Conversion and Design

Equation
Dr Josephine Lai Chang Hui
Stoichiometric Table
Species Initial (mol) Change (mol) Remaining (mol)
Particular species Number of moles of each Change in the number of Number of moles
species initially present moles brought about by remaining in the system
reaction at time t
Batch system 𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑
𝑏𝑏 𝑐𝑐 𝑑𝑑
𝐴𝐴 + 𝐵𝐵 → 𝐶𝐶 + 𝐷𝐷
𝑎𝑎 𝑎𝑎 𝑎𝑎
Batch system
• Number of moles of A remaining in reactor:
• 𝑁𝑁𝐴𝐴 = 𝑁𝑁𝐴𝐴𝐴 − 𝑁𝑁𝐴𝐴𝐴 𝑋𝑋 = 𝑁𝑁𝐴𝐴𝐴 (1 − 𝑋𝑋)
Species Initial (mol) Change (mol) Remaining (mol)
A 𝑁𝑁𝐴𝐴𝐴 −(𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐴𝐴 = 𝑁𝑁𝐴𝐴𝐴 − 𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
B 𝑁𝑁𝐵𝐵𝐵 𝑏𝑏 𝑏𝑏
− (𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐵𝐵 = 𝑁𝑁𝐵𝐵𝐵 − 𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑎𝑎 𝑎𝑎
C 𝑁𝑁𝐶𝐶𝐶 𝑐𝑐 𝑐𝑐
+ (𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐶𝐶 = 𝑁𝑁𝐶𝐶𝐶 + 𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑎𝑎 𝑎𝑎
D 𝑁𝑁𝐷𝐷𝐷 𝑑𝑑 𝑑𝑑
+ (𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐷𝐷 = 𝑁𝑁𝐷𝐷𝐷 + 𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑎𝑎 𝑎𝑎
I 𝑁𝑁𝐼𝐼𝐼 - 𝑁𝑁𝐼𝐼 = 𝑁𝑁𝐼𝐼𝐼
Totals 𝑁𝑁𝑇𝑇𝑇 𝑑𝑑 𝑐𝑐 𝑏𝑏
𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑇 + ( + − − 1)𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑎𝑎 𝑎𝑎 𝑎𝑎
Batch system
𝑑𝑑 𝑐𝑐 𝑏𝑏
• Stoichiometric coefficient, 𝛿𝛿 = + − − 1
𝑎𝑎 𝑎𝑎 𝑎𝑎
• Total number of moles per mole of A reacted:
• 𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑇 + 𝛿𝛿𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
Equations for batch concentration
• Concentration of A
𝑁𝑁𝐴𝐴
• 𝐶𝐶𝐴𝐴 =
𝑉𝑉
𝑏𝑏
𝑁𝑁𝐵𝐵 𝑁𝑁𝐵𝐵𝐵 −𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐵𝐵 = =
𝑉𝑉 𝑉𝑉
𝐶𝐶
𝑁𝑁𝐶𝐶 𝑁𝑁𝐶𝐶0 +𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐶𝐶 = =
𝑉𝑉 𝑉𝑉
𝑑𝑑
𝑁𝑁𝐷𝐷 𝑁𝑁𝐷𝐷0 +𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐷𝐷 = =
𝑉𝑉 𝑉𝑉
Equations for batch concentration
𝑁𝑁𝑖𝑖𝑖 𝐶𝐶𝑖𝑖𝑖 𝑦𝑦𝑖𝑖𝑖
• Θ 𝑖𝑖 = = =
𝑁𝑁𝐴𝐴𝐴 𝐶𝐶𝐴𝐴𝐴 𝑦𝑦𝐴𝐴𝐴
𝑁𝑁 𝑏𝑏
𝑁𝑁𝐵𝐵0
𝑏𝑏
𝑁𝑁𝐵𝐵𝐵 −𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋 𝑁𝑁𝐴𝐴𝐴 [ 𝐵𝐵𝐵 −𝑎𝑎𝑋𝑋] 𝑏𝑏
𝑁𝑁𝐴𝐴𝐴 [Θ 𝐵𝐵 −𝑎𝑎𝑋𝑋]
𝑁𝑁𝐴𝐴0
• Θ 𝐵𝐵 = , 𝐶𝐶𝐵𝐵 = = =
𝑁𝑁𝐴𝐴𝐴 𝑉𝑉 𝑉𝑉 𝑉𝑉
