Chapter 4

Fundamental of Material
Balances (Part B)
 Chemical Reaction Stoichiometry Constant
04591 I ox neuocleaour JI Yi carbon input out
reaction
• Material balance on a reactive system substance does not have the simple form
input=output, but must include a generation and /or consumption term.

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

The following statements are always true:

1. The number of atoms of each atomic species must be the same on both sides of
a reaction equation
2. Atoms can neither be created or destroyed in a chemical reaction.
3. Atoms can be destroyed in a nuclear reaction.

Examples:
SO2 + O2  SO3 incorrect [ not balanced ]
2SO2 + O2  2SO3 correct!
02 Imo503
SO2 + 0.5O2  SO3 correct! 1m01SO t 42m01

*Stoichiometric ratio of two molecular species participating in a reaction is the ratio

of their stoichiometric coefficients in the balanced reaction equation
 How can you balance a chemical reaction?

Example: Complete combustion of C4H8.

6 4 4
C4H8 + aO2  bCO2 + cH2O H O Jl is

What are values of stoichiometric coefficients a, b, & c?

C balance:
4=bb=4

H balance:
8 = 2c  c = 4

O balance:
2a = 2b + c  a = 6

∴ C4H8 + 6O2  4CO2 + 4H2O

Limiting & Excess Reactants Fractional conversion & extent of reaction

Limiting & Excess Reactants:

Two reactants A & B are present in stoichiometric proportion if mol (A) /
mol (B) = stoichiometric ratio.
limiting reactant
Example: Products o
C4H8 + 6O2  4CO2 + 4H2O
𝑛𝑛̇ C4H8 141616s
If = 1/6  stoichiometric Proportion o g
𝑛𝑛̇ O2
𝑛𝑛̇ C4H8
If < 1/6  Oxygen is in excess (C4H8 is limiting reactant )
𝑛𝑛̇ O2
𝑛𝑛̇ C4H8
If > 1/6  Oxygen is limiting reactant (C4H8 is in excess reactant )
𝑛𝑛̇ O2

• Limiting reactant: is reactant that will finish first ( run out first ) if a
reaction proceed to completion
• Excess reactant: all other reactants that will not be totally consumed (
will not run out )
 LA BB NC t 8D
2C D
2A 3 B

2.5
NI I Np
6m01

B
2
3
13 reaction
B is limiting
ME
W
ow
If
or I
 Limiting & Excess Reactants Fractional conversion & extent of reaction

• Fractional excess of the reactant is the ratio of the excess to stoichiometric

requirement
(𝐹𝐹𝐴𝐴 )𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 −(𝐹𝐹𝐴𝐴 )𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑒𝑒𝑒𝑒𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝐴𝐴 = reaction
(𝐹𝐹𝐴𝐴 )𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆
equation
Where
(𝐹𝐹𝐴𝐴 )𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 is 𝐹𝐹𝑎𝑎𝐹𝐹𝑎𝑎𝐹𝐹𝐹𝐹 𝐹𝐹𝑜𝑜 𝑒𝑒𝑠𝑠𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑒𝑒 𝐴𝐴 𝑜𝑜𝑒𝑒𝑓𝑓 𝐹𝐹𝐹𝐹 𝐹𝐹𝑡𝑒𝑒 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
(𝐹𝐹𝐴𝐴 )𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆 is 𝐹𝐹𝑎𝑎𝐹𝐹𝑎𝑎𝐹𝐹𝐹𝐹 𝐹𝐹𝑜𝑜𝑒𝑒𝑠𝑠𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑒𝑒 𝐴𝐴 𝐹𝐹𝑒𝑒𝑟𝑟𝑎𝑎𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝐹𝐹𝐹𝐹 𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑎𝑎𝑎𝑎𝑒𝑒 𝐹𝐹𝑎𝑎𝑎𝑎 𝐹𝐹𝑜𝑜 𝐹𝐹𝑡𝑒𝑒 𝑎𝑎𝐹𝐹𝑎𝑎𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝑙𝑙 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹

% percentage excess of A = 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝑒𝑒𝑒𝑒𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝐴𝐴 * 100%

