Chapter 3 – Stoichiometry

 Size CSTRs and PFRs given –rA=f(X)

 Reaction Orders
 Arrhenius Equation

 Stoichiometric Table
 Definitions of Concentration
 Calculate the Equilibrium Conversion, Xe

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 We shall set up Stoichiometry Tables using species A as our basis
of calculation in the following reaction. We will use the
stochiometric tables to express the concentration as a function
of conversion. We will combine Ci = f(X) with the appropriate
rate law to obtain -rA = f(X).

b c d
A + B→ C + D
a a a
A is the limiting Reactant.

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 NA = NA 0 − NA 0 X
For every mole of A that react, b/a moles of B react. Therefore
moles of B remaining:
b  NB 0 b 
N B = N B 0 − N A 0 = N A 0 − X
a  NA 0 a 
Let ΘB = NB0/NA0
Then:
 b 
N B = N A 0  B − X 
 a 
c  c 
NC = NC 0 + N A 0 X = N A 0 C + X 
3 a  a 
Species Symbol Initial Change Remaining
A A NA0 -NA0X NA=NA0(1-X)
B B NB0=NA0ΘB (-b/a)NA0X NB=NA0(ΘB-b/aX)
C C NC0=NA0ΘC (+c/a)NA0X NC=NA0(ΘC+c/aX)

D D ND0=NA0ΘD (+d/a)NA0X ND=NA0(ΘD+d/aX)

Inert I NI0=NA0ΘI ---------- NI=NA0ΘI
NT0 NT=NT0+δNA0X
N i 0 Ci 0 0 Ci 0 yi 0 and  = d + c − b − 1
Where: i = = = =
N A0 C A0 0 C A0 y A0 a a a

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δ = change in total number of mol per mol A reacted
 Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel) batch reactor
Then V = V0
N A N A 0 (1 − X )
CA = = = CA 0 (1 − X )
V V0
 NB NA 0  b   b 
CB = =  B − X  = C A 0  B − X 
V V0  a   a 
 etc.
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 Suppose − rA = k AC AC B

Batch: V = V0

 b 
− rA = k AC A0
2
(1 − X )  B − X 
 a 
Equimolar feed: B = 1
b
Stoichiometric feed: B =
a

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 if −rA = k A CA2 CB then

 b 
−rA = CA 0 3
(1 − X ) B − X  ConstantVolume Batch
2

 a 

and we have −r = f (X )
A

1
 − rA

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X
 Calculating the equilibrium conversion
for gas phase reaction,Xe
Consider the following elementary reaction with KC=20 dm3/mol
and CA0=0.2 mol/dm3.
Xe’ for both a batch reactor and a flow reactor.

2A  B
 2 CB 
− rA = k A C A − 
 KC 
8
 Calculate Xe
C A0 = 0.2 mol dm 3

K C = 20 dm3 mol

Step 1: dX −rAV
=
dt NA 0
Step 2: rate law, − rA = k A C 2A − k BC B
 2 CB 
− rA = k A C A − 
  K C

kA
KC =
9 kB
 Calculate Xe
Symbol Initial Change Remaining
A NA0 -NA0X NA0(1-X)
B 0 ½ NA0X NA0 X/2

Totals: NT0=NA0 NT=NA0 -NA0 X/2

@ equilibrium: -rA=0 C Be
0=C −2
Ae
KC
CBe N Ae
Ke = 2 CAe = = CA 0 (1 − X e )
CAe V
Xe
CBe = CA 0
10 2
 Calculating the equilibrium conversion
for gas phase reaction
Solution:
At equilibrium  2 C Be 
− rA = 0 = k A C Ae − 
 K C 

C Be
KC = 2
C Ae
Stoichiometry A → B/ 2
Constant volume V = V0
Batch
Species Initial Change Remaining
A NA0 -NA0X NA=NA0(1-X)
B 0 +NA0X/2 NB=NA0X/2
11 NT0=NA0 NT=NA0-NA0X/2
 Xe
CA0
2 Xe
Ke = =
C A 0 (1 − X e ) 2C A 0 (1 − X e )
2 2

= 2(20)(0.2) = 8
Xe
2K e C A 0 =
(1 − X e )2

X eb = 0.703

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 Writing -rA Solely as a Function of X.

Write the rate law for the elementary liquid

phase reaction solely in terms of conversion.
The feed to the batch reactor is equal molar A & B
with CA0 = 2 mol/dm3 and kA= .01 (dm3/mol)41/s.