𝑁𝑁 𝑐𝑐
𝑁𝑁𝐶𝐶0
𝐶𝐶
𝑁𝑁𝐶𝐶𝐶 +𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋 𝑁𝑁𝐴𝐴𝐴 [ 𝐶𝐶0 +𝑎𝑎𝑋𝑋] 𝑐𝑐
𝑁𝑁𝐴𝐴𝐴 [Θ 𝐶𝐶 +𝑎𝑎𝑋𝑋]
𝑁𝑁𝐴𝐴𝐴
• Θ 𝐶𝐶 = , 𝐶𝐶𝐶𝐶 = = =
𝑁𝑁𝐴𝐴𝐴 𝑉𝑉 𝑉𝑉 𝑉𝑉
𝑁𝑁 𝑑𝑑
𝑁𝑁𝐷𝐷0
𝑑𝑑
𝑁𝑁𝐷𝐷𝐷 +𝑎𝑎𝑁𝑁𝐴𝐴𝐴 𝑋𝑋 𝑁𝑁𝐴𝐴𝐴 [ 𝐷𝐷0 +𝑎𝑎𝑋𝑋] 𝑑𝑑
𝑁𝑁𝐴𝐴𝐴 [Θ 𝐷𝐷 +𝑎𝑎𝑋𝑋]
𝑁𝑁𝐴𝐴𝐴
• Θ 𝐷𝐷 = , 𝐶𝐶𝐷𝐷 = = =
𝑁𝑁𝐴𝐴𝐴 𝑉𝑉 𝑉𝑉 𝑉𝑉
Constant-volume batch reaction systems
• Constant-volume: 𝑉𝑉 = 𝑉𝑉0
𝑁𝑁𝐴𝐴0 (1−𝑋𝑋)
• 𝐶𝐶𝐴𝐴 = = 𝐶𝐶𝐴𝐴𝐴 (1 − 𝑋𝑋)
𝑉𝑉0
𝑁𝑁𝐵𝐵𝐵 𝑏𝑏 𝑏𝑏
𝑁𝑁𝐴𝐴𝐴 [ − 𝑋𝑋] 𝑁𝑁𝐴𝐴𝐴 [Θ 𝐵𝐵 −𝑎𝑎𝑋𝑋] 𝑏𝑏
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐵𝐵 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑎𝑎 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0
𝑁𝑁𝐶𝐶𝐶 𝑐𝑐 𝑐𝑐
𝑁𝑁𝐴𝐴𝐴 [ + 𝑋𝑋] 𝑁𝑁𝐴𝐴𝐴 [Θ 𝐶𝐶 +𝑎𝑎𝑋𝑋] 𝑐𝑐
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐶𝐶 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0 𝑎𝑎
𝑁𝑁𝐷𝐷𝐷 𝑑𝑑 𝑑𝑑
𝑁𝑁𝐴𝐴𝐴 [ + 𝑋𝑋] 𝑁𝑁𝐴𝐴𝐴 [Θ 𝐷𝐷 +𝑎𝑎𝑋𝑋] 𝑑𝑑
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐷𝐷 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0 𝑎𝑎
Rate law for liquid phase reaction
2 𝑏𝑏
• −𝑟𝑟𝐴𝐴 = 𝑘𝑘𝐶𝐶𝐴𝐴 𝐶𝐶𝐵𝐵 = 𝑘𝑘𝐶𝐶𝐴𝐴𝐴 1 − 𝑋𝑋 ((Θ 𝐵𝐵 − 𝑋𝑋) = 𝑓𝑓(𝑋𝑋)
𝑎𝑎
Example 1
• Soap consists of the sodium and potassium salts of various fatty acids
such as oleic, stearic, palmitic, lauric and myristic acids. The
saponification for the formation of soap from aqueous caustic soda
and glyceryl stearate is
3𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁(𝑎𝑎𝑎𝑎) + (𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶)3 𝐶𝐶3 𝐻𝐻5 → 3𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 + 𝐶𝐶3 𝐻𝐻5 (𝑂𝑂𝑂𝑂)3

• Set up the stoichiometric table expressing the concentration of each

species.
Example 1
• 3𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 + (𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶)3 𝐶𝐶3 𝐻𝐻5 → 3𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 + 𝐶𝐶3 𝐻𝐻5 (𝑂𝑂𝑂𝑂)3
1 1
• 𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 + (𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶)3 𝐶𝐶3 𝐻𝐻5 → 𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 + 𝐶𝐶3 𝐻𝐻5 (𝑂𝑂𝑂𝑂)3
3 3
1 1
•A + B → C + D
3 3

• Since this is liquid phase reaction, density is considered to be

constant, therefore, 𝑉𝑉 = 𝑉𝑉0 .
