm Hg = 101.325 kPa
A (m2)

Gauge pressure, Pgauge

Fluidtodensity
pressure relative
atmospheric pressure
h (m)

P (N/m2)

(kg/m3)

Absolute pressure, Pabs.

relative to a perfect P
vacuum
= Po + which
(g / gisc)given
h
a pressure of zero
P(mm Hg) = Po(mm Hg) + h (mm Hg)

Pabs. = Pgauge + Patm.

12

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Temperature
Absolute
The degree
temperature
of hotnessscales
or coldness
is scalesofthat
a
substance
began
at absolute
measured
zero
on some definite scale
Conversion between temperature
units
Fahrenheit
Kelvin
(K)
(oF)

0K
= -273.15oCo
0oC = 273.15 K
Most
common
T(K)
=
T(
C)
+
273.15
temperature
scales o
o
oF = 459.67oR
o
o
0 RT(
= -459.67
F F) +0459.67
Rankine
Celsius ((ooC)
R)
R) = T(

T(oR) = 1.8 T(K)

T(oF) = 1.8 T(oC) + 32

Process Classification

Process Classification
Batch Process

Continuous Process Semibatch Process

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2/12/15

Batch Process
Feed is charged into the system at the begining of
the process and product is removed all at once at
sometime later

Continuous Process
Input and outputs flow continuously throughout
the duration of the process

Semibatch Process
Any process that is neither batch nor continuous

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2/12/15

Material Balances
Law of Conservation of Mass :
Mass can neither be created nor destroyed
(except in nuclear reactions)
General balance equation:
Input + Generation Output Consumption = Accumulation

enter thru
system
boundaries

Produced
within
system

leaves thru
system
boundaries

consumed
within
system

Buildup
within
system

Balance on Non-reactive System

Continous Steady-State Processes:
Material balance is simply
Input = Output

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Balance on Reactive System

Balance on a reactive substance does not have
the simple form input = output, but must
include a generation or consumption term.
Input + Generation = Output + Consumption

Calculation Procedure for

Material Balance Calculations
1. Draw flowchart with known values
400 mol/h

2. Label
allO2unknowns
0.21 mol
/mol
3.
4.
5.

0.79 mol N2/mol

Q mol/h
400
mol/h
T = 320oC,aP basis
= 1.4 atm
Choose
x0.21
mol
mol
O2O
/mol
2/mol
10.79
- x molgiven
N22/mol
flow
rate eg.
mol/hwith
feeda
Or Use
assume
an
amount
of 400
a stream
oC, P =
T = 320the
1.4 atm
Write
material
known composition
e.g. Qbalances
= 100 mol/h feed
400 mol/h
Q 0.21
mol/hmol O /mol
2
0.21problems
mol O2/mol
Solve
for unknowns
0.79 mol N
2/mol
0.79
mol
N
/mol
o
2
T = 320
C, P = 1.4
atm
Check
material balance
T = answer
320oC, Pusing
= 1.4redundant
atm

16

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Continous Distillation Process

1000 kg/hr of mixture benzene (B) and toluene (T)
that contains 50% benzene by mass are separated
by distillation into two fractions. The mass flow
rate of benzene in the top stream is 450 kg B/hr and
the toluene in the bottom stream is 475 kg T/hr.
The operation is at steady state. Calculate the
unknown component flow rate in the output
streams.

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2/12/15

Solution :

Step 31
L a b e l chart
Flow
u n k n with
own
known values
variables

450 kg B/h
1000 kg/hr of mixture
contains 50% benzene

q1 kg T/h

1000 kg/h
0.5 kg B/kg
0.5 kg T/kg
475 kg T/h
q2 kg B/h

Step 542

Basis of
Material
Solve
unknowns
Calculation
Balance

Basis: 1000 kg/h feed

Input = Output

450 kg B/h
q1 kg T/h

Benzene balance:
0.5(1000) kg B/h = 450 kg B/h + q2
q2 = 50kg B/h

1000 kg/h
0.500 kg B/kg
0.500 kg T/kg

Toluene balance:
475 kg T/h
q2 kg B/h

0.5(1000) kg T/h = 475 kg T/h + q1

q1 = 25kg T/h

Checking: Total Mass Balance:

1000kg/h = (450 +q1 + q2+475) kg/h
1000kg/h = 1000 kg/h

18

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Multiple-unit Processes
Material
Most
processes
balances
consists
(boundaries)
of a number
can be written
of interconnected
around
any
unit subsystem
processes. of the plant. Material balances can also be
written for mixing points or splitters.
Feed 2

