Principles of Chemical Engineering

Dr. Yuxia Sun

Oct.16, 2024
 Lecture 5

Fundamentals for Reactor Design

Stainless steel stirred tank bioreactors Petroleum Refining factory

A typical manufacturing process
 Methanol to Olefins (DMTO)

Reactor
Value-added Unit
A typical manufacturing process
 Yeast generation

activation of culture

Steam
Sterilisation

Seeds growth

T
Air
DO

Sterilizations control
ventilation Reactor
Value-added Unit
Power Crushing Dehydro Filtration
Dry
Products Screening Decolor
Reactor design-key to success of the process

Recycle
Reactor Design!
For separation Unit operations

For reaction
How far? Thermodynamics
How fast? Kinetics & Catalysis
How to? Reactor Engineering
Reactor design-key to success of the process
Mass balance Energy balance

Input Output

Performance equation relates input to output

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑓(𝑖𝑛𝑝𝑢𝑡, 𝑘𝑖𝑛𝑒𝑡𝑖𝑐𝑠, 𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑖𝑛𝑔)

C
Selectivity = × 100%
𝐶+D

Conversion
Reactor design-understand the reactions
Mass balance
A C
C Desired product
A
D +
By products and waste
= Feed
A C D

How to get more desired products?

Reactions Reactors
Reaction rate 𝑓 𝑇, 𝑃, 𝑥 Design optimization Small volume to reduce the cost
Reaction selectivity Operation optimization Optimal reaction t and T
Homogeneous/Heterogeneous (Diffusion) Energy consumption = ƒ (T, t, x,…) Minimum

understand the reactions→ Optimized design and operation of reactors

crucial for the development of green technologies
Ideal reactor types
Ideal contacting or flow patterns

Batch reactor Continuously stirred tank reactor Plug-flow reactor (PFR)

(CSTR)

Uniform mixing No mixing

ƒ ( t)
unsteady state steady state steady state
Batch reactor

Charged via ports.

Stirring is efficient Nothing else is put in or taken out until the reaction is finished.

Uniform composition throughout the reactor

Cooling
jacket Composition are time dependent

Closed, unsteady state

Easily heated or cooled by an external jacket

Advantages low investment cost; high flexibility; adjustable productivity

Disadvantages low efficiency; more labor; difficult to monitor the reaction by DCS or PLC
Continuous stirred tank reactor

Continuous stirred tank reactor (CSTR)

The feed mixture continuously enters.

The outlet mixture is continuously withdrawn.

Feed in An equal volume of reactor contents is discharged.

Concentration could be stable during the reaction

Uniform composition throughout the reactor

Open, Steady-state

The exit stream has the same composition as that in any position of the tank.
Feed out
 Plug-flow reactor (PFR)

Perpendicular to the axis direction--little or no radial variation in reaction rate and concentration.

flows through the reactor in a uniform

and continuous manner, like a plug or
piston
one long reactor or many
short reactors in a tube bank.

conversion of reactants and the reaction

rate vary along the reactor length

Concentration changes with

length down the reactor.
Ideal reactor types
Ideal reactor types

CSTR first, then flows out of stomach to gastrointestinal tract (胃肠道, more like a plug flow reactor).
reactors in “series”
 Reaction types
Single reaction A C Homogeneous reaction: Gas-Gas;
Multiple Liquid-Liquid
C
Parallel reaction A
D Heterogeneous reaction: Gas-Solid;
Series reaction A C D Gas-Liquid;
Liquid-Solid;
Series-parallel reaction A + B Liquid-Liquid
C
Gas-Liquid-Solid
C + B D
Description by a single chemical equation or multiple equations In single phase or multiple phases

By Irreversible reaction
P Product
P Reversible reaction: ⇌
the existence of a forward reaction and an appreciable
back reaction,
R not approach completion at the pressure and
temperatures of interest, equilibrium
Reaction time
 Reaction rate in fundamental chemistry
Full Combustion
Homogeneous reaction
of H2 and O2
1 𝑑𝑁𝑖 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑜𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
𝑟𝑖 = =
𝑉 𝑑𝑡 (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑)(𝑇𝑖𝑚𝑒) 108 Kg/s
60 cm
H2O (g)
Heterogeneous reaction
1 𝑑𝑁𝑖 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑜𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 75 cm 𝑟𝐻2 = ?
𝑟𝑖 = = rocket engine
𝑊 𝑑𝑡 (𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑)(𝑇𝑖𝑚𝑒) 𝑟𝑂2 = ?
1 𝑑𝑁𝑖 𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑜𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
𝑟𝑖 = =
𝑉𝑠 𝑑𝑡 (𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑)(𝑇𝑖𝑚𝑒)

chemical reactions in body at rest catalytic reactions in solid-gas interface

10-4 10-3 10-2 10-1 1 10

N/t

Waste water treatment chemical reactions in body at work coal combustion

Input Output

Performance equation relates input to output

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑓(𝑖𝑛𝑝𝑢𝑡, 𝑘𝑖𝑛𝑒𝑡𝑖𝑐𝑠, 𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑖𝑛𝑔)

Material balance
Reaction kinetics
Energy balance
Material Balance
Calculations
Reaction stoichiometry

The overall stoichiometry of a reaction given the amounts of each reactant that exactly
react together and the amounts of each product formed.