Example #1 20 kmol/h C2H2 2,1

Products
50 kmol/h H2 529 25

sis
Calculate the percentage excess.
 By By
limiting rectant
i Katz
4 25
I H2 excess

feed Nst x100

Percent
Risto

12th 40 Kmol h
North 2 20
2
Nst
25 of H2
5
1 100
Limiting & Excess Reactants Fractional conversion & extent of reaction
% Conversion:
• It is not necessary that all the reactants get completely consumed,
even the limiting one. Therefore, fractional conversion is used to
indicate the degree of conversion for each reactant.
product
limiting Fed
reactant 𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝐹𝐹𝑜𝑜 𝐹𝐹𝐹𝐹𝑎𝑎𝑠𝑠𝐹𝐹𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹 𝐹𝐹 (𝐹𝐹𝑆𝑆 )𝑆𝑆𝑛𝑛 −(𝐹𝐹𝑆𝑆 )𝑆𝑆𝑜𝑜𝑆𝑆
𝑜𝑜𝑆𝑆𝑆𝑆𝑛𝑛𝑐𝑐𝑓𝑓𝑐𝑐𝑐𝑐𝑆𝑆𝑆𝑆𝑛𝑛 = =
𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝑜𝑜𝑒𝑒𝑓𝑓 𝐹𝐹𝑜𝑜 𝐹𝐹𝐹𝐹𝑎𝑎𝑠𝑠𝐹𝐹𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹 𝐹𝐹 (𝐹𝐹𝑆𝑆 )𝑆𝑆𝑛𝑛

Example#2:
If 100 mol/h of component A is fed to the reactor and 10 mol/h exits
out of the reactor. Calculate % conversion of A
9 Noo

409ft g
o
90
conversion
100M
reader Imotth
 Balances on a Reactor System
Three types of material balances can be performed
on a system that includes a reactor:
02 H2 0242.4 in out
a) Balances on molecular species ( illustrate only ).
o 015
s
4.55 Gil VC
or H in out
b) Balances on atomic species ( utilize fully ).
in out
c) Extent of reaction ( utilize fully ).
Menochear reaction
 Balances on a Reactor System
A) Molecular species balance: in reactor
Accumulation o
Continuous Reactor:
Input + generation – consumption= output
Batch Reactor:
Initial input + generation – consumption = Final output
• Note: Number of molecular species balances that can
be used equals the number of independent molecular
species in the reactor.
Example :

A, B A,B,C
Q aA + bB  cC
nAout = nAin + nAgen – nAcons
= nAin – nAcons
nBout = nBin + nBgen – nBcons
= nBin – nBcons

y
nCout = nCin + nCgen – nCcons
= nCgen

From the reaction:

If a moles of A reacted, then b moles of B should be consumed and c moles of C are
produced. This will yield the following relation:
nAconsumed 𝑎𝑎
nBconsumed = 𝑏𝑏  nAconsumed = (a/b) nBconsumed

nAconsumed 𝑎𝑎
nCgen. = 𝑆𝑆  nAconsumed = (a/c) nCgen.
nBconsumed = (b/c) nCgen.
 limiting
reactant Is
Example#3 d g
20 mol A /sec 10 mol A/s A 5546 21
50 mol B /sec 𝐹𝐹̇ B weibo.LI
OG Sis
𝐹𝐹̇ C
EMEI UW
Ul s 2 er no
2A + B  3C 8114611
Find 𝐹𝐹̇ B, 𝐹𝐹̇ C, 𝐹𝐹̇ Acons, 𝐹𝐹̇ Bcons, 𝐹𝐹̇ Cgen
reactant LR
A is limiting
ME
If 11 g 10 mol A Is
20 10
NAcons
NAout NAin Ma cons
NBout NBin NB cons
45 mot's
More I
Mr out 50 5 nacong
Meout Magen 15 mot 5molls
Megan

ng I 10
15mole
he gon fo
B) Atomic Balance:
• Atoms are neither destroyed, nor generated
except in a nuclear reaction.