C
D

Feed 1

Product 3

Unit 2

Unit 1
B

E
Product 1 Product 2 Feed 3

A Entire process

C Process unit 1

B mixing point

D Splitter point

E Process unit 2

A labeled flowchart of a continous steady-state two-unit

distillation process is shown below. Each stream contains two
Components, A and B, in different proportions. Three streams
whose flow rates and/or compositions are not known are labeled
1,2, and 3. Calculate the unknown flow rates and compositions
of streams 1, 2, and 3.
40 kg/h
0.900 kg A/kg
0.100 kg B/kg
100 kg/h
0.5 kg A/kg
0.5 kg B/kg

Unit 1

30 kg/h
0.600 kg A/kg
0.400 kg B/kg

30 kg/h

Unit 2

0.300 kg A/kg
0.700 kg B/kg

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Solution:
40 kg/h
0.900 kg A/kg
0.100 kg B/kg
100 kg/h
0.5 kg A/kg
0.5 kg B/kg

Unit 1

1 Q1(kg/h)
x1(kg A/kg)
1x1(kg B/kg)
30 kg/h

30 kg/h
0.600 kg A/kg
0.400 kg B/kg

2 Q2(kg/h)
x2(kg A/kg)
1x2(kg B/kg)

Unit 2

3 Q3(kg/h)
x3(kg A/kg)
1x3(kg B/kg)

0.300 kg A/kg
0.700 kg B/kg

Basis : Given flow rates

Steady-state without reaction :

40 kg/h
0.900 kg A/kg
0.100 kg B/kg
100 kg/h
0.5 kg A/kg
0.5 kg B/kg

Unit 1

30 kg/h
0.600 kg A/kg
0.400 kg B/kg

Q1(kg/h)

Q2(kg/h)

x1(kg A/kg)
1x1(kg B/kg)

x2(kg A/kg)
1x2(kg B/kg)

30 kg/h

Entire process

Input = Output

Unit 2

Q3(kg/h)
x3(kg A/kg)
1x3(kg B/kg)

0.300 kg A/kg
0.700 kg B/kg

Overall Mass Balance :

(100 + 30) = (40 + 30) + Q3
Q3 = 60 kg/h

Overall Balance on A :
0.5(100) + 0.3(30) = 0.9(40) + 0.6(30) + x3(60)
x3 = 0.0833 kg A/kg

20

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30 kg/h
0.600 kg A/kg
0.400 kg B/kg

40 kg/h
0.900 kg A/kg
0.100 kg B/kg
100 kg/h
Unit 1

0.5 kg A/kg
0.5 kg B/kg

Q1(kg/h)

Q2(kg/h)

x1(kg A/kg)
1x1(kg B/kg)

x2(kg A/kg)
1x2(kg B/kg)

30 kg/h

60 kg/h
Unit 2

0.0833 kg A/kg
0.9167 kg B/kg

0.300 kg A/kg
0.700 kg B/kg

Total Mass Balance :

Unit 1

100 kg/h = 40 kg/h + Q1

Q1 = 60 kg/h

Mass Balance on A :
0.5(100) = 0.9(40) + x1(60)
x1 = 0.233 kg A/kg

40 kg/h
0.900 kg A/kg
0.100 kg B/kg
100 kg/h
0.5 kg A/kg
0.5 kg B/kg

Q2 (kg/h)

60 kg/h
Unit 1

0.233 kg A/kg
0.767 kg B/kg
30 kg/h

Stream Mixing Point

30 kg/h
0.600 kg A/kg
0.400 kg B/kg

x2 (kg A/kg)
1x2(kg B/kg)

60 kg/h
Unit 2

0.0833 kg A/kg
1x3(kg B/kg)

0.300 kg A/kg
0.700 kg B/kg

Total Mass Balance :

60 + 30 = Q2
Q2 = 90 kg/h

Mass Balance on A :
0.233(60) + 0.3(30) = x2(90)
x2 = 0.255 kg A/kg

21

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Recycle & Purge

Purge
Recycleisis a stream
stream that
bledreturns
off tomaterial
removefrom
an
accumulation
downstream ofof ainerts
process
or unwanted
unit backmaterial
to the
that
process
might
unit otherwise
(or to a unitbuild
upstream
up inofthe
the unit).
recycle
stream
Recycle R

Feed

Mixer

Process

Divider

Separator

Purge

Product

Bypass
A stream that skips one or more stages of the
process and goes directly to another
downstream stage. Here a fraction of the feed to
a process unit is diverted around the unit and
combined with the output stream from the unit.
Feed

Product
Process Unit
Bypass stream

22

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Recycle in Distillation Column

A distillation column separates 10,000 kg/hr of a 50%
benzene (B) 50% toulene (T) mixture. The product D
recovered from the condenser at the top of the column
contains 95% benzene, and the bottom W from the
column contains 96% toulene. The vapour stream V
entering the condenser from the top of the column is
8000 kg/hr. A portion of the product from the
condenser is returned to the column as reflux, and the
rest is withdrawn for use elsewhere. Assume that the
compositions of the streams at the top of the column
(V), the product withdrawn (D) and the reflux (R) are
identical because the V stream is condensed completely.
Find the ratio of the amount refluxed R to the product
withdrawn (D).

