Multiple reactions

che362
Engr. Kirsten Gail T. Miaga
Selectivity in Multiple Reactions
A + B ⎯⎯→
kD
D rD = k DC A2CB (Desired)
A + B ⎯⎯→
kU
U rU = kU C ACB2 (Undesired)
Selectivity Yield
Instantaneous SD/U = rD/rU YD = rD / − rA

Overall ŜD/U = FD/FU YˆD = FD /( FA0 − FA )

rD k D C A2C B k D C A
S D /U = = 2
=
rU ku C AC B kU C B
Keep CA high and CB low.

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Semibatch Reactors
• Semibatch reactors can be very effective in maximizing selectivity in
liquid phase reactions.
• The reactant that starts in the reactor is always the limiting reactant.

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Semibatch Reactors
Semibatch reactors
A+B→C+D
B, v0
m

Initial V
A

Liquid level and volume

increase

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Semibatch Reactors
dm
1) Mass Balance: = m
dt
m = 0  0 and m = V0
dm dV
= 0 =  00
dt dt
dV
= 0
dt
t = 0 V = V0
V = V0 + 0t

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Semibatch Reactors
1) Mole Balance on Species A:
[in] – [out] + [gen] = [acc]
dN A
0 − 0 + rAV =
dt
dN A d [C AV ] dC A dV
= =V + CA
dt dt dt dt
dV
= 0
dt
dC A  0C A
= rA −
dt V
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Semibatch Reactors

1) Mole Balance on Species B:

dN B
FB 0 − 0 + rBV =
dt
dN B d [CBV ] dCB dV
= =V + CB
dt dt dt dt
dV
FB 0 = CB 00 = 0
dt

dC B
= rB +
(C B 0 − C B )0
dt V 7
Semibatch Reactors
1) Mass and Mole Balance Summary
 0C A
(1) dC A
= rA −
dt V
0 (CB 0 − CB )
(2) dC B
= rB −
dt V
0CC
(3) dCC
= rC −
dt V
 0C D
(4) dC D
= rD −
dt V
(5) V = V0 + 0t
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Semibatch Reactors
2) Rate Laws (6) rA = kC AC B
− rA − rB rC rD
3) Stoichiometry = = =
1 1 1 1

(7 ) rB = rA
(8) rC = −rA
(9) rD = −rA
N A0 − N A
(10) X=
N A0
(11) N A0 = C A0V0
(12) N A = C AV
4) Parameters C A0 , V0 , 0 , k , CB 0 9
Semibatch Reactors
Polymath 2.1_[Surname]

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Semibatch Reactors

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Equilibrium Conversion in Semibatch Reactors with Reversible
Reactions

Consider the following reaction:

⎯⎯→
A + B
⎯⎯ C + D

Everything is the same as for the irreversible

case, except for the rate law:

 CC CD 
− rA = k A C ACB − 
 K C 

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Equilibrium Conversion in Semibatch Reactors with Reversible
Reactions
Where: N A0 (1 − X )
C A=
V

C B=
( FB 0t − N A0 X )
V
N X
C C = C D = A0
V
At equilibrium, − rA = 0 then
CCe C De N Ce N De N A0 X e2
K C= = =
C Ae C Be N Ae N Be (1 − X e )(FB 0t − N A0 X e )
Xe changes with time.

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P6-6B - Semibatch Reactors
Sodium Bicarbonate + Ethylene Chlorohydrin → Ethylene Glycol + NaCl +
CO2

NaCHO3 + CH2OHCH2Cl → (CH2OH)2 + NaCl + CO2 

A + B → C + D + CO2 

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P6-6B - Semibatch Reactors
Semibatch Reactors in terms of Moles
A + B → C + D + CO2
dN a
Mole Balances A (1) = rAV
dt
dN b
B (2) = FB 0 + rBV
dt
dN c
C (3) = rCV
dt
D (4) N D = NC
CO2 0 = − FCO2 + rCO2V
(5) FCO2 = rCO2V
Stoichiometry − rA = −rB = rC =r D = rCO2
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 dV
(6) = 0 − CO2
dt
FCO2 MWCO 2
(7 ) CO2 =
RHO
(8) MW = 44
(9) RHO = 1000
(10) Ca = N A V
(11) CB = N B V
Rate Laws (12) rA = −kC AC B
N a0 − N a
(13) X=
N a0
(14) N a 0 = V0Ca 0
Rest of the Polymath Statements
Similar to Concentration Program 16
P6-6 Semibatch: Moles, Na, Nb, etc.
Polymath 2.2_Surname
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P6-6 Semibatch: Concentrations CA, CB, CC
Polymath 2.3_Surname
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 Semibatch Reactors
Three Forms of the Mole Balances applied to Semibatch Reactors:

dN A
1. Molar Basis dt = rAV
dN B
= FB 0 + rBV
dt
dC A 0 dN A
2. Concentration = rA − C A = rAV
Basis dt V dt
0
= rB + (CB 0 − CB )
dC B dN B
= FB 0 + rBV
dt V dt

dX − rAV
3. Conversion =
dt N A0
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 Semibatch Reactors
Consider the following elementary reaction:
A+B → C+D
-rA=kCACB
The combined Mole Balance, Rate Law, and
Stoichiometry may be written in terms of number of
moles, conversion, and/or concentration:

Conversion Concentration No. of Moles

dX k (1 − X )(N Bi + FB 0t − N A0 X ) dC A 
= rA − C A 0
dN A
= rAV
=
dt V0 + 0t dt V dt


= rA + (CB 0 − CB ) 0
dC B dN B
= FA0 + rBV
dt V dt
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Polymath Equations

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Activity #8

• Run the Polymath Programs (vary time intervals)

• Submit screen recordings
• Write graph analysis for the 3 problems and consolidate it in one file (pdf
format)

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