Stoichiometric coefficient (ν)

νA= -a, νB= -b, νC= c, ν d= d

0 = 𝑐𝐶 + 𝑑𝐷 − 𝑎𝐴 − 𝑏𝐵 = νcC+ νDd+ νBB+ νaA= σ𝑖 𝜈𝑖 𝑀𝑖
Stoichiometric proportions 𝑀𝑖
Molecules of chemical species i

Stoichiometric proportion of B to A is b to a→θB

C to A is b to a→θc
Conversion
Limiting reactant—the reactant used up first if the reaction proceed sufficiently.
Excess reactant—reactants that would remain even if all the limiting reactant were consumed.
In a batch operation
—the fraction of the limiting reactant used up in any way during the reaction
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒖𝒔𝒆𝒅 𝒖𝒑 𝒏𝑨𝟎 −𝒏𝑨
X=Conversion= × 𝟏𝟎𝟎% =
𝒕𝒐𝒕𝒂𝒍 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒊𝒏 𝒕𝒉𝒆 𝒇𝒆𝒆𝒅 𝒏𝑨𝟎

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑎𝑐𝑡𝑢𝑎𝑙𝑙𝑦 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑

Y=Yield= × 100%
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑓𝑜𝑟 100% 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑠𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑎𝑐𝑡𝑢𝑎𝑙𝑙𝑦 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑

S=Selectivity= × 100%
𝒎𝒐𝒍𝒆 𝒐𝒇 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝒂𝒏𝒅 𝒃𝒚𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝒈𝒆𝒏𝒆𝒓𝒂𝒕𝒆𝒅 𝒃𝒚 𝒕𝒉𝒆 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔 𝒖𝒔𝒆𝒅 𝒖𝒑

νaA+νBB→ νcC+ νDD With A as the limiting reactant Moles of A used up—nA0XA
nA0 nB0 0 0 ? moles of component B, C, and D retained in this system with
conversion of XA
Conversion
In continuous operation
—the mole or concentration varies with location
— in terms of mole flow rate (F) at steady state
Mole flow rate (F) =mole/time (measurement of moles per unit time)

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒖𝒔𝒆𝒅 𝒖𝒑 𝒏𝑨𝟎 −𝒏𝑨

X=%Conversion= × 𝟏𝟎𝟎% =
𝒕𝒐𝒕𝒂𝒍 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒍𝒊𝒎𝒊𝒕𝒊𝒏𝒈 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 𝒊𝒏 𝒕𝒉𝒆 𝒇𝒆𝒆𝒅 𝒏𝑨𝟎

Replacing n with F, similar equations are obtained:

𝒎𝒐𝒍𝒆 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒇𝒆𝒆𝒅 𝒊𝒏− 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒂𝒕 𝒕𝒉𝒆 𝒆𝒙𝒊𝒕 𝑭𝑨𝟎 −𝑭𝑨
X=%Conversion= × 𝟏𝟎𝟎% =
𝒎𝒐𝒍𝒆 𝒇𝒍𝒐𝒘 𝒓𝒂𝒕𝒆 𝒇𝒆𝒆𝒅 𝒊𝒏 𝑭𝑨𝟎

𝑛𝐴 = 𝑛𝑜 × (1 − 𝑋𝐴 ) 𝐹𝐴 = 𝐹𝑜 × (1 − 𝑋𝐴 )
Number of moles from gas volume and molar volumes
𝑹𝒎 𝑻
molar volumes 𝑽𝑷𝑮
𝒎 = = 𝟖. 𝟑𝟏𝟒𝟒𝑻/𝑷
𝑷
• 𝑇 Absolute temperature in K molar volume for a
• P Pressure in N/m2 or Pa perfect gas at STP (0 oC, 1 atm)
• 𝑉𝑚𝑃𝐺 Molar volume in m3/mol.
• R =8.3144, Molar gas constant m3 Pa /(mol∙ 𝐾) 𝑉𝑚𝑃𝐺 𝑆𝑇𝑃 = 0.2241 𝑚3
𝑽 𝑺𝑻𝑷 𝑷𝑽 𝑷 𝑷
Number of moles 𝒏 = = 𝒄= =
𝟎.𝟐𝟐𝟒𝟏 𝟖.𝟑𝟏𝟒𝟒𝑻 𝑹𝒎 𝑻 𝟖.𝟑𝟏𝟒𝟒𝑻

𝑷𝒕𝒐𝒕𝒂𝒍 𝒏𝒙
Partial Pressure 𝑷𝒙 = = 𝐩(𝟏 − 𝐱) 𝑪 = 𝑪𝟎 (𝟏 − 𝒙)
𝒏𝒕𝒐𝒕𝒂𝒍

What if a≠c under constant pressure?

Material Balance on reactor systems
Example Synthetic ammonia maybe produced by the reaction N2+3H2⇌2NH3. The
reaction is reversible and it does not approach completion. If the mole ratio
of hydrogen to nitrogen entering the reactor is 4 to 1 and the mole ratio of
the hydrogen to nitrogen leaving the reactor is 4.25 to 1, how many ton
moles per day of gases must enter the reactor to produce 300 tons per day
of ammonia?