Solution:
Basis : 10,000 kg/h of feed
D
0.95 kg B/kg
0.05 kg T/kg

V = 8000 kg/h
0.95 kg B/kg
0.05 kg T/kg
R
F = 10000 kg/h
0.5 kg B/kg
0.5 kg T/kg

0.95 kg B/kg
0.05 kg T/kg

W
0.04 kg B/kg
0.96 kg T/kg

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Basis : 10,000 kg/h of feed

D
0.95 kg B/kg
0.05 kg T/kg

V = 8000 kg/h
0.95 kg B/kg
0.05 kg T/kg
F = 10000 kg/h

0.95 kg B/kg
0.05 kg T/kg

0.5 kg B/kg
0.5 kg T/kg

Entire process

W
0.04 kg B/kg
0.96 kg T/kg

Overall Mass Balance:

10000 kg/h = (D + W) kg/h

Overall Mass Balance on B:

0.5(10000) kg/h = 0.95D + 0.04W

Solving simultaneously,

D = 5050 kg/h
W = 4950 kg/h

D = 5050 kg/h
0.95 kg B/kg
0.05 kg T/kg

V = 8000 kg/h
0.95 kg B/kg
0.05 kg T/kg
F = 10000 kg/h
0.5 kg B/kg
0.5 kg T/kg

Condenser

R
0.95 kg B/kg
0.05 kg T/kg
W = 4950 kg/h
0.04 kg B/kg
0.96 kg T/kg

Total Material Balance:

8000 kg/h = (R + 5050) kg/h
R = 2950 kg/h
Hence, R/D = 2950/5050 = 0.58

24

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Stoichiometry
Stoichiometry is the theory of the proportions in
which chemical species combine with one another

Stoichiometry Equation:
2 SO2 + 1 O2 2 SO3
Stoichiometric coefficients

Stoichiometric Ratio
2 mol SO3 produced
2 mole SO3 produced
1600 kg SO3 produced
1 kmol O2 or
reacted
1 kmol SO3
1 mol O2 reacted 80 kg SO32 mole
SO2SO
reacted
h
2 kmol
3 produced
= ?10 kmol O2
h

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Limiting Reactant
Reactant that would disappear first if a
reaction proceeded to completion
Reactant that has the lowest ratio of nio/i
nio = moles of reactant i in feed
i = stoichiometric coefficient for reactant i
Excess reactants
reactants present in excess of the
limiting reactant
% excess = 100% non-sns

no = moles feed
ns = moles corresponding to stoichiometric
proportion

Fractional Conversion
Fractional conversion,f = moles reacted
moles fed
f = i / nio
= extent of reaction

Overall conversion
reactant input to process - reactant output from process
reactant input to process

Single-pass conversion
reactant input to reactor - reactant output from reactor
reactant input to reactor

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Balance Equation
Single reaction:

ni = nio i
Where

ni = mole of reactant i
nio = mole of reactant i in feed

i = stoichiometric coefficient for reactant I

= extent of reaction

+ when reactant i is being produced

when reactant i is being consumed

Single reaction
Acrylonitrile is produced by the reaction of propylene,
ammonia and oxygen
C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O
propylene

ammonia

oxygen

acrylonitrile

water

The feed contains 10 mole % propylene, 12%

ammonia, and 78% air. A fractional conversion of 30%
of the limiting reactant is achieved. Determine which
reactant is limiting, the percentage by which each of
the other reactants is in excess, and the molar flow
rates of all product gas constituents.

27

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Solution:
C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O
n1 mol C3H6
n2 mol NH3
Q mol = 100 mol
0.10 mol C3H6 / mol

Process

n3 mol O2
n4 mol N2

0.12 mol NH3 / mol

n5 mol C3H3N

0.78 mol air

0.21 mol O2/mol
0.79 mol N2/mol

n6 mol H2O

Basis: 100 mol Feed

C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

100 mol
0.10 mol C3H6 / mol
0.12 mol NH3 / mol
0.78 mol air
0.21 mol O2/mol
0.79 mol N2/mol

n1 mol C3H6
n2 mol NH3
n3 mol O2
n4 mol N2
n5 mol C3H3N
n6 mol H2O

Feed to the reactor contains

(C3H6)o = 10.0 mol
(NH3)o = 12.0 mol
(O2)o = 78.0 mol air 0.21 mol O2 = 16.4 mol
mol air
(N2)o = 16.4 mol O2 0.79 mol N2 = 61.7 mol
0.21 mol O2