Therefore,
Generation of atoms = consumption of atoms = 0

∴ Atomic Balance is:

𝐴𝐴𝐹𝐹𝐹𝐹𝑎𝑎𝑒𝑒 𝐹𝐹𝐹𝐹 = 𝐴𝐴𝐹𝐹𝐹𝐹𝑎𝑎𝑒𝑒 𝐹𝐹𝑎𝑎𝐹𝐹
 Example#4:
10 mol C2H4/s
20 mol C2H4 /sec 𝐹𝐹̇ Ȯ
2
30 mol O2 /sec 𝐹𝐹̇ C H O 10m01
2 4

Jol Enl do
IN 2C2H4+ O2 2 C2H4O
H balance
into
Calculate 𝐹𝐹̇ C H O and 𝐹𝐹̇ Ȯ 80142 atomic balance
2 4 2
Sol 1m81c c balance
221 10 It 39 30 mM
EYE
µ
NII Oz is
excessreactant
myth
20

Catty is LR hath Imojczkuo

balance on 20 Moons 10mot1sec 40 20 t 2neatly0
nconsumed

0 4out
rfano in
noron 30 5
2540 nczH40 40
221
10molls

54th
consumed
orout noin
noens
smol
Ytg no
to

I amogeneratin No
60 10 25 molls
ninoout 10mol 2
Agony 22 reaction
 A Reactive
C) Extent of Reaction Method (ξ).
2 nonreactive
Bowns nonreactive
Extent of reaction is a measure of how far a reaction has
proceeded.
Z
freactantes
(𝑛𝑛𝐴𝐴 )𝑜𝑜𝑜𝑜𝑜𝑜 −(𝑛𝑛𝐴𝐴 )𝑖𝑖𝑖𝑖
Oξ=
𝜈𝜈𝐴𝐴

y
where,𝜈𝜈𝐴𝐴 = stoichiometric coefficient of component A = -ve
for reactant = +ve for product.

- In general, for a single reaction:

(𝐹𝐹𝐴𝐴 )𝑆𝑆 = (𝐹𝐹𝐴𝐴 )𝑆𝑆 +𝜈𝜈𝐴𝐴 𝜉𝜉
 Acid Base 5 Salt water
Example#5: atomic
10 mol C2H4/s
20 mol C2H4 /sec in out
11.5154 𝐹𝐹̇ Ȯ
2
30 mol O2 /sec 𝐹𝐹̇ C H O
COLTH2O 2 4 molecular
in out
their is gon cons
oxidation 2C2H4+ O2 2 C2H4O
Nout Nin 8 reactant
E
Calculate 𝐹𝐹̇ C H O and 𝐹𝐹̇ Ȯ 8 8 product t
2 4 2

10 201 5
z
1 21 reactant

30 115 25 molls
Noro

0 1215 molls
Matty
first J Ch Chemical Equilibrium z

• Two fundamental questions of chemical reaction engineering:

1. What will be the final equilibrium composition of a reaction
system?
Refer to chemical equilibrium thermodynamics
2. How long will the system take to reach equilibrium?
Refer to chemical kinetics

• Equilibrium Reaction: equilibrium

- Chemical reactions are either Irreversible or Reversible
- Irreversible reactions:
reactions proceed in a single direction ( reactant  products )
- Reversible reactions:
reactants from products & products from reactants.
e.g. C2H4 + H2O ⇌C2H5OH equilibrium
rateofforward rate of
reaction backword
 e

Chemical Equilibrium
fraction

 Equilibrium reaction would eventually reach equilibrium

g or concentration

composition, i.e. where composition does not change with time.

 This is governed by a thermodynamics property called Equilibrium
Constant.
product
Gnc
ia
Keq = Equilibrium Constant = ∏ 𝐶𝐶𝐹𝐹𝜈𝜈𝐹𝐹 [for liquids] CRCccp
= ∏ 𝑃𝑃𝐹𝐹𝜈𝜈𝐹𝐹 [for gases] keg Ci
d CcCB
compoananti Keg
pm 𝑛𝑛𝑆𝑆 𝑛𝑛𝑆𝑆𝑆𝑆𝑆𝑆𝑎𝑎𝑠𝑠 CA CB
Ci = molar concentration of component i = = yi
𝑉𝑉𝑐𝑐𝑆𝑆𝑠𝑠 𝑉𝑉𝑐𝑐𝑆𝑆𝑠𝑠
Pi = partial pressure of component i = yi P
P = total pressure of the system.
𝜈𝜈𝐹𝐹 = stoichiometric coefficient. ( +ve for products, -ve for reactants )

Note: If Keq is given, then it is treated as an extra equation used with

material balance equations to solve the process variables.
 420
nCO 0.333 go
Example#6 1 mol CO /sec nH2O 1.333
2 mol H2O /sec nCO2 1
0.667
nH2 0 667
Co
1 1