Reversible reaction: ⇌the existence of a forward reaction and an appreciable back reaction,

N2+H2 N2+H2
N2 + 3H2 ⇌ 2NH3 1:4 1:4.25
Material Balance on reactor systems
Synthetic ammonia maybe produced by the reaction N2+3H2⇌2NH3. The reaction is
Example reversible and it does not approach completion. If the mole ratio of hydrogen to nitrogen
entering the reactor is 4 to 1 and the mole ratio of the hydrogen to nitrogen leaving the
reactor is 4.25 to 1, how many moles per day of gases must enter the reactor to produce
300 tons per day of ammonia?
Solution N2+H2 N2+H2
1:4 1:4.25
N2 + 3H2 ⇌ 2NH3
NH3

N2 is the limiting reactant, Let the amount of N2=n, conversion of N2=X,

then the amount of N2 leaving the reactor= n-Xn
the amount of H2 leaving the reactor= 4n-3Xn
The ratio (n-Xn)/(4n-3Xn)=1/4.25 ∴ X=0.2=20%
1 mol N2—(20%✕1 )✕ 2 mol NH3 ∴ 1 mol N2—(20% ✕ 1 ) ✕ 2 ✕ 17 g NH3
300×1×106
per day, 𝑛 𝑁2 = 20% ×34 = 44 × 106 𝑚𝑜𝑙 𝑛 𝐻2 =4 × 𝑛 𝑁2 = 177 × 106 mol

∴ 𝑛 𝑡𝑜𝑡𝑎𝑙 = 221 × 106 mol

Material Balance on reactor systems
An exothermic reaction between reactants A and B in a series
Example
of catalyst beds with 'colds hot' intercooling between the beds.
F The intercooling is necessary to retain the beds of catalyst
By pass Cooler within the recommended operating temperature range and to
Heater maintain favorable conversion. The inlet to the 1st bed is at
300 oC and reactant A is the 'limiting reactant’. The feed
F01 T1 Tc mixture consists of 20 mol% of A and 80 mol% of B and the
Reactor 1 total flow rate at F is 5000 kmol/h. The proposed bed depth is
Tout such that 65% of the component A entering the first bed is
Z By pass
converted within the bed. Before passing the outlets stream
F02 T1 from bed 1 to the next bed, it is proposed to return the stream
temperature to 300 oC by injecting fresh feed cooled to 40 oC,
Reactor 2
necessary to by-pass 15% of the initial feed to obtain the
necessary degree of cooling.
Calculate the conversion of component A as it enters the second reactor bed and the
mole flow rate of this component.
Material Balance on reactor systems
Solution Basis = 1 hour operation
Total feed (F) entering the reactor system = 5000 kmol
F Reactant A in the feed (F)entering=0.20x5000=1000 kmol
BP Cooler Feed (BP) flowing around the by-pass =0.15 x5000=750 kmol
Heater Feed (Fo) entering the first reactor bed =0.85 x5000 =4250 kmol
Reactant A entering first reactor bed =0.20 x4250=850 kmol
F01 T1 Tc Reactant A leaving first reactor bed =0.35 x 850 =297.5 kmol
Reactor 1 Reactant A flowing around by-pass =0.20x750=150 kmol
Tout
Z BP Taking material balance on component A at point Z

F02 T1 Reactant A entering bed 2 = A from reactor 1 + A in by-pass=. 2975 + 150 = 447.5 kmol
Reactor 2 Conversion of A as it enters second bed=[(1000-447.5)/1000]=55.3%
(Had it not been for the cold shot cooling this would have been 65%)
Flow rate of A entering second reactor bed = 447.5 kmol h-1.
Reactant concentrations as function of conversion
---in ideal gas reactions with volume change
𝑛𝐴 𝑛𝐴0 1−𝑋𝐴 𝑉0 𝑉0
◼ Volume changes→ 𝐶𝐴 = = = 𝐶𝐴0 (1 − 𝑋𝐴 )
𝑉 𝑉0 𝑉 𝑉

𝑛𝑖 𝑛𝑖0 − 𝑣𝑖 /𝑣𝐴 )𝑛𝐴0 𝑋𝐴 𝑉0 𝑉0

𝐶𝑖 = = = (𝐶𝑖0 − 𝑣𝑖 /𝑣𝐴 )𝐶𝐴0 𝑋𝐴
𝑉 𝑉0 𝑉 𝑉
𝑉0
◼ For liquid phase reactions →
𝑉
≈1，with constant volume
◼ For gas phase reactions →
𝑉0
𝑉
≉1 when the number of moles of products differs from that of reactants
𝑉0 𝑛0 𝑇0 𝑃
= ( )( )( ) a + b ≠ c +d
𝑉 𝑛 𝑇 𝑃0
Reactant concentrations as function of conversion
---in ideal gas reactions with volume change
ɛA : The fractional change in volume of the system between no conversion and complete
conversion of reactant A. 𝑉𝑋𝐴=1 − 𝑉𝑋𝐴=0
𝜀𝐴 =
𝑉𝑋𝐴=0
𝑛0 1
𝑛 = 𝑛0 + 𝑛0 𝜀𝐴 𝑋𝐴 =
𝑛 1 + 𝜀𝐴 𝑋𝐴