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 Rate Law: -rA=kC3AC2B

Stoichiometry:
Species A
Liquid phase, v = vo (no volume change)

Species B

Species A is the limiting reactant because the

feed is equal molar in A and B, and two moles of
14
B consumes 3 moles of A.
 We now have -rA=f(X) and can size reactors or
determine batch reaction times.
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 Flow System Stochiometric Table

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)

Where: i = Fi0 = Ci0 0 = Ci0 = y i0

16 FA 0 CA 0 0 CA 0 yA 0
 Flow System Stochiometric Table
Species Symbol Reactor Feed Change Reactor Effluent
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)

D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)

Inert I FI0=A0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X

Where: i = Fi 0 = Ci 0 0 = Ci 0 = yi 0
FA 0 C A 0 0 CA0 yA0

and d c b
 = + − −1
a a a
Concentration – Flow System C A = FA
17

 Species Symbol Reactor Feed Change Reactor Effluent
A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=FA0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X

Fi 0 C  C y d c b
Where: i = = i0 0 = i0 = i0 and = + − −1
FA 0 C A 0 0 C A 0 y A 0 a a a

FA
Concentration – Flow System C A =
18 
 FA
Concentration Flow System: C A =

Liquid Phase Flow System:  = 0

FA0 (1 − X )
= C A0 (1 − X ) Flow Liquid Phase
FA
CA = =
 0
N B N A0  b   b 
CB = = 
 B − X  = C A0   B − X
V V0  a   a 
etc.
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 If the rate of reaction were − rA = kC AC B

 b 
then we would have − rA = C A0
2
(1 − X )  B − X 
 a 

This gives us − rA = f ( X )
FA0
− rA

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X
 Combining the compressibility factor equation of
state with Z = Z0
Stoichiometry: P
CT =
ZRT
P0
CT 0 =
Z 0 R0T0
FT = CT
FT 0 = CT 00
We obtain:
FT P0 T
 = 0
FT 0 P T0
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 FA  P  T0  FT 0  FA  P  T0 
C A = FA  =    =    
 FT   P0  T  0  FT  P0  T 
0  
 F0 
CT 0 = FT 0 0

 FB  P  T0 
C B = CT 0    
 FT  P0  T 

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23
 The total molar flow rate is: F = F + F X
T T0 A0


Substituting FT gives:  =  0  FT 0 + FA0X
 T P0
 
 FT 0  T0 P
 FA0  T P0
 = 0 1 + X 
 FT 0  T0 P
 = 0 (1 + y A0X )
T P0
T0 P

 = 0 (1 + X )
T P0
24 T0 P
 FA
Concentration Flow System: C A =


 = 0 (1 + X )
T P0
Gas Phase Flow System:
T0 P

FA FA0 (1 − X ) C (1 − X ) T0 P
CA = = = A0
 0 (1 + X )
T P0 (1 + X ) T P0
T0 P

 b   b 
FA0   B − X  C A0   B − X 
CB =
FB
=  a 
=  a  T0 P
  (1 + X ) T P0 (1 + X ) T P0
0
25 T0 P
 If –rA = kCACB

  b  
 (1 − X )   B − a X   P T  2 
− rA = k AC A0 
2    0
 
 (1 + X ) (1 + X )  P0 T  
 

This gives us
FA0/-rA

26 X
 Xef
Consider the following elementary reaction with KC=20 dm3/mol
and CA0=0.2 mol/dm3.
Calculate Equilibrium Conversion or both a batch reactor (Xeb)
and a flow reactor (Xef).
2A  B
 2 CB 
− rA = k A C A − 
27  KC 
 2A  B
X eb = 0.703
X ef = ?
 Solution:
  2 CB 
 Rate law: − rA = k A C A − 
 K C 

1
A→ B
2
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 Species Fed Change Remaining
A FA0 -FA0X FA=FA0(1-X)
B 0 +FA0X/2 FB=FA0X/2
FT0=FA0 FT=FA0-FA0X/2

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 A FA0 -FA0X FA=FA0(1-X)
B 0 FA0X/2 FB=FA0X/2

Stoichiometry: Gas isothermal T=T0, isobaric P=P0

V = V0 (1+ X )
FA 0 (1 − X ) CA 0 (1 − X )
CA = =
V0 (1+ X ) (1+ X )
FA0 X 2 C A0 ( X )
CB = =
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V0 (1 + X ) 2(1 + X )
  C (1 − X )  2 C A0 X 
− rA = k A  A0
 − 
 (1 + X )  2(1 + X )K C 
Pure A → yA0=1, CA0=yA0P0/RT0, CA0=P0/RT0

1 
 = y A0 = (1) − 1 = −
1
2  2
@ eq: -rA=0

X e (1 + X e )
2 K C C A0 =
31 (1 − X e )2
  dm3  mol 
2 K C C A0 = 2 20  0.2 3  = 8
 mol  dm 

1  1
 = y A 0 = 1 −1 = −
2  2

X e − 0.5X e 2
8=
(1 − 2X e + X e
2
)
8.5X e 2 −17X e + 8 = 0

Flow: X ef = 0.757 Recall Batch: X eb = 0.70

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 Heat Effects
Isothermal Design
Stoichiometry
Rate Laws
Mole Balance

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