1120 2
B 2
a CO is the limiting
equilibrium reactant
The above reaction proceeds to equilibrium in a batch reactor.
The reactor is initially fed with 1 mol CO and 2 mol H2O only.
If Keq = 1.0, find:

a) Limiting reactant. noFeed notch

b) % excess of the excess reactant. excess
notch
c) Composition of final output.
d)
Foriniting
% conversion of CO and H2O.
 100
exassinthongsten
2,1
1

Fifty
Nco I 712

BHO 2 z

N coz Ot Z N coz
n Az
z
H2 O

Coo Ie 9 20 41
City GHz NHA
Coz Bpoe

extant

EST a

0.667
E 3

Composition
 0.333 Mol ya 0331 0.111
Nco 1 0.667
333 Ml 0 444
Muzo 2 0.667 Yuzo 1.331
01667 mo 0.222
Nco Of 0.667 ya 0.6361
0 667 Nd 20.222
0.667
haze 0
y 03661
3m01
Not 2
4 1

Limiting reactient

d
fo mules reated noon
noon
93311

moles feed Tin 0.6674100

66.7
2 21.333 33.39
20
ftp.mnt
 am reactio
I Example#7 single
notequilibrium
C3H3N is produced in the reaction of C3H6, NH3 and O2 N air
U'M T 9 6 N pain 0.78
conversion
C3H6+ NH3 + 1.5 O2 C3H3N+ 3H2O 21
N
The feed contains 10 mole % C3H6 , 12% NH3 and 78%4oz
I 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 reactant is in
excess, and the molar composition of the product. H est
I Bases 100m01 Ar offed

III
i insmonth
Inoue hint n'ni 62 got h
42MHz 0.12
8 M's
43 0 16389 n mo z a moi h ti
0.783 0.21

ANz 0.781 0.79 Ed Ish E N of mot

0.62
ja jiff
 10.6
100,101
210 Nuts 12 Moz
Ig
Nyt É s smallest ratio

L R is a
D Stach 4100
need
excess
Nstoich B NH3
10 100 20
12 coz
MHz excess
6 67 I Na
16
or excess
is D CAN
T Y E Ho
Astoich MHS 885mg
Iggy wi SH
101 15 851 a
no stoich joy
94 Xx
Stoic

A B 15C D 3 E 7m01
out A snout
reactant 10

1
limiting
Min nont 10
conversion
nin
MOA 3mn01
z Ni
IF
in reactant y
her
NOB 12 3 9 moi
NB Nin E 11.5 moi h
311.51
Noe 16
1.5 Z
3 Moth
Nc Nin
Do
Np Yin
t Z th
33 9 moi
Nt Vin 37 MEO
0.068
91 15 1
8 89
TA 1 5 0.089
0.611 go.gs
Yo 0.113
YI Eg Yg
solve byatomic
 Multiple Reactions, Yield & Selectivity
• If we have multiple reactions, where molecular species react and/or are produced
in several reactions, then the following can be used to perform a material
balance:
#𝑐𝑐𝑓𝑓𝑎𝑎𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑆𝑛𝑛

𝐹𝐹𝑆𝑆,𝑆𝑆𝑜𝑜𝑆𝑆 = 𝐹𝐹𝑆𝑆,𝑆𝑆𝑛𝑛 + � 𝜈𝜈𝑆𝑆𝑗𝑗 𝜉𝜉𝑗𝑗

𝑗𝑗=1
gym
• Two terms can be used to describe the degree to which a desired reaction
predominates over competing side reactions:
in ski unitless
𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝑓𝑓𝑒𝑒𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝐹𝐹 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝑒𝑒𝑓𝑓
𝑌𝑌𝐹𝐹𝑒𝑒𝑎𝑎𝑓𝑓 =
𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝑓𝑓𝑒𝑒𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝐹𝐹 𝐹𝐹𝑜𝑜 𝐹𝐹𝐹𝐹 𝑒𝑒𝐹𝐹𝑓𝑓𝑒𝑒 𝐹𝐹𝑒𝑒𝐹𝐹𝑒𝑒 𝑒𝑒𝑒𝑒𝐹𝐹𝑒𝑒𝐹𝐹
𝐹𝐹𝐹𝐹𝑓𝑓 𝐹𝐹𝑡𝑒𝑒 𝑎𝑎𝐹𝐹𝑎𝑎𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝑙𝑙 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝑒𝑒 𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑎𝑎𝑎𝑎𝑒𝑒𝑓𝑓 𝐹𝐹𝐹𝐹𝑎𝑎𝑠𝑠𝑎𝑎𝑒𝑒𝐹𝐹𝑒𝑒𝑎𝑎𝑐𝑐 1 1 AW
 Yield is dimensionless
i I
𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝑓𝑓𝑒𝑒𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝐹𝐹 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝑒𝑒𝑓𝑓 witless
𝑆𝑆𝑒𝑒𝑎𝑎𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝑆𝑆𝐹𝐹𝐹𝐹𝑐𝑐 =
𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝑜𝑜 𝑎𝑎𝐹𝐹𝑓𝑓𝑒𝑒𝑒𝑒𝐹𝐹𝐹𝐹𝑒𝑒𝑓𝑓 𝑠𝑠𝐹𝐹𝐹𝐹𝑓𝑓𝑎𝑎𝐹𝐹𝐹𝐹 𝑜𝑜𝐹𝐹𝐹𝐹𝑎𝑎𝑒𝑒𝑓𝑓
y
 Selectivity has units of moles desired/ moles undesired
Example gesined