𝐶𝐴0 (1 − 𝑋𝐴 ) 𝑇0 𝑃 Isothermal
𝐶𝐴 = ( )( )( ) 𝐶𝐴0 (1 − 𝑋𝐴 )
1 + 𝜀𝐴 𝑋𝐴 𝑇 𝑃0 𝐶𝐴 = ( )
1 + 𝜀𝐴 𝑋𝐴

𝐶
𝐶𝐴0 (1 − 𝑋𝐴 ) 1 − 𝐶𝐴
0
𝐶𝐴 = 𝑋𝐴 =
1 + 𝜀𝐴 𝑋𝐴 𝐶
1 + 𝜀𝐴 𝐶𝐴
0

1 𝑑𝑁
−𝑟𝐴 = − 𝐶𝐴0 1 𝑑𝑋𝐴
𝑉 𝑑𝑡 −𝑟𝐴 = −
(1 + 𝜀𝐴 𝑋𝐴 ) 𝑑𝑡
Reactant concentrations as function of conversion
---in ideal gas reactions with volume change

Example N2 limiting reactant

The initial concentration of N2 and O2 are CA0 and CB0. Calculate the concentration of N2 and O2 at X=50%
Before reaction n0 CA0 V0 CB0 V0 0
n=n0
∆n CA0 V0 𝑋𝐴 CA0 V0 𝑋𝐴 2CA0 V0 𝑋𝐴 𝑉0
=1
n 𝑛𝐴0 1 − 𝑋𝐴 𝑛𝐵0 − 𝑛𝐴0 𝑋𝐴 2𝑛𝐴0 𝑋𝐴 𝑉

(a) 𝑉0 𝑛0 𝑇0 𝑃
1+1=2, ∴No change of volume under constant T and P = ( )( )( )
𝑉 𝑛 𝑇 𝑃0
𝑛𝐴 𝑛𝐴0 1−𝑋𝐴
→ 𝐶𝐴 = = = 𝐶𝐴0 (1 − 𝑋𝐴 )=0.5 𝐶𝐴0
𝑉 𝑉0
𝑛𝐵 𝐶𝐵0 𝑉0 −𝑛𝐴0 𝑋𝐴 𝐶𝐵0 𝑉0 −𝐶𝐴0 𝑉0 𝑋𝐴 𝐶𝐵0
→ 𝐶𝐵 = = = = 𝐶𝐴0 ( − 𝑋𝐴 )
𝑉 𝑉0 𝑉0 𝐶𝐴0
Reactant concentrations as function of conversion
---in ideal gas reactions with volume change
Example CO limiting reactant

The initial concentration of CO is CA0. Only CO and O2 are in the feed and mole fraction of CO is 1/4. Calculate
the concentration of CO and O2 at X=50%

2+1≠2, ∴ the total volume change after reactionunder constant T and P

𝑉0 𝑛0 𝑇0 𝑃
= ( )( )( )
𝑉 𝑛 𝑇 𝑃0

ɛA : The fractional change in volume of the system between no conversion and complete conversion of
reactant A.
𝑉𝑋𝐴 =1 −𝑉𝑋𝐴 =0 𝑛𝑋𝐴 =1 −𝑛𝑋𝐴 =0
𝜀𝐴 = =
𝑉𝑋𝐴 =0 𝑛𝑋𝐴 =0
 Reactant concentrations as function of conversion
---in ideal gas reactions with volume change
Example CO limiting reactant

The initial concentration of CO is CA0. Only CO and O2 are in the feed and mole fraction of CO is 1/4. Calculate
the concentration of CO and O2 at X=50%
n0 CA0 V0 3CA0 V0 0 n≠n0
≠1
𝑉0 𝑛0 𝑇0 𝑃 𝑉0
= ( )( )( ) ∆n CA0 V0 𝑋𝐴 0.5 CA0 V0 𝑋𝐴 CA0 V0 𝑋𝐴 ∴
𝑉 𝑛 𝑇 𝑃0 𝑉
n CA0 V0 1 − 𝑋𝐴 3CA0 V0 - 0.5 CA0 V0 𝑋𝐴 CA0 V0 𝑋𝐴
𝑉𝑋𝐴=1 − 𝑉𝑋𝐴=0 (3CA0 V0 − 0.5 CA0 V0 + CA0 V0 ) − (CA0 V0 +3CA0 V0)
𝜀𝐴 = = = −0.125
𝑉𝑋𝐴=0 CA0 V0 + 3CA0 V0