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C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

n1 mol C3H6
n2 mol NH3
n3 mol O2
n4 mol N2
n5 mol C3H3N
n6 mol H2O

100 mol
10 mol C3H6
12 mol NH3
16.4 mol O2
61.7 mol N2

A) Limiting reactant has the lowest nio/i

nio = initial feed for component i
i = stoichiometric coefficient for component i

(C3H6)o / C3H6 = 10.0/1 = 10.0

Lowest ratio
(NH3)o / C3H6 = 12.0/1 = 12.0
(O2)o / C3H6 = 16.4/1.5 = 10.9
Propylene (C3H6) is the limiting reactant

C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

n1 mol C3H6
n2 mol NH3
n3 mol O2
n4 mol N2
n5 mol C3H3N
n6 mol H2O

100 mol
10 mol C3H6 (L)
12 mol NH3
16.4 mol O2
61.7 mol N2

% by which NH3 & O2 are in excess:

% excess = 100% non-sns

no =moles feed
ns = moles corresponding to stoichiometric proportion
Stoichiometric

C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

10

10

1.5(10)

10

3(10)

12 - 10
= 20%
(% excess)NH3 = 100%
10

(% excess)O2 = 100% 16.4 - 15 = 9.3%

15

proportion
based
on propylene

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C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

100 mol
10 mol C3H6 (L)
12 mol NH3
16.4 mol O2
61.7 mol N2

n1 mol C3H6
n2 mol NH3
n3 mol O2
n4 mol N2
n5 mol C3H3N
n6 mol H2O

Product gas constituents:

moles C3H6 reacted
Given f C3H6 = 0.3 = moles C3H6 fed
Moles C3H6 reacted = 0.3(moles C3H6 fed)
= 0.3 (10) = 3 mol = C3H6 = 1( )
=3
Components C3H6 NH3
O2
N2
C3H3N H2O
Input (mol)
10
12
16.4
61.7
i mol
-1(3) -1(3) -1.5(3) 0(3)
+(3)
+3(3)
Output (mol) n1 = 7 n2 = 9 n3 =11.9 n4 =61.7 n5 = 3 n6 = 9

Multiple reaction:
ni = nio i
Need to consider each reaction in the process separately

Yield
moles of desired product formed
moles that would have been formed if without side
reaction & reaction proceed to completion

Selectivity
moles of desired product formed
moles of undesired product formed

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Multiple reactions
C2H6 C2H4 + H2
C2H6 + H2 2CH4

reaction (1)
reaction (2)

The feed contains 85.0 mole% ethane (C2H6) and the balance inerts
(I). The fractional conversion of ethane is 0.501, and the fractional
yield of ethylene is 0.471.
Required: the molar composition of the product gas &
selectivity of C2H4 to CH4.
fC2H6 = 0.501

Fractional yield of C2H4 =0.471

F
0.85 mol C2H6/mol
0.15 mol I/mol

Process

n1 mol C3H6
n2 mol C2H4
n3 mol H2
n4 mol CH4
n5 mol I

Solution:
fC2H6 = 0.501

Fractional yield of C2H4 =0.471

F =100 mol
0.85 mol C2H6/mol
0.15 mol I/mol
C2H6 C2H4 + H2
C2H6 + H2 2CH4

n1 mol C3H6
n2 mol C2H4
Process
n3 mol H2
n4 mol CH4
n5 mol I
reaction 1
reaction 2

Basis : 100 mol feed

Given : fC2H6 = 0.501 = moles of C2H6 reacted
moles
0.85(100)
of C2H6 fed
Therefore, moles of C2H6 reacted = 0.501(85 mol)
= 42.585 mol
1 + 2 = 42.585 mol

(1)

31

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C2H6 C2H4 + H2
C2H6 + H2 2CH4

reaction 1
reaction 2

F= 100 mol
0.85 mol C2H6/mol
0.15 mol I/mol

Process

1 + 2 = 42.585 mol

(1)

n1 mol C3H6
n2 mol C2H4
n3 mol H2
n4 mol CH4
n5 mol I

moles of C2H4 formed

Fractional yield =
moles
C
H
of C2H4
2 4 that would have been
formed if reaction 1 reacted completed
0.471 = moles of C2H4 formed
85 mol C2H4
Therefore, moles of C2H4 formed = 0.471(85 mol)
= 40 mol
1 = 40 mol
(2)