 Example 1
Species Symbol Initial Change Remaining (mol) Concentration
(mol) (mol) (mol/m3)
𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 A 𝑁𝑁𝐴𝐴𝐴 −(𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐴𝐴 = 𝑁𝑁𝐴𝐴𝐴 (1 − 𝑋𝑋) 𝐶𝐶𝐴𝐴𝐴 (1 − 𝑋𝑋)
(𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶)3 𝐶𝐶3 𝐻𝐻5 B 𝑁𝑁𝐵𝐵𝐵 1 1 1
− (𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐵𝐵 = 𝑁𝑁𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋) 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋)
3 3 3
𝐶𝐶17 𝐻𝐻35 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 C 𝑁𝑁𝐶𝐶𝐶 +(𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐶𝐶 = 𝑁𝑁𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋) 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋)
𝐶𝐶3 𝐻𝐻5 (𝑂𝑂𝑂𝑂)3 D 𝑁𝑁𝐷𝐷𝐷 1 1 1
+ (𝑁𝑁𝐴𝐴𝐴 𝑋𝑋) 𝑁𝑁𝐷𝐷 = 𝑁𝑁𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋) 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋)
3 3 3
Water (inert) I 𝑁𝑁𝐼𝐼𝐼 - 𝑁𝑁𝐼𝐼 = 𝑁𝑁𝐼𝐼𝐼 𝐶𝐶𝐼𝐼 = 𝐶𝐶𝐼𝐼𝐼
Totals 𝑁𝑁𝑇𝑇𝑇 1 1 𝐶𝐶𝑇𝑇 = 𝐶𝐶𝑇𝑇𝑇
𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑇 + ( + 1 − − 1)𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
3 3
𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑇
Example 2
• Based on example 1, if the initial mixture consists solely of sodium
hydroxide at a concentration of 10 mol/L and of glyceryl stearate of 2
mol/L, what is the concentration of glycerine when the conversion of
sodium hydroxide is (a) 20% and (b) 90%?
Example 2
• Only reactants are initially present, therefore, Θ 𝐶𝐶 =Θ 𝐷𝐷 =0.
• (a) For conversion of NaOH:
1 1
• 𝐶𝐶𝐷𝐷 = 𝐶𝐶𝐴𝐴𝐴 Θ 𝐷𝐷 + 𝑋𝑋 = (10)(0 + 0.2) = 0.67 mol/L
3 3
1 2 0.2
• 𝐶𝐶𝐵𝐵 = 𝐶𝐶𝐴𝐴𝐴 Θ 𝐵𝐵 − 𝑋𝑋 = 10 − = 1.33 mol/L
3 10 3
Example 2
• (b) For 90% conversion of NaOH:
1 1
• 𝐶𝐶𝐷𝐷 = 𝐶𝐶𝐴𝐴𝐴 Θ 𝐷𝐷 + 𝑋𝑋 = (10)(0 + 0.9) = 3 mol/L
3 3
1 2 0.9
• 𝐶𝐶𝐵𝐵 = 𝐶𝐶𝐴𝐴𝐴 Θ 𝐵𝐵 − 𝑋𝑋 = 10 − = −1 mol/L
3 10 3

• This means that 90% of NaOH conversion is not possible, because

glyceryl stearate is the limiting reactant.