𝑛 = 𝑛0 + 𝑛0 𝑋𝐴 𝜀𝐴 𝑉0 𝑛0 1 1
∴ = = =
𝑉 𝑛 1 + 𝜀𝐴 𝑋𝐴 1 − 0.125 × 50%

𝐶𝐴0 (1 − 𝑋𝐴 ) 𝑇0 𝑃 Isothermal 0.5𝐶𝐴0 0.5

𝐶𝐴 = ( )( )( ) 𝐶𝐴 = = 𝐶
1 + 𝜀𝐴 𝑋𝐴 𝑇 𝑃0 1 − 0.125 × 0.5 0.9375 𝐴0
Reaction
kinetics
Reaction kinetics

Rate Law for elementary reactions -𝑟 = 𝑘[𝐶𝐴𝑎 𝐶𝐵𝑏 … ]

the rate equation corresponds to a stoichiometric equation

Rate Law for non-elementary reactions

no direct correspondence between stoichiometry and rate

what we observe as a single reaction is in reality the overall effect

of a sequence of elementary reactions.
Order of Reaction

Rate Law -𝑟 = 𝑘[𝐶𝐴𝑎 𝐶𝐵𝑏 … ] Reaction order : the powers to which the concentrations are raised

ath order with respect to A bth order with respect to B nth order overall

Rate constant 𝑘

Unit of 𝑘 for a nth order reaction?

𝑑𝐶𝐴 ?𝑘
First order reaction = 𝑟 = −𝑘𝐶𝐴
𝑑𝑡

𝑑𝐶𝐴
Unit of 𝑘?
Second Order reaction =𝑟= −𝑘𝐶𝐴2
𝑑𝑡
Order of Reaction

Rate Law -𝑟 = 𝑘[𝐶𝐴𝑎 𝐶𝐵𝑏 … ]

Experimental
How to determination the reaction order and rate constant? measurements of CA
as a function of t
First order reaction
𝑑𝐶𝐴 𝐶𝐴
= −𝑘𝐶𝐴 ∴ ln = −𝑘𝑡
𝑑𝑡 𝐶𝐴0

Second Order reaction

𝑑𝐶𝐴 1 1
= −𝑘𝐶𝐴2 ∴ − = 𝑘𝑡
𝑑𝑡 𝐶𝐴 𝐶𝐴0
For reaction with little prior knowledge
𝑑𝐶𝐴 𝑑𝐶𝐴
= −𝑘′𝐶𝐴𝑚 ∴ ln − = 𝑙𝑛𝑘 + 𝑚𝑙𝑛𝐶𝐴
𝑑𝑡 𝑑𝑡
 Reaction kinetics
Example
Use the batch reactor data given below to show that the reaction is second order and
determine the rate constant for the liquid phase reaction 2A→Product.
(0.1 dm3mol-1min-1)

Time (min) 0 2 4 6 8 15 30 50

Conc.(kmol m-3) 1.25 1.01 0.825 0.715 0.625 0.435 0.264 0.172
8

6 y = 0.1002x + 0.798
R² = 1
1 1 4
− = 𝑘𝑡
𝐶𝐴 𝐶𝐴0 2

0
(k=0.1 dm3mol-1min-1) 0 10 20 30 40 50 60
 Reaction kinetics
Example
Use the batch reactor data given below to show that the reaction is second order and
determine the rate constant for the liquid phase reaction 2A→Product.
(0.1 dm3mol-1min-1)

Time (min) 0 2 4 6 8 15 30 50

Conc.(kmol m-3) 1.25 1.01 0.825 0.715 0.625 0.435 0.264 0.172

What if we donot know the reaction order? 0

-2 -1.5 -1 -0.5 0 0.5
𝑑𝐶𝐴 𝑚 𝑑𝐶𝐴
= −𝑘′𝐶𝐴 ln − = 𝑙𝑛𝑘 + 𝑚𝑙𝑛𝐶𝐴 y = 1.8019x - 2.159 -2
𝑑𝑡 𝑑𝑡 R² = 0.9931
-4

𝑘 = 0. 11, m=1.8 -6

Approximately the actual situation

Rate Law for Nonelementary reactions
3/2
−𝑟𝐶𝑂 = 𝑘𝐶𝐶𝑂 𝐶𝐶𝑙2

Not follow simple elementary rate laws

k1
A+E ⇌k A* + E • *A high-energy molecule that reacts virtually as fast as it is formed
• *Present in very small concentrations
→

2 k3
B+C
𝑘1 𝐶𝐴 𝐶E 𝑘1 𝑘3 𝐶𝐴 𝐶E
−𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶𝐸 − 𝑘2 𝐶𝐴∗ 𝐶𝐸 −𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶E − 𝑘2 𝐶E =
𝑘2 𝐶E + 𝑘3 𝑘2 𝐶E + 𝑘3

𝑘1 𝐶𝐴 𝐶E
𝑟𝐴∗ = 𝑘1 𝐶𝐴 𝐶𝐸 − 𝑘2 𝐶𝐴∗ 𝐶𝐸 −𝑘3 𝐶A∗ =0 𝐶𝐴∗ =
𝑘2 𝐶E + 𝑘3
 Rate Law for Nonelementary reactions
k1
A+E ⇌k A*k + E