A 11.5 B C 2D
undesired

B ZE

ni ni Vij Z j

cow Ncin Zo Ej
 Z 72 4335 2
Example#8 41.65 85 21 22
Z 0.471
Matt neatly yield a fly
The reactions I
85m01 desired
o.gl bothreaction
1 reactant C2H6 C2H4+ H2
so we dont undesierd
have C2H6 + H2 2CH4
Reactant
limiting

Take place in a continuous reactor at steady state. The feed contains 85 mole
out
% ethane (C2H6) and balance inert (I). The fractional
desired
conversion of ethane is
0.51, and the fractional yield of ethylene(C2H4) is 0.471. Calculate the molar y
composition of the product gas and the selectivity of ethylene to methane
f contusion
Iii
(CH4) production. 100motfeed

0.51 85 cat
Catty 40
85 4 YoHe 085
0.45185
8g 0.51185 0.15 Mz
ga YI
heart any 6.6
ME NIi 15 not
Mol of desired onereaction
Yeild desired if
mot of
EAI
 0.471
É
conversion
sidereaction and tooo
n no
mother
40.03
NC244 NE Hy
0.47 0.851100

Noth
reaction and tooo conversion 88114
nice if no side

overall
carbon balance
40.03 Menu l
2141 65 2
2185
NCHy 6.64 mock

Zi 6.02
0244 48.64
Selectivity Metin 22 2

91 4 it
N Hut Z
nutty
ACHU 222

DX
no HE 1222

21 6.02 2 22
É 12.0422
2 12.04 2.32
72 43
35
21 12.04 22
4335
13.0422
Zz 3.32
332
MHz X ez zz
39.97
36 65 moi h
Example#9

Methane(CH4) and oxygen (O2) react in the presence of a catalyst to form

formaldehyde (HCHO). In a parallel reaction, methane is oxidized to carbon
dioxide (CO2) and water( H2O)
D
selectivity Tun
CH4 + O2 HCHO+ H2O

CH4 + 2O2 CO2+ 2H2O Yeild

tf
Yim0.5 you O 5
The feed to the reactor contains equimolar amounts of methane and oxygen.
The fractional conversion of methane is 0.9 and the fractional yield of
formaldehyde is 0.855. Calculate the molar composition of the reactor output
stream and the selectivity of formaldehyde production relative carbon dioxide
production. Assume a basis of 100 mol feed/s .

100 molls
Nt
fay 0.9 N CH4 5 molls
0.855 100molls 02 2
Yield 0
molls
902205 14170 42.75 molls
1120 47.3 molls
Ym 05
CO2 2.25 molls
10030.5 nout
og
f Nettingngchout 0010 5

NCHy out 5 molls

nonfHy
2
Nin Z 22
21 22 45 equ
5 50 7 1 22

Yieldaction here 0.855 Maggot

sfumatothat note 4150
mot of E III
Lakin if no
Mont Hoo 42.75 molls
Sidereaction

ZI
NACHOout
Yn
Zi 4275 molls
4275 7 2 45
from eq
22 225 molls
1120 balance
02balance 222
227 hout Min Z
Mont Nin Z
250 37,3 24 42.7 262.251 47.3
27
2