Flow systems 𝑎𝑎𝑎𝑎 + 𝑏𝑏𝑏𝑏 → 𝑐𝑐𝑐𝑐 + 𝑑𝑑𝑑𝑑
𝑏𝑏 𝑐𝑐 𝑑𝑑
𝐴𝐴 + 𝐵𝐵 → 𝐶𝐶 + 𝐷𝐷
𝑎𝑎 𝑎𝑎 𝑎𝑎
Flow systems
Species Feed rate to reactor Change within reactor Effluent Rate from Reactor (mol/time)
(mol/time) (mol/time)
A 𝐹𝐹𝐴𝐴𝐴 −(𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐴𝐴 = 𝐹𝐹𝐴𝐴𝐴 (1 − 𝑋𝑋)
B 𝐹𝐹𝐵𝐵𝐵 = Θ 𝐵𝐵 𝐹𝐹𝐴𝐴𝐴 𝑏𝑏 𝑏𝑏
− (𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐵𝐵 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋)
𝑎𝑎 𝑎𝑎
C 𝐹𝐹𝐶𝐶𝐶 = Θ 𝐶𝐶 𝐹𝐹𝐴𝐴𝐴 𝑐𝑐 𝑐𝑐
+ (𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐶𝐶 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋)
𝑎𝑎 𝑎𝑎
D 𝐹𝐹𝐷𝐷𝐷 = Θ 𝐷𝐷 𝐹𝐹𝐴𝐴𝐴 𝑑𝑑 𝑑𝑑
+ (𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐷𝐷 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋)
𝑎𝑎 𝑎𝑎
I 𝐹𝐹𝐼𝐼𝐼 = Θ 𝐼𝐼 𝐹𝐹𝐴𝐴𝐴 - 𝐹𝐹𝐼𝐼 = 𝐹𝐹𝐼𝐼𝐼
Totals 𝐹𝐹𝑇𝑇𝑇 𝑑𝑑 𝑐𝑐 𝑏𝑏
𝐹𝐹𝑇𝑇 = 𝐹𝐹𝑇𝑇𝑇 + ( + − − 1)𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
𝑎𝑎 𝑎𝑎 𝑎𝑎
𝐹𝐹𝑇𝑇 = 𝐹𝐹𝑇𝑇𝑇 + 𝛿𝛿𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
Equations for flow systems concentration
• Concentration of A
𝐹𝐹𝐴𝐴 𝐹𝐹𝐴𝐴0 (1−𝑋𝑋)
• 𝐶𝐶𝐴𝐴 = =
𝑉𝑉 𝑉𝑉
𝑏𝑏
𝐹𝐹𝐵𝐵 𝐹𝐹𝐵𝐵𝐵 −𝑎𝑎𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐵𝐵 = =
𝑉𝑉 𝑉𝑉
𝐶𝐶
𝐹𝐹𝐶𝐶 𝐹𝐹𝐶𝐶0 +𝑎𝑎𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐶𝐶 = =
𝑉𝑉 𝑉𝑉
𝑑𝑑
𝐹𝐹𝐷𝐷 𝐹𝐹𝐷𝐷0 +𝑎𝑎𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
• 𝐶𝐶𝐷𝐷 = =
𝑉𝑉 𝑉𝑉
Constant-volume batch reaction systems
• Constant-volume: 𝑉𝑉 = 𝑉𝑉0
𝐹𝐹𝐴𝐴0 (1−𝑋𝑋)
• 𝐶𝐶𝐴𝐴 = = 𝐶𝐶𝐴𝐴𝐴 (1 − 𝑋𝑋)
𝑉𝑉0
𝑁𝑁𝐵𝐵𝐵 𝑏𝑏 𝑏𝑏
𝐹𝐹𝐴𝐴𝐴 [ − 𝑋𝑋] 𝐹𝐹𝐴𝐴𝐴 [Θ 𝐵𝐵 −𝑎𝑎𝑋𝑋] 𝑏𝑏
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐵𝐵 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑎𝑎 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0
𝑁𝑁𝐶𝐶𝐶 𝑐𝑐 𝑐𝑐
𝐹𝐹𝐴𝐴𝐴 [ + 𝑋𝑋] 𝐹𝐹𝐴𝐴𝐴 [Θ 𝐶𝐶 +𝑎𝑎𝑋𝑋] 𝑐𝑐
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐶𝐶 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0 𝑎𝑎
𝑁𝑁𝐷𝐷𝐷 𝑑𝑑 𝑑𝑑