C2H6 C2H4 + H2
C2H6 + H2 2CH4
F= 100 mol
0.85 mol C2H6/mol
0.15 mol I/mol
1 + 2 = 42.585 mol
1 = 40 mol
From equation (1),

reaction 1
reaction 2
n1 mol C3H6
n2 mol C2H4
n3 mol H2
n4 mol CH4
n5 mol I

Process
(1)
(2)

40 + 2 = 42.585 mol
2 = 2.585 mol

Table of component amounts for all input and output streams

Components

C2H6

C2H4

Input (mol)

85

Generated/Consumed (+i 1 mol) -1(40)

Generated/Consumed (+i 2 mol) -1(2.585)
Output (mol)

H2
-

+1(40) +1(40)
-

CH4
-

I
15
0(40)

-1(2.585) +2(2.585) 0(2.585)

n1= 42.4 n2= 40 n3 =37.4 n4 = 5.2 n5 = 15

32

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F = 100 mol
0.85 mol C2H6
0.15 mol I

Total moles = 42.4 + 40 + 37.4

+ 5.2 + 15 = 140 mol
42.4 mol C3H6
40 mol C2H4
37.4 mol H2
5.2 mol CH4
15 mol I

Process

The molar composition of the production gas

Components
Molar
composition

C2H6

C2H4

H2

CH4

100% x
(42.4/140)

100% x
(40/140)

100% x
(37.4/140)

100% x
(5.2/140)

100% x
(15/140)

= 30.3 %

= 28.6 %

= 26.7 %

= 3.7 %

= 10.7 %

Selectivity of C2H4 to CH4 = moles of desired product formed

moles of undesired product formed
= (40 mol C2H4) / (5.2 mol CH4) = 7.7

Dehydrogenation of Propane
C3H8 C3H6 + H2
Propane
propylene
The process is to be designed for a 95% overall conversion of
propane. The reaction products are separated into two streams; the
first, which contains H2, C3H6 and 0.555 % of the propane that leaves
the reactor, is taken off as product; the second stream, which
contains the balance of the unreacted propane and 5% of the
propylene in the product stream, is recycled to the reactor.
Required:composition of the product, the ratio (moles recycled)/(moles
fresh feed), and the single-pass conversion.
F mol
C3H8

Reactor

100 + Qr1 mol C3H8

Qr2 mol C3H6

P1 mol C3H8
P2 mol C3H6
P3 mol H2

Separator

Product
Q1 mol C3H8
Q2 mol C3H6
Q3 mol H2

Qr1 mol C3H8

Qr2 mol C3H6

33

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Solution:
C3H8 C3H6+ H2
F mol
C3H8

= 100

Reactor

Separator

P1 mol C3H8
P2 mol C3H6
P3 mol H2

100 + Qr1 mol C3H8

Qr2 mol C3H6

Product
Q1 mol C3H8
Q2 mol C3H6
Q3 mol H2

Qr1 mol C3H8

Qr2 mol C3H6

Basis : 100 mol fresh feed

Overall Process:

100 - Q1
100
Q1 = 5 mol C3H8
moles of C3H8 reacted = 1() = 100 - 5 = 95 mol
foverall C3H8

100 mol
C3H8

Reactor

100 + Qr1 mol C3H8

Qr2 mol C3H6

= 0.95 =

C3H8 C3H6+ H2

= 95

P1 mol C3H8
P2 mol C3H6
P3 mol H2

Separator

Product
5 mol C3H8
Q2 mol C3H6
Q3 mol H2

Qr1 mol C3H8

Qr2 mol C3H6

Table of component amounts for the entire process

Components
Input (mol)
i mol
Output (mol)

C3H8
100
-1(95)
Q1 = 5

C3H6
+1(95)
Q2 = 95

H2
+1(95)
Q3 =95

34

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C3H8 C3H6+ H2
100 mol
C3H8

Reactor

100 + Qr1 mol C3H8

Qr2 mol C3H6

P1 mol C3H8
P2 mol C3H6
P3 mol H2

Separator

195 moles
5 mol C3H8
95 mol C3H6
95 mol H2

Qr1 mol C3H8

Qr2 mol C3H6

The composition of the product:

C3H8 = 100%(5/195) = 2.6%
C3H6 = 100%(95/195) = 48.7%
H2 = 100%(95/195) = 48.7%
Given: 5% of C3H6 in the product stream is recycled.
Qr2 = 0.05(95) = 4.75 mol C3H6