CO2
nowt Mix 22
944 005
0.027
Yo

Zl
NHON a
selectivity zig
n coz

18.5 molof mol

74275 of
CO2
 Overall
Product Separation and Recycle
singlein Reactor
W
N
O O
0
Recycle
Two definitions of reactant conversion are used in the analysis of chemical
reactors with product separation and recycle of unconsumed reactants:

𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝐹𝐹𝐹𝐹 𝑠𝑠𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒 − 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝑎𝑎𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝑜𝑜𝐹𝐹𝐹𝐹𝑎𝑎 𝑠𝑠𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒

𝑂𝑂𝑆𝑆𝑒𝑒𝐹𝐹𝑎𝑎𝑎𝑎 𝐹𝐹𝐹𝐹𝐹𝐹𝑆𝑆𝑒𝑒𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹 =
𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝐹𝐹𝐹𝐹 𝑠𝑠𝐹𝐹𝐹𝐹𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒

𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝐹𝐹𝐹𝐹 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 − 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝑎𝑎𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝑜𝑜𝐹𝐹𝐹𝐹𝑎𝑎 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹

𝑆𝑆𝐹𝐹𝐹𝐹𝑙𝑙𝑎𝑎𝑒𝑒 𝑠𝑠𝐹𝐹𝑒𝑒𝑒𝑒 𝐹𝐹𝐹𝐹𝐹𝐹𝑆𝑆𝑒𝑒𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹 =
𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 𝐹𝐹𝐹𝐹𝑠𝑠𝑎𝑎𝐹𝐹 𝐹𝐹𝐹𝐹 𝐹𝐹𝑒𝑒𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹
 overall conversion 3 Single conversion
Example#10
É Idb 94 Is 75 mol B/s
5 mol A/s
Jebb Is
30 mol A/s
75 mol A/s 75 mol B/s
100 mol A/s
25 mol A/s

O Z

4100 707
in reactor 100 30
Single pass conversion of A =
100 0.93
75 5
Overall conversion of A = 100 93 33
75
Example#11

Propane (C3H8)is dehdrogenated to form propylene (C3H6) in a catalytic reactor

A B C
C3H8 C3H6 + H2

The process is to be designed for a 95% overall of propane. The reaction products are
separated into two streams: the first, which contains H2, C3H6 and 0.555% of the C3H8
that leaves the reactor, is taken off as product: the second stream which contains the
balance of the unreacted C3H8 and 5 % of the C3H6 in the first steam, is recycled to the
reactor. Calculate the composition of the product, the ratio(moles recycled/mole fresh
feed), and the single-pass conversion
Foverall B 0.95

mixingpoint

o r o
u

To
 no 0.95 100 1
f 1090

NG 5

no 0.51 n 5 0.55ft M3

M3 900.9 mol

Its balance in separator

nz NG t ng
900.9 5 99

ng 895.9 moi
propane balance Cst
mixingpoint

100 t Ta na

100 895.9 995.9

I Ain not M
now extent of reaction
N
Dz Ni z Z n
9009 95

mo hs
2 995.9

Yin Z 95m01
 Product Separation and Recycle
single 11 a 51 My
How can we achieve high overall conversions?
a) Design a reactor with a high single pass
conversion
b) Design a reactor with low single pass
conversion and follow it with a separation unit
to recover and recycle unconsumed reactant

singleconversions in reactor
h
PT J't
 Purging
• Purging is used to prevent material buildup
• A portion of the recycled stream must be withdrawn as a purge
stream to rid the process of the substance that is accumulating

Example Ethylene + air Ethylene oxide

2C2H4 + O2 2C2H4O

loss

inert buildup N2
CoatH2O Oz Jule in 9154
Combustion Reactions
• Combustion is a rapid reaction of a fuel with oxygen
• Combustion reactions are important because of the É A
tremendous amount of energy they release conversion 100
f
Complete Combustion
(No CO is formed) CO211120
• Combustion reactions
A
A Incomplete combustion
Exothermic IM
(CO is formed) CO2 H2O
i

t
2 Diffrenet reaction Yield and
selectivity
• The product gas that leaves a combustion furnace
is referred to as the stack gas or flue gas.
 Combustion Reactions
Incompletereaction
Atom Product
C 
g
CO2 or CO H2O
H  H2O
S  SO2
0
N  NO2
O
Examples of combustion reactions
C + O2  CO2 Complete combustion
C3H8 + 5O2  3CO2 + 4H2O Complete combustion
O
C3H8 + 3.5O2  3COO+ 4H2O Incomplete combustion
CS2 + 3O2  CO2 + 2SO2 Complete combustion

• For economic reasons, air is the source of oxygen.