𝐹𝐹𝐴𝐴𝐴 [ + 𝑋𝑋] 𝐹𝐹𝐴𝐴𝐴 [Θ 𝐷𝐷 +𝑎𝑎𝑋𝑋] 𝑑𝑑
𝑁𝑁𝐴𝐴𝐴 𝑎𝑎
• 𝐶𝐶𝐷𝐷 = = = 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋)
𝑉𝑉0 𝑉𝑉0 𝑎𝑎
Reactions in gas phase that have a change in
the total number of moles
1. Batch reactors with variable volume
2. Flow reactors with variable volumetric flow rate
Batch reactors with variable volume
• 𝑃𝑃𝑃𝑃 = 𝑍𝑍𝑁𝑁𝑇𝑇 𝑅𝑅𝑅𝑅
• V = volume
• 𝑁𝑁𝑇𝑇 = total number of moles as before
• T = temperature, K
• P = total pressure, atm (kPa; 1 atm = 101.3 kPa)
• Z = compressibility factor
• R = gas constant = 0.08206 dm3.atm/mol.K
Batch reactors with variable volume
• At t = 0,
• 𝑃𝑃0 𝑉𝑉0 = 𝑍𝑍0 𝑁𝑁𝑇𝑇0 𝑅𝑅𝑇𝑇0

𝑃𝑃0 𝑇𝑇 𝑍𝑍 𝑁𝑁
• 𝑉𝑉 = 𝑉𝑉0
𝑃𝑃 𝑇𝑇0 𝑍𝑍0 𝑁𝑁𝑇𝑇𝑇
• 𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑇 + 𝛿𝛿𝑁𝑁𝐴𝐴𝐴 𝑋𝑋
𝑁𝑁𝑇𝑇 𝑁𝑁𝐴𝐴𝐴
• =1+ 𝛿𝛿𝛿𝛿
𝑁𝑁𝑇𝑇𝑇 𝑁𝑁𝑇𝑇0
𝑁𝑁𝐴𝐴𝐴
• = 𝑦𝑦𝐴𝐴𝐴 , 𝛿𝛿 𝑦𝑦𝐴𝐴𝐴 = ε
𝑁𝑁𝑇𝑇𝑇
𝑁𝑁𝑇𝑇
• = 1 + εX
𝑁𝑁𝑇𝑇𝑇
Batch reactors with variable volume
𝑁𝑁𝑇𝑇 −𝑁𝑁𝑇𝑇𝑇
•ε=
𝑁𝑁𝑇𝑇𝑇 𝑋𝑋
• At complete conversion (X=1, 𝑁𝑁𝑇𝑇 = 𝑁𝑁𝑇𝑇𝑓𝑓 )
𝑁𝑁𝑇𝑇𝑓𝑓 −𝑁𝑁𝑇𝑇𝑇
•ε=
𝑁𝑁𝑇𝑇𝑇
𝑃𝑃0 𝑇𝑇 𝑍𝑍
• 𝑉𝑉 = 𝑉𝑉0 1 + ε𝑋𝑋
𝑃𝑃 𝑇𝑇0 𝑍𝑍0
• Compressibility factor, 𝑍𝑍0 ≅ 𝑍𝑍
𝑃𝑃0 𝑇𝑇
• 𝑉𝑉 = 𝑉𝑉0 (1 + εX)
𝑃𝑃 𝑇𝑇0
Flow reactors with variable volumetric flow
rate
• Total concentration,
𝐹𝐹𝑇𝑇 𝑃𝑃
• 𝐶𝐶𝑇𝑇 = =
𝑉𝑉 𝑍𝑍𝑍𝑍𝑍𝑍
• At the feed reactor,
𝐹𝐹𝑇𝑇0 𝑃𝑃0
• 𝐶𝐶𝑇𝑇0 = =
𝑉𝑉0 𝑍𝑍0 𝑅𝑅𝑇𝑇0
• Gas phase reaction:
𝐹𝐹𝑇𝑇 𝑇𝑇 𝑃𝑃0
• 𝑉𝑉 = 𝑉𝑉0
𝐹𝐹𝑇𝑇𝑇 𝑇𝑇0 𝑃𝑃
Flow reactors with variable volumetric flow
rate
𝐹𝐹𝑇𝑇 𝐹𝐹𝑇𝑇 𝐹𝐹𝑇𝑇𝑇 𝐹𝐹𝑇𝑇 𝑃𝑃 𝑇𝑇0
• 𝐶𝐶𝑇𝑇 = = 𝐹𝐹 𝑇𝑇 𝑃𝑃0
=
𝑉𝑉 𝑉𝑉0 𝐹𝐹 𝑇𝑇 𝑇𝑇 𝑉𝑉0 𝐹𝐹𝑇𝑇 𝑃𝑃0 𝑇𝑇
𝑇𝑇𝑇 0 𝑃𝑃
𝐹𝐹𝑇𝑇 𝑃𝑃 𝑇𝑇0
• 𝐶𝐶𝑇𝑇 = 𝐶𝐶𝑇𝑇𝑇
𝐹𝐹𝑇𝑇 𝑃𝑃0 𝑇𝑇

• Total molar flow rate

• 𝐹𝐹𝑇𝑇 = 𝐹𝐹𝑇𝑇𝑇 + 𝐹𝐹𝐴𝐴𝐴 𝛿𝛿𝛿𝛿
𝐹𝐹𝑇𝑇 𝐹𝐹𝑇𝑇0 𝐹𝐹𝐴𝐴0
• = + 𝛿𝛿𝛿𝛿
𝐹𝐹𝑇𝑇𝑇 𝐹𝐹𝑇𝑇𝑇 𝐹𝐹𝑇𝑇𝑇
Flow reactors with variable volumetric flow
rate
𝐹𝐹𝑇𝑇𝑇 𝐹𝐹𝐴𝐴𝐴 𝑇𝑇 𝑃𝑃0 𝐹𝐹𝐴𝐴𝐴 𝑇𝑇 𝑃𝑃0
• 𝑉𝑉 = 𝑉𝑉0 + 𝛿𝛿𝛿𝛿 = 𝑉𝑉0 1 + 𝛿𝛿𝛿𝛿
𝐹𝐹𝑇𝑇𝑇 𝐹𝐹𝑇𝑇𝑇 𝑇𝑇0 𝑃𝑃 𝐹𝐹𝑇𝑇𝑇 𝑇𝑇0 𝑃𝑃
𝑇𝑇 𝑃𝑃0
• = 𝑉𝑉0 1 + 𝑦𝑦𝐴𝐴𝐴 𝛿𝛿𝛿𝛿
𝑇𝑇0 𝑃𝑃
𝑇𝑇 𝑃𝑃0
•V = 𝑉𝑉0 1 + 𝜀𝜀𝑋𝑋
𝑇𝑇0 𝑃𝑃
• Molar flow rate of species A