C3H8 C3H6+ H2
100 mol
C3H8

Reactor

100 + Qr1 mol C3H8

Qr2 mol C3H6

P1 mol C3H8
P2 mol C3H6
P3 mol H2

Separator

195 moles
5 mol C3H8
95 mol C3H6
95 mol H2

Qr1 mol C3H8

4.75 mol C3H6

Given:
0.555% of C3H8 leaving the reactor is in the product stream.
0.555P1 = 5 mol C3H8
P1 = 900 mol C3H8
Separation Unit

H2 balance:

P3 = 95 mol H2

35

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C3H8 C3H6+ H2
100 mol
C3H8

Reactor

100 + Qr1 mol C3H8

4.75 mol C3H6

900 mol C3H8 Separator

P2 mol C3H6
95 mol H2

195 moles
5 mol C3H8
95 mol C3H6
95 mol H2

Qr1 mol C3H8

4.75 mol C3H6

Table of component amounts for the reactor:

Components
Input (mol)
i mol
Output (mol)

C3H8
100 +Qr1
-1(95)
900

C3H6
4.75
+1(95)
P2 = 99.75

H2
+1(95)
95

C3H8 C3H6+ H2
100 mol
C3H8

Reactor

100 + Qr1 mol C3H8

4.75 mol C3H6

900 mol C3H8 Separator

P2 mol C3H6
95 mol H2

195 moles
5 mol C3H8
95 mol C3H6
95 mol H2

Qr1 mol C3H8

4.75 mol C3H6

Table of component amounts for the reactor:

Components
Input (mol)
i mol
Output (mol)

C3H8
100 +Qr1
-1(95)
900

C3H6
4.75
+1(95)
P2 = 99.75

H2
+1(95)
95

100 + Qr1 - 95 = 900

Qr1 = 895 mol

36

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C3H8 C3H6+ H2
100 mol
C3H8

Reactor

100 + 895 mol C3H8

4.75 mol C3H6

900 mol C3H8 Separator

99.75 mol C3H6
95 mol H2

195 moles
5 mol C3H8
95 mol C3H6
95 mol H2

895 mol C3H8

4.75 mol C3H6

Ratio of

moles recycled
Q + Qr2 = 895 + 4.75 =9.0
= r1
moles fresh feed
100
100

Single-pass conversion = 100% (100 + Qr1) - 900

(100 +Qr1)
(100 + 895) - 900
= 100%
= 9.55%
(100 +895)

Combustion
Combustion reactions are one of the most
common and important classes of reactions
used in chemical processing due to the large
amounts of heat released by the reaction :
Heat

Fuel

O2

Flue Gas

37

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The fuels are either coal, fuel oil, gaseous fuel (e.g.
natural gas) or liquefied petroleum gas. When
burned, the products are :

C + O2 CO2 (complete combustion)

C + O2 CO (incomplete combustion)
H + O2 H2O
S + O2 SO2
N + O2 NO (only T > 1800oC)

The composition of the flue / stack gas are given

either on a wet basis or a dry basis , depending
on whether water is included
Moles

Wet Basis

Dry Basis

50 mole CO2

33.3% CO2

50% CO2

50 mole N2

33.3% N2

50% N2

50 mole H2O

33.3% H2O

0% H2O

38

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Air is the source of the oxygen for combustion and its

composition is simplified to 79% N2 and 21% O2.
Theoretical air (or theoretical oxygen)
Moles of air (or O2) needed for complete combustion of the
fuel and does not depend on how much is actually burned
Excess air (or excess oxygen)
Moles supplied beyond the theoretical requirements. It
depends only on the theoretical air (or O2) and the air (or O2)
feed rate, and not on how much is consumed in the reactor
or whether combustion is complete or partial.
% = (moles air or O2)fed - (moles air or O2)theo. x 100%
excess air
(moles air or O2)theo.

Combustion
Ethane (C2H6) is burned with 50% excess air. The
percentage conversion of the ethane is 90%; of the
ethane burned, 25% reacts to form CO and the
balance to form CO2. Calculate the composition of the
flue gas on a dry basis and the ratio of water to dry
flue gas.
Solution:
C2H6 + 7/2O2 2CO2 + 3H2O
C2H6 + 5/2O2 2CO + 3H2O

reaction 1
reaction

39

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Solution:
C2H6 + 7/2O2 2CO2 + 3H2O
C2H6 + 5/2O2 2CO + 3H2O
50% excess air
Q mol O2
3.76Q mol N2

reaction (1)
reaction (2)
q1 mol C2H6
q2 mol O2
q3 mol N2
q4 mol CO
q5 mol CO2
q6 mol H2O

Process

100 mol C2H6

Basis : 100 mol ethane fed

Given: 50% excess air
0.5 = (moles O2)fed (moles O2)theo
(moles O2)theo
= Q (nO2)s
(nO2)s