Air ≈ 79 mol% N2, 21 mol% O2 “ MW = 29 “ of air
Or air has 3.76 mol N2 per mol O2.
pair
Nz dib d
it ox reactor
reactor d i 315 reader si e or
Composition of wet & dry basis:

• Composition on wet basis: mole fractions includes that

of H2O
• Composition on dry basis: mole fractions of dry gas
only ( no H2O ) 420
ME
Example #12: Wet  Dry
A stack gas contains:
60 mol% N2 Inert
s
15 mol% CO2
10 mol% O2 reactant
15 mol% H2O

Calculate the molar composition of the gas on a dry basis.

 MA tuk
4002 51120 H2O YI 9W
Gatto 13202
gas is
C2Hiv 9202 40 5420
1420
only condensable gas
Catto
ON

94th CO2
02
Mr HO my
É
C's
did

Example 12
100m01 of wet
basis

60mot Nz
15m01 CO2
10 mot 02
15 Mol HO Ae NH2O

Tdray 85mot

Nur 60m01
Ncos
15 mot
70 6 17.6
10 mot
No
gg
Yu dray
Lig 0 176
0706170.644
17.6
Yoon
dray yoga 11g
11.7
Iy IT 0117
Example #13: Dry  Wet
If a stack gas has the following dry basis molar composition:
65mol% N2
14 mol% CO2
11 mol% CO
10 mol% O2

Also, it is known that the molar composition of H2O in the

stack gas is equal to 0.07. Calculate the molar composition
of the stack gas on a wet basis: Ruz
RNewet dry
Yazwet tyre dry
 basis Neary 100mot of dry
10m01
Nco 11m01 Roz
NN2 65 mol Ncoz 14 mot

0.07
pontiff
Tho É n1
7.52 Mol
Muzo
107.52 Mal
NTdry nH2o 100 7.52
Tweet

57752
Treswet FYI
Your wet 17.52

Ycomet
F52
Yo met ftp.go

0 07 int or 52
1
Yuzo
 excess air I
Theoretical & Excess Air. fate limiting
reacting
Theoretical Oxygen: exact amount of needed oxygen to reacting
completely burn all fuel molecules, assuming all carbon in the jjjt
Wf
fuel is oxidized to CO2 and all hydrogen is oxidized to H2O. Air free
Theoretical air: amount of air that contains theoretical oxygen
the complete Y WI Y
is
46151 comp let
Stoich
reaction

É
𝑀𝑀𝑆𝑆𝑠𝑠𝑓𝑓𝑐𝑐 𝑆𝑆𝑓𝑓 𝑇𝑇𝑆𝑓𝑓𝑆𝑆𝑐𝑐𝑓𝑓𝑆𝑆𝑆𝑆𝑆𝑆𝑎𝑎𝑠𝑠 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑓𝑓𝑛𝑛
Theoretical air =
0.21
a É if i

n Incomplete
Excess Air : The amount by which the air fed to the reactorUbos Th
exceeds the theoretical air. JgId 1bW1 G complete it

(𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝐹𝐹𝐹𝐹)𝑓𝑓𝑓𝑓𝑓𝑓 −(𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝐹𝐹𝐹𝐹)𝑆𝑆𝑆𝑓𝑓𝑆𝑆𝑐𝑐𝑓𝑓𝑆𝑆𝑆𝑆𝑆𝑆𝑎𝑎𝑠𝑠

TÉ
% 𝐸𝐸𝑒𝑒𝐹𝐹𝑒𝑒𝑒𝑒𝑒𝑒 𝐴𝐴𝐹𝐹𝐹𝐹 = 𝑒𝑒𝑥𝑥𝑥 w
(𝑎𝑎𝐹𝐹𝑎𝑎𝑒𝑒𝑒𝑒 𝐹𝐹𝐹𝐹𝐹𝐹)𝑆𝑆𝑆𝑓𝑓𝑆𝑆𝑐𝑐𝑓𝑓𝑆𝑆𝑆𝑆𝑆𝑆𝑎𝑎𝑠𝑠
spin
4002 51120
complite Gatto 1302
% Excess air = % Excess O2 gym go 400 540
In
compli d It
Theorifical stock H
Example#14
C4H10 + 6.5O2  4CO2 + 5H2O
100
nair,in = 5000 mol/s 101
Nctc
n𝐶𝐶 𝐻𝐻 ,in = 100 mol/s 5000 0 21 161.5
4 10
65
650m01
Mine 02 6.51100 84th is L R

Calculate
(1) Theoretical air mot of Theoretical oxygen
3,095
Effie
0.21
(2) % Excess air Pair in hair Theor
yo
hair Theor
31095
15000 11100 61 5
3,095
 5000 0 21131095
Excess 02 0 21

021 3,095
Excess of air 6154
Example#15 keyword E I

A fuel of unknown composition (CxHy) is burned in a furnace with excess air.