• 𝐹𝐹𝐴𝐴 = 𝐹𝐹𝐴𝐴0 + 𝑣𝑣𝑇𝑇 𝐹𝐹𝐴𝐴0 𝑋𝑋 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐴𝐴 + 𝑣𝑣𝐴𝐴 𝑋𝑋)
𝐹𝐹𝐴𝐴 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐴𝐴 +𝑣𝑣𝐴𝐴 𝑋𝑋) 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐴𝐴 +𝑣𝑣𝐴𝐴 𝑋𝑋) 𝑃𝑃 𝑇𝑇0
• 𝐶𝐶𝐴𝐴 = = 𝑇𝑇 𝑃𝑃0 =
𝑉𝑉 𝑉𝑉0 1+𝜀𝜀𝜀𝜀 𝑇𝑇 1+𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
0 𝑃𝑃
Concentrations in a variable-volume gas flow
system
𝐹𝐹𝐴𝐴 𝐹𝐹𝐴𝐴0 (1 − 𝑋𝑋) 𝐹𝐹𝐴𝐴𝐴 (1 − 𝑋𝑋) 𝑃𝑃 𝑇𝑇0 𝐶𝐶𝐴𝐴𝐴 (1 − 𝑋𝑋) 𝑃𝑃 𝑇𝑇0
𝐶𝐶𝐴𝐴 = = = =
𝑉𝑉 𝑉𝑉 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
𝑏𝑏 𝑏𝑏 𝑏𝑏
𝐹𝐹𝐵𝐵 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋) 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋) 𝑃𝑃 𝑇𝑇0 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋) 𝑃𝑃 𝑇𝑇0
𝐶𝐶𝐵𝐵 = = 𝑎𝑎 = 𝑎𝑎 = 𝑎𝑎
𝑉𝑉 𝑉𝑉 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
𝑐𝑐 𝑐𝑐 𝑐𝑐
𝐹𝐹𝐶𝐶 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋) 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋) 𝑃𝑃 𝑇𝑇0 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐶𝐶 + 𝑋𝑋) 𝑃𝑃 𝑇𝑇0
𝐶𝐶𝐶𝐶 = = 𝑎𝑎 = 𝑎𝑎 = 𝑎𝑎
𝑉𝑉 𝑉𝑉 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
𝑑𝑑 𝑑𝑑 𝑑𝑑
𝐹𝐹𝐷𝐷 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋) 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋) 𝑃𝑃 𝑇𝑇0 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐷𝐷 + 𝑋𝑋) 𝑃𝑃 𝑇𝑇0
𝐶𝐶𝐷𝐷 = = 𝑎𝑎 = 𝑎𝑎 = 𝑎𝑎
𝑉𝑉 𝑉𝑉 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
𝐹𝐹𝑗𝑗 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐼𝐼 ) 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐼𝐼 ) 𝑃𝑃 𝑇𝑇0 𝐶𝐶𝐴𝐴𝐴 (Θ 𝐼𝐼 ) 𝑃𝑃 𝑇𝑇0
𝐶𝐶𝑗𝑗 = = = =
𝑉𝑉 𝑉𝑉 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇 1 + 𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
Summary of expressing concentration as a
function of conversion for both liquid and gas
phase
Example 3
• Prove that CB for a gas flow system reduces in terms of CA0 and V0.