→
2 3

B+C
𝑘1 𝐶𝐴 𝐶E 𝑘1 𝑘3 𝐶𝐴 𝐶E
−𝑟𝐴 = 𝑘1 𝐶𝐴 𝐶E − 𝑘2 𝐶 =
𝑘2 𝐶E + 𝑘3 𝑀 𝑘2 𝐶E + 𝑘3

At high concentration of enzyme, 𝑘3 insignificant compared with the first term

𝑘1 𝑘3 𝐶𝐴 𝐶𝑀 𝑘1 𝑘3
−𝑟𝐴 =
𝑘2 𝐶𝑀 + 𝑘3
≈
𝑘2 𝐴
𝐶 = 𝑘𝐴 𝐶𝐴 Apparent reaction order (n=1) and rate constant

At low concentration of enzyme, 𝑘2 𝐶𝑀 insignificant compared with the second term

𝑘1 𝑘3 𝐶𝐴 𝐶𝑀 𝑘1 𝑘3
−𝑟𝐴 = ≈ 𝐶 𝐶 = 𝑘1 𝐶𝐴 𝐶𝑀 Apparent reaction order (n=2) and rate constant
𝑘2 𝐶𝑀 + 𝑘3 𝑘3 𝐴 𝑀
Reaction Rates as Functions of Temperature
Temperature Dependency from Arrhenius' Law
−Ea
k =Ae RT

• k Reaction rate constant

• Ea Molar activation energy.
• A Frequency or Pre-exponential factor
• R =8.3144, Molar gas constant m3 Pa /(mol∙ 𝐾)
• T Temperature, K

lnk = lnA − 𝐸𝑎 /𝑅𝑇

Reaction Rates as Functions of Temperature
Example Milk is pasteurized if it is heated to 63oC for 30 min, but if it is heated to 74°C it only needs 15 s for
the same result. Find the activation energy of this sterilization process.

−Ea
k =Ae RT

lnk = lnA − 𝐸𝑎 /𝑅𝑇

Reaction Rates as Functions of Temperature
Example Milk is pasteurized if it is heated to 63oC for 30 min, but if it is heated to 74°C it only needs 15 s for
the same result. Find the activation energy of this sterilization process.

Solution −Ea
k =Ae RT

lnk = lnA − 𝐸𝑎 /𝑅𝑇

Note:The unit of temperature for calculation should be K=oC+273
T1=63+273=336 K; T2=74+273=347 K
t1=30 min=1800 s; t2=15 s ∴t1/t2=1800/15=120
Now the rate is inversely proportional to the reaction time, or rate ∝ 1/time so
𝑘2
𝑙𝑛 = E=422000 J/mol
𝑘1
 Reaction Rates as Functions of Temperature
Example Consider a chemical elementary reaction system where reactants A and B can react through two
different pathways to form products C and D, respectively. The reaction pathway leading to product C
has a higher activation energy than the pathway leading to product D. A research team aims to
maximize the yield of product D in a reactor.
1.Explain why the reaction pathway with the higher activation energy (leading to D) would normally
proceed slower under the same conditions.
2.Discuss how the choice of reactor temperature could be optimized to achieve the highest possible
yield of product D.
C Ea1 −Ea
Ea1 > Ea2 A+B lnk = lnA − 𝐸𝑎 /𝑅𝑇
D Ea2 k =Ae RT
↑ ↓
−Ea 1
k1 = A e RT

−Ea 1 𝒌𝟐 −Ea2 Ea1 Ea1 −Ea2 𝒌𝟐 Ea1 − Ea2

k2 = A e RT = 𝑒 RT + RT = 𝑒 RT > 𝑒 0 ln =
𝒌𝟏 𝒌𝟏 RT
Lower temperature could be better
Chemical Equilibrium
Calculations
 Le Chatelier’s principle
◼ If a restraint is imposed on a reacting system which is initially at equilibrium,
the system will react in a manner which tends to oppose the restraint.

⇌
XA XA
νA= -a, νB= -b, νC= c, νd= d
−𝑟𝐴→ = 𝑘1 𝐶𝐴𝑎 𝐶𝐵𝑏 −𝑟𝐴← = 𝑘2 𝐶𝐴𝑐 𝐶𝐵𝑑
Endothermic Exothermic
At equilibrium, the forward and backward reaction rates are equal
T T 𝑽 𝑽
𝒌𝟏 𝑪𝑪𝒆𝒄 𝑪𝑫𝒆
𝑫
For a reversible reaction Equilibrium Constant 𝑲𝒄 = =
𝒌𝟐 −𝑽 −𝑽
𝑪𝑨𝒆 𝑨 𝑪𝑩𝒆 𝑩
−Ea1 −Ea2
k1 = A e RT k2 = A e RT

𝒌𝟏 −Ea1 Ea2
+
𝑲𝒄 = = 𝑒 RT RT
𝒌𝟐
Equilibrium conversion in reactor
Components A and B in aqueous solution react according to equation A+B ⇌ C+D .
Equilibrium constant at 25°C being 30. If an 2 M solution of A is mixed with an equal volume
Example of a 4 M solution of B in a batch reactor maintained at 25°C, what will be the equilibrium
conversion (XAe) of component A?
 Components A and B in aqueous solution react according to equation A+B ⇌ C+D .
Equilibrium constant at 25°C being 30. If an 2 M solution of A is mixed with an equal volume
Example of a 4 M solution of B in a batch reactor maintained at 25°C, what will be the equilibrium
conversion (XAe) of component A?