C2H6 + 7/2O2 2CO2 + 3H2O

C2H6 + 5/2O2 2CO + 3H2O
50% excess air
Q mol O2
3.76Q mol N2

reaction (1)
reaction (2)
q1 mol C2H6
q2 mol O2
q3 mol N2
q4 mol CO
q5 mol CO2
q6 mol H2O

Process

100 mol C2H6

(nO2)s = 100 mol C2H6

0.5 =

3.5 mol O2
1 mol C2H6

(moles O2)fed (moles O2)theo

(moles O2)theo

= 350

Q 350
350

Moles O2 fed = 525 mol = Q

Moles N2 fed = 3.76(525) = 1974 mol

40

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C2H6 + 7/2O2 2CO2 + 3H2O

C2H6 + 5/2O2 2CO + 3H2O
50% excess air
525 mol O2
1974 mol N2

reaction (1)
reaction (2)

75% C2H6
25% C2H6

q1 mol C2H6
q2 mol O2
q3 mol N2
q4 mol CO
q5 mol CO2
q6 mol H2O

Process

100 mol C2H6

Given: Percentage conversion of the ethane is 90%

0.9 = moles C2H6 reacted = moles C2H6 reacted
moles C2H6 fed
100
moles C2H6 reacted = 90 mol
0.25 (90) = 22.5 mol C2H6 reacts to form CO = 2
90 22.5 = 67.5 mol C2H6 reacts to form CO2 = 1
1 = 67.5 mol
2 = 22.5 mol

C2H6 + 7/2O2 2CO2 + 3H2O

C2H6 + 5/2O2 2CO + 3H2O
50% excess air
525 mol O2
1974 mol N2

Process

100 mol C2H6

1 =67.5 mol
2 = 22.5 mol
q1 mol C2H6
q2 mol O2
q3 mol N2
q4 mol CO
q5 mol CO2
q6 mol H2O

Table of amounts for all input and output component

Components

C2H6

O2

N2

CO

CO2

H2O

Input (mol)

100

525

1974

-1(67.5)

-3.5(67.5)

0(67.5)

2(67.5)

3(67.5)

-1(22.5)

-2.5(22.5)

0(22.5)

2(22.5)

3(22.5)

q1=10

q2=232.5

q3=1974

q4 = 45 q5=135

Generated/Consumed (+i 1 mol)

Generated/Consumed (+i 2 mol)
Output (mol)

q6=270

41

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50% excess air

525 mol O2
1974 mol N2

Process

100 mol C2H6

10 mol
C2H6
232.5 mol O2
1974 mol N2
45 mol CO
135 mol CO2
270 mol H2O

Total moles on a dry basis

=10 + 232.5 + 1974 + 45 + 135
= 2396 mol dry gas

Hence the flue gas composition on a dry basis is

C2H6 = 10 / 2396 = 0.00417 mol C2H6 / mol
O2 = 232.5 / 2396 = 0.0970 mol O2 / mol
N2 = 1974 / 2396 = 0.824 mol N2 / mol
CO = 45 / 2396 = 0.019 mol CO / mol
CO2 = 135 / 2396 = 0.0563 mol CO2 / mol
And
Mole ratio of H2O to dry flue gas = 270 / 2396
= 0.113 mol H2O / mol

42

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Ideal Gas
Ideal Gas Law :

PV = nRT

or

= RT
PV

where
P = absolute pressure of gas
V = volume of gas occupied by the gas
n = number of moles of the gas
R = gas constant
T = absolute temperature of gas

= molar volume (V/n) of the gas

V

Gas Constant
8.314 m3.Pa/mol.K
0.08314 liter.bar/mol.K
0.08206 liter.atm/mol.K
62.36 liter.mm Hg/mol.K
0.7302 ft3.atm/lb-mole.oR
10.73ft3.psia/lb-mole.oR
8.314 J/mol.K
1.987 cal/mol.K
1.987 Btu/ lb-mole.oR

43

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Standard Conditions for Gases

System

Ts

Ps

Vs

ns

SI

273 K

1 atm 0.022415 m3

1 mol

CGS

273 K

1 atm 22.415 liter

1 mol

American
Engineering

492oR

1 atm

359.05 ft3

1 lb-mole

which leads to the abbreviations STP for

Standard Temperature and Pressure

Example:
o
o
10 ftn3 oflb-mole
air at 530
to 1070
air R and 1 atm are heated
n2 lb-mole
air R
1
and compressed to 2.5 atm. What volume does the gas
occupy
itsofinal
T1 =in530
R state
T2 = 1070oR
P1 = 1 atm
P2 = 2.5 atm
V1 = 10 ft3
V = ? ft3

Assume ideal gas behavior, n1 = n2

P2V2 = n2RT2
P1V1

n1RT1

V2 = V1P1T2 = 10.0 ft3 1.00 atm 1070 oR = 8.08 ft3

P2T1
2.50 atm 530 oR

44

2/12/15

Ideal Gas Mixtures

PV = ntotRT
ntot = total moles of all species in the ideal gas mixtures
pA +pB + = P
where pA = partial pressure of component A
yA =

PA
P

% mol = % vol.