𝐹𝐹𝐵𝐵
• Step 1: 𝐶𝐶𝐵𝐵 =
𝑉𝑉
𝑏𝑏
• Step 2: 𝐹𝐹𝐵𝐵 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋)
𝑏𝑏 𝑎𝑎
𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 −𝑎𝑎𝑋𝑋)
• Step 3: 𝐶𝐶𝐵𝐵 =
𝑉𝑉
𝑇𝑇 𝑃𝑃0
• Step 4: V = 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀
𝑇𝑇 𝑃𝑃
𝑏𝑏 0
𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 −𝑎𝑎𝑋𝑋)
• Step 5: 𝐶𝐶𝐵𝐵 = 𝑇𝑇 𝑃𝑃
𝑉𝑉0 1+𝜀𝜀𝜀𝜀 𝑇𝑇 𝑃𝑃0
0 𝑏𝑏
𝐹𝐹𝐴𝐴𝐴 𝐶𝐶 𝐴𝐴𝐴 (Θ 𝐵𝐵 𝑎𝑎𝑋𝑋) 𝑃𝑃 𝑇𝑇0
−
• Step 6: 𝐶𝐶𝐴𝐴𝐴 = ,𝐶𝐶 = (proven)
𝑉𝑉0 𝐵𝐵 1+𝜀𝜀𝜀𝜀 𝑃𝑃0 𝑇𝑇
Example 4
• A mixture of 28% SO2 and 72% air is charged to a flow reactor in
which SO2 is oxidized.
2𝑆𝑆𝑆𝑆2 + 𝑂𝑂2 → 2𝑆𝑆𝑆𝑆3
1
𝑆𝑆𝑆𝑆2 + 𝑂𝑂2 → 𝑆𝑆𝑆𝑆3
2
1
A + B → C
2
Air contains 79% N2 (inert) and 21% O2.
(a) Set up a stoichiometric table using only symbols (𝐹𝐹𝑖𝑖 , Θ 𝑖𝑖 ).
(b) Evaluate the species concentration when the total pressure is 1485
kPa (14.7 atm) and the temperature is constant at 227℃.
Example 4
• 𝐹𝐹𝐴𝐴0 = (0.28)𝐹𝐹𝑇𝑇0
• 𝐹𝐹𝐵𝐵0 = (0.72)(0.21)𝐹𝐹𝑇𝑇𝑇
𝐹𝐹𝐵𝐵𝐵 (0.72)(0.21)𝐹𝐹𝑇𝑇𝑇
•Θ 𝐵𝐵 = 𝐹𝐹 = = 0.54
𝐴𝐴0 (0.28)𝐹𝐹𝑇𝑇𝑇
𝐹𝐹𝐼𝐼0 (0.72)(0.79)𝐹𝐹𝑇𝑇𝑇
•Θ 𝐼𝐼 = 𝐹𝐹 = = 2.03
𝐴𝐴𝐴 (0.28)𝐹𝐹𝑇𝑇𝑇
Example 4
Species Symbol Feed rate to Change within Effluent Rate from Reactor (mol/time)
reactor reactor (mol/time)
(mol/time)
𝑆𝑆𝑆𝑆2 A 𝐹𝐹𝐴𝐴𝐴 −(𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐴𝐴 = 𝐹𝐹𝐴𝐴𝐴 (1 − 𝑋𝑋)
𝑂𝑂2 B 𝐹𝐹𝐵𝐵𝐵 = Θ 𝐵𝐵 𝐹𝐹𝐴𝐴𝐴 1 1