Concentration of A immediately after mixing but before reaction CA0 =1 M

Concentration of B immediately after mixing but before reaction CB0=2 M
Solution Volume changes during the reaction are negligible.
CAe= concentration of A when equilibrium has been reached= CA0(1 -XAe)
CBe= concentration of B when equilibrium has been reached= CB0-CA0XAe=CA0(2-XAe)
CCe= concentration of C when equilibrium has been reached= CA0XAe
CAe= concentration of D when equilibrium has been reached= CA0XAe
𝑪𝑪𝒆 𝑪𝑫𝒆 𝑿𝟐𝑨𝒆
𝑲𝒄 = = = 𝟑𝟎
𝑪𝑨𝒆 𝑪𝑩𝒆 (𝟏 − 𝑿𝑨𝒆 )(𝟐 − 𝑿𝑨𝒆 )
𝑿𝑨𝒆 = 𝟎. 𝟗𝟕
 Thermal
Calculations
Mode Operation
Isothermal Operation A thermodynamic process whose temperature remains constant. A
system exchange heat with its surroundings. The rate at which heat is
exchanged is so slow that the system attains thermal equilibrium at
every step. In some processes, the system exchanges heat with a
reservoir.

Adiabatic Operation No heat is added or removed from the reactor (i.e., Q = 0).
The system is thermally isolated. Heat given up by the reaction is
entirely used within the system to change its enthalpy
 Energy Balance on Reactor Systems
Enthalpy 𝐻 = 𝑈 + 𝑃𝑉

U Internal energy P Pressure V Volume

Enthalpy changes in closed system Enthalpy changes in a steady flow system

(∆𝐻 = ∆𝑄 + ∆Ws ) 𝐻𝑜𝑢𝑡 − 𝐻𝑖𝑛 = ∆𝑄 + ∆W
∆Ws Stirrer/Recirculating pump energy input ∆W Zero or small
Negligible except when the contents are very viscous 𝐻in 𝐻in
∆Ws ∆Ws

∆𝐻 ∆𝑄 𝐻𝑜𝑢𝑡 − 𝐻𝑖𝑛 = ∆𝑄
∆𝐻 = ∆𝑄 𝑝
∆𝐻
𝐻out

8
∆𝑄 ∆𝑄
8

𝐻out
Enthalpies of reactor fluids in batch reactor
𝐻 = 𝑓(𝑚, T, 𝑋𝐴)
Changes of enthalpy with temperature—heat capacity of the reactor fluid
Changes of enthalpy with conversion-----enthalpy of reaction
Enthalpy of reaction
∆𝐻𝑅,𝐴 𝑇 = 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑜𝑓 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 𝑓𝑙𝑢𝑖𝑑 𝑝𝑒𝑟 𝑚𝑜𝑙𝑒 𝑜𝑓 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑎𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇

Heat capacity

For a mixture of nAA and nBB 𝐶𝑃 = 𝑛𝐴 𝐶𝑝𝑚𝐴 + 𝑛𝐵𝐶𝑝𝑚𝐵 Cpm molar heat capacity of the pure component