Example:
A natural gas has the following composition :
CH4
C2H6
C3H8

87% mol
12% mol
1% mol

77.5 % wt.
20% wt.
2.5% wt.

Compute the volume occupied by 80kg of the gas

at 9oC (282.15K) and 600 kPa. The molecular
weight of the gas is 17.96 kg/kgmol.

45

2/12/15

Solution:
ntot =

80 kg kgmol
17.96 kg

= 4.45 kgmol

Using the ideal gas law:

PV = ntotRT
V=
V = 4.45 kgmol

ntotRT
P
282.15 K 8.314 kPa.m3
60 kPa
kgmol.K

= 174 m3

46

2/12/15

Real Gases
PV = znRT

or

= zRT
PV

where z = compressibility factor

= 1 (ideal gas behavior)

Generalized Compressibility Chart

47

2/12/15

Calculation Procedure
1. Look up the critical temperature Tc &
critical pressure Pc
2. Calculate reduced values
temperature,
Tr =to
T / Tc
3.Reduced
Use compressibility
chart
Reduced compressibility
pressure, Pr = P factor,
/ Pc z.
determine

Reduced volume, Vr = VPc / RTc

4. Solve for the unknown gas variable
For H2 and He,
(Tc) adjusted = Tc + 8 K
(Pc) adjusted = Pc + 8 atm

Example
100 mol of N2 are contained in a 5 liters vessel
at 20.6oC. Estimate the pressure in the
cyclinder
100 mol N2
5 liters
-20.6oC

P = ? atm

48

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Solution:
Step 1: Critical value
Tc = 126.2K
Pc = 33.5 atm
Step 2: Reduced temperature
Tr = T/Tc
= (-20.6 + 273.2) K/ 126.2 K
=2
Reduce volume:
P /RT
Vr = V
c
c

100 mol N2
5 liters
-20.6oC
P = ? atm

= 5 liter 33.5 atm

mol.K
100 mol 126.2 K 0.08206 liter.atm
= 0.161

3. From the generalized

compressibility chart,
intersection Tr = 2.00 and Vr
= 0.161 occurs at z = 1.77

Tr = 2.00
Vr = 0.161
z = 1.77

49

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100 mol N2
5 liters
-20.6oC
z = 1.77

Step 4: Calculate P = zRT/ V

P = zRT/ V

P = ? atm

= 1.77 0.08206 liter.atm

252.4 K
mol.K
0.05liter/mol
= 73.3 atm

Real Gas Mixtures

Kay s rule:

PV = zmnRT

or

= z RT
PV
m

Compressibility factor, zm, is found from the generalized

compressibility factor chart using pseudocritical
constants given by
Tc = yaTca + ybTcb + ycTcc +
Pc = yaPca + ybPcb + ycPcc +
where
ya,yb,yc..= mole fractions of a mixture of gases A,B,C

50

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Example
A mixture of 75% H2 and 25% N2 (molar
basis) is contained in a tank at P=800 atm and
T=-70oC. Estimate the specific volume of the
mixture in liters/mol.

Solution:
H2:

Tc = 33K
Pc = 12.8 atm

N2:

Tc = 126.2K
Pc = 33.5 atm

Step 21
Pseudocritical
Look
H
Reduced
up T
values
2: Adjusted
c & Pc
values
for
critical values
mixture

(Tc)adj. = Tc +8K =33 + 8 = 41 K

(Pc)adj= Pc + 8 atm = 12.8 + 8 = 21.8 atm
Tc = yaTca + ybTcb = 0.75(41) + 0.25(126.2) = 62.3K
Pc = yaPca + ybPcb = 0.75(20.8) + 0.25(33.5) = 24.0 atm
Tr = T
Tc

= 203 = 3.26
62.3

Pr =

P
Pc

800
= 33.3
24.0

51

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3. From the generalized

compressibility chart,
intersection Tr = 3.26 and Pr
= 33.3 occurs at zm = 1.86

Step 3
Zm from
compressibility
chart

zm = 1.86

Tr = 3.26

Pr = 33.3

Step 4
Using Kay s rule:

Solve for V

= z RT
PV
m

= zmRT
V
P

= 1.86 0.08206 liter.atm

mol. K

(-70+273)K
800 atm

= 0.0387 liter
mol

52