− (𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐵𝐵 = 𝐹𝐹𝐴𝐴𝐴 (Θ 𝐵𝐵 − 𝑋𝑋)
2 2
𝑆𝑆𝑆𝑆3 C 0 + (𝐹𝐹𝐴𝐴𝐴 𝑋𝑋) 𝐹𝐹𝐶𝐶 = 𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
𝑁𝑁2 I 𝐹𝐹𝐼𝐼𝐼 = Θ 𝐼𝐼 𝐹𝐹𝐴𝐴𝐴 - 𝐹𝐹𝐼𝐼 = 𝐹𝐹𝐼𝐼𝐼 = Θ 𝐼𝐼 𝐹𝐹𝐴𝐴𝐴

Totals 𝐹𝐹𝑇𝑇𝑇 1
𝐹𝐹𝑇𝑇 = 𝐹𝐹𝑇𝑇𝑇 + (1 − − 1)𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
2
1
𝐹𝐹𝑇𝑇 = 𝐹𝐹𝑇𝑇𝑇 − 𝐹𝐹𝐴𝐴𝐴 𝑋𝑋
2
Example 4
𝐹𝐹𝐴𝐴
• Step 1: 𝐶𝐶𝐴𝐴 =
𝑉𝑉
𝑇𝑇 𝑃𝑃0
• Step 2: V = 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀
𝑇𝑇0 𝑃𝑃
𝑇𝑇
• Step 3: Neglect Pressure drop, P = 𝑃𝑃0 , V = 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀
𝑇𝑇0
• Step 4: Assuming isothermal condition, T = 𝑇𝑇0 , V = 𝑉𝑉0 1 + 𝜀𝜀𝜀𝜀
𝐹𝐹𝐴𝐴 𝐹𝐹𝐴𝐴𝐴 (1−𝑋𝑋) 1−𝑋𝑋
• Step 5: 𝐶𝐶𝐴𝐴 = = = 𝐶𝐶𝐴𝐴𝐴
𝑉𝑉 𝑉𝑉0 1+𝜀𝜀𝜀𝜀 1+𝜀𝜀𝜀𝜀
𝑃𝑃0 1485
• Step 6: 𝐶𝐶𝐴𝐴𝐴 = 𝑦𝑦𝐴𝐴𝐴 𝐶𝐶𝑇𝑇0 = 𝑦𝑦𝐴𝐴𝐴 = 0.28 = 0.1 𝑚𝑚𝑚𝑚𝑚𝑚/𝑑𝑑𝑑𝑑3
𝑅𝑅𝑇𝑇0 8.314𝑥𝑥𝑥𝑥𝑥
𝐹𝐹 𝐹𝐹 +𝑦𝑦 𝛿𝛿𝑋𝑋𝐹𝐹 𝐹𝐹 (1+𝜀𝜀𝜀𝜀) 𝐹𝐹 𝑃𝑃0
• Step 7:𝐶𝐶𝑇𝑇 = 𝑇𝑇 = 𝑇𝑇0 𝐴𝐴𝐴 𝑇𝑇𝑇 = 𝑇𝑇0 = 𝑇𝑇𝑇 = 𝐶𝐶𝑇𝑇0 = = 0.357
3 𝑉𝑉 𝑉𝑉0 1+𝜀𝜀𝜀𝜀 𝑉𝑉0 1+𝜀𝜀𝜀𝜀 𝑉𝑉0 𝑅𝑅𝑇𝑇0
𝑚𝑚𝑚𝑚𝑚𝑚/𝑑𝑑𝑑𝑑
Example 4
1
• ε = 𝛿𝛿 𝑦𝑦𝐴𝐴𝐴 = 0.28 1−1− = −0.14
2
1−𝑋𝑋 1−𝑋𝑋
• 𝐶𝐶𝐴𝐴 = 𝐶𝐶𝐴𝐴𝐴 = 0.1 𝑚𝑚𝑚𝑚𝑚𝑚/𝑑𝑑𝑑𝑑3
1+𝜀𝜀𝜀𝜀 1−0.14𝑋𝑋
1
Θ 𝐵𝐵 −2𝑋𝑋 0.54−0.5𝑋𝑋
• 𝐶𝐶𝐵𝐵 = 𝐶𝐶𝐴𝐴𝐴 = 0.1( ) 𝑚𝑚𝑚𝑚𝑚𝑚/𝑑𝑑𝑑𝑑3
1+𝜀𝜀𝜀𝜀 1−0.14𝑋𝑋
𝑋𝑋Θ 𝐼𝐼 2.03
• 𝐶𝐶𝐼𝐼 = 𝐶𝐶𝐴𝐴𝐴 = 0.1( ) 𝑚𝑚𝑚𝑚𝑚𝑚/𝑑𝑑𝑑𝑑3
1+𝜀𝜀𝜀𝜀 1−0.14𝑋𝑋
1
1−𝑋𝑋 Θ 𝐵𝐵 −2𝑋𝑋 1−𝑋𝑋 0.54−0.5𝑋𝑋
2
• −𝑟𝑟𝐴𝐴 = 𝑘𝑘𝐶𝐶𝐴𝐴 𝐶𝐶𝐵𝐵 = 𝑘𝑘𝐶𝐶𝐴𝐴𝐴 = 0.01𝑘𝑘
1+𝜀𝜀𝜀𝜀 2 1−0.14𝑋𝑋 2
Thank You