The product gas gives the following results on a dry basis: complete
because we don't
10.5% CO2 complete have CO
5.3% O2
84.2% N2
C H
A. Determine molar ratio of carbon to hydrogen in the fuel. (x/y) complete
B. Determine % excess of air. feed 116 am gs osa conversion
Nt
cays
5 atomic
xcoz 0 s
Catty
2 5
02 2 ftp catty fro
LXII gÉÉmÉ
CxHy É 02 X CO2 11120 Air
0
10658
Yg 10 5 Mel
8425 n CO2
NH2O
x 141am
Inert in out
NNz 6
M 0.79
Nair
 basis 100mot of dry stack

carbon balance

NCxtly x 10.5111 eq

dt gg 2
84.212
106.58mot
Aire

l
nino
3,1 114 5.3610.5 2

06.58
mol
Nino 13 33

Hbalance 26.66
mot
Muzo 2
YNexty
TMexty 26.66 not cq 21

dividing eft over 09121

10.5 0.394

gift
25
26 66 q4t
y
a 9250
9 5
x 2 y 5
245
251120
4 2 202
Hst 2 3502 out
in
53 02110651 5.25 mo

Z Morty 3.25
 NexHy Z
5.251 17.06
noostock tyg
Mfg 3,1 mo

17.06 100 31.09

excess
181
Independent
in coffesion
 Example#16 excess of Oz

Ethane burned with 50% excess air. The percentage conversion of the
ethane is 90% : of the ethane burned, 25% reacts to form CO and the
t
inco out
balance reacts to form CO2.

Calculate molar composition of the stack gas on dry basis & mole ratio
of H2O to dry gas stack.
complete Can I 02 2002 3720
Catto 02 20 3420
Incomplete
I z 10m
i n Gift

Basis 100 mot Of 22516 out

hair
tool
2500
IEEE135
Moz
0 21 neo 45
No 525m Y 02 n 420 27
79
y Ma O
mot
ANz 1975
 f conversion
Nathingfightt
to mot
Matto
0.9 go to't

Nastochitheoviticall
Main
Theoriticall
Moz excess Nor Stoch

N catkin
No stock in complice reaction 88g
100 350 mot
Iz 525 mo
nozin
0.5
N2inj3
2500 mot
Nair 51
1975 mol
2500 0.79
AM

napkin Z 72
Heart
72 90 3
Z
4
75
3 22
z mot
22.5 moi
22 90 Zz 67.5
322
3 225
422 90 71
 525

now in
EY zits
nor out 232 5

271
coz out Yin 1.35
216751
Nco out

co out Xin 272

Nco 45 mot
3122.51
3167.57
321 372

420,5
H2O in 270
Raf
n accept tho
Mary basis sum of all

0.1126

5
It
23
Example#17

A hydrocarbon gas is burned with air . The dry –basis product

gas composition is 1.5 mole% CO, 6 % CO2, 8.2 % O2 and
84.3% N2. There is no atomic oxygen in the fuel. Calculate the
ratio of hydrogen to carbon in the fuel gas.
CO2 H2O
02
Cx Hy
10000
dry Basis Product guy Catty
Mary
Basis too mot

III s

N 102 6

hair 1007 no 2 8 2
4
02 22 Nns 843
N H2 84.3
nH20I
 No balance

843 AM out
8 106.7 moi
Nairfeed 39
0.21 22 4 moi
Moz 106.7

O balance
NH2O l
1.547 612 8 212
22 4121

NH20 14.9 mol

A balance
N 20 12
Mary Y
2114.9 2918 mot eyes
Y Nary

Chulance

X 15 64 75 Mol eyes
Natty
3.97 4
gray 241g
xna
x 4 Y
X I 9 4
CH4 method group