νaA+νBB→ νcC+ νDD 𝐶𝑃 = 𝑛𝐴 𝐶𝑝𝑚𝐴 + 𝑛𝐵𝐶𝑝𝑚𝐵 + 𝑛𝐶𝐶𝑝𝑚𝐶 + 𝑛𝐷𝐶𝑝𝑚𝐷 + 𝑛𝐼 𝐶𝑝𝑚𝐼 = σ 𝑛𝑖 𝐶𝑝𝑚𝑖

𝑖
𝑣𝑖
𝐶𝑃 = ෍ 𝑛𝑖𝑜 𝐶𝑝𝑚𝑖 − 𝑛𝐴0 𝑋𝐴 ෍[( )𝐶𝑝𝑚𝑖 ]
𝑣𝐴
𝑖 𝑖

Enthalpy change 𝑑𝐻 = 𝐶𝑝 (𝑋𝐴 , 𝑇)dT + 𝑛𝐴0 ∆𝐻𝑅,𝐴 (𝑇)d𝑋𝐴

𝑇
Batch reactor ∆𝑄 = 𝐻𝐹 − 𝐻0 = 𝑛𝐴0 ∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ]+‫ 𝐹𝐴𝑋 𝑃𝐶 𝐹 𝑇׬‬, 𝑇 𝑑𝑇
0
Thermal Calculation on batch reactor
Example
Thermal effects accompanying isomerization in a batch reactor. The reaction A →B is a first-
order isomerisation reaction. Both A and B are liquids of very low volatility with a 'relative
molecular mass’(or molecular weight) of 250. Both liquids have average molar heat
capacities C, of 525 J mol-1 K-1 in the temperature range of interest. The reaction is to be
carried out in the liquid phase in a batch reactor and a final conversion of 0.97 is specified.
The reactor size is such that 500 kg of A can be processed per batch. The enthalpy of
reaction per mole of A consumed at 436 K is given by ∆H R,A (436) = -87.15 kJmol-1.
(a) If the reactor is to be operated isothermally at full capacity at 436 K, calculate the
heat which must be removed from the reactor shell over the entire period of reaction.
(b) lf the reactor is operated adiabatically with a starting temperature of 436 K, calculate
the reactor temperature when the conversion reaches 0.97.
Thermal Calculation on batch reactor
Thermal effects accompanying isomerization in a batch reactor. The reaction A →B is a first-order
Example isomerisation reaction. Both A and B are liquids of very low volatility with a 'relative molecular mass’(or
molecular weight) of 250. Both liquids have average molar heat capacities C, of 525 J mol-1 K-1 in the
temperature range of interest. The reaction is to be carried out in the liquid phase in a batch reactor and a
final conversion of 0.97 is specified. The reactor size is such that 500 kg of A can be processed per batch. The
enthalpy of reaction per mole of A consumed at 436 K is given by ∆H R,A (436)=-87.15 kJmol-1.

Solution 𝑛0 = 500 ×
1000
= 2000 𝑚𝑜𝑙 𝑑𝐻 = 𝐶𝑝 (𝑋𝐴 , 𝑇)dT + 𝑛𝐴0 ∆𝐻𝑅,𝐴 (𝑇)d𝑋𝐴
250
(a) isothermal, ∆T=0
∆𝑄 = ∆𝐻 = 𝑛𝐴0 ∆𝐻𝑅,𝐴 (𝑇)d𝑋𝐴 =2000*(-87.15 )*0.97= 169 MJ

(b) adiabatic, ∆Q=0

𝐶𝑃 = 𝑛𝐴 𝐶𝑝𝑚𝐴 + 𝑛𝐵𝐶𝑝𝑚𝐵 =𝑛𝐴0 1 − 𝑋𝐴 𝐶𝑝𝑚𝐴 + 𝑛𝐴0 𝑋𝐴 𝐶𝑝𝑚𝐵 = 𝑛𝐴0 𝐶𝑝𝑚𝐴 = 2000 × 0.525 𝑘𝐽 ∙ 𝐾 −1

∆𝐻𝑅,𝐴 𝑇 0.97
𝐶𝑝 𝑋𝐴 , 𝑇 dT = − 𝑛𝐴0 ∆𝐻𝑅,𝐴 𝑇 d𝑋𝐴 = 𝑛𝐴0 𝐶𝑝𝑚 dT ∴∆𝑇 = 𝐶𝑝
= 161 𝐾
Enthalpies of flow fluids in CSTR and PFR
𝐻 = 𝑓(𝒎, 𝑻, 𝑿𝑨 ) A function of state,
Changes of enthalpy with temperature—heat capacity of the reactor fluid
Changes of enthalpy with conversion-----enthalpy of reaction
Enthalpy of reaction A hypothetical route-a batch of the inlet liquid containing nAo
𝑏𝑎𝑡𝑐ℎ 𝑏𝑎𝑡𝑐ℎ moles of A with other components to react until the conversion
𝐻𝑜𝑢𝑡 − 𝐻𝑖𝑛 = 𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙 reaches XA equal to that in the outlet stream

𝑇
Flow reactor ∆𝑄 = 𝐻𝑜𝑢𝑡 − 𝐻𝑖𝑛 = 𝑛𝐴0 ∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ]+‫ 𝐹𝐴𝑋 𝑃𝐶 𝐹 𝑇׬‬, 𝑇 𝑑𝑇
0

𝑣𝑖
𝐶𝑃 = ෍ 𝑛𝑖𝑜 𝐶𝑝𝑚𝑖 − 𝑛𝐴0 𝑋𝐴 ෍[( )𝐶𝑝𝑚𝑖 ]
𝑣𝐴
𝑖 𝑖
.
Q= 𝐹𝐴0 ∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ]+ σ 𝐹𝑖 𝐶𝑝𝑚𝑖 𝑑𝑇

F 0=moles of A entering reactor in unit time = molar flow rate of A at entry

Fi = moles of i in unit time cross the boundary where conversion of A is XA
. = molar flow rate of i at this boundary
Q= heat entering reactor or reactor system in unit time= rate of heat input
Thermal Calculation on tubular reactor
Example Temperature rise accompanying adiabatic oxidation of SO2 in a tubular reactor operating at
steady state.
The feed to the reactor has the following composition in mole percentages: SO2 = 9.0, O2=
12.0, and N2 = 79.0. The feed temperature is 750 K and the reactor pressure is close to 1
atmosphere. If the outlet conversion of SO2 (moles of SO2 reacted per mole of SO2 in the feed)
is 0.60, what is the temperature of the product stream?

Data: The oxidation reaction will be written in the form SO₂ + (1/2)O2 → SO3
the enthalpy of reaction at 750 K being ∆HR =-89 300 J per mole of S0₂ consumed
The mean molar heat capacities (in J mol-1K-1) over the temperature range of interest are
taken to be as follows:
SO2 = 52.0, O2 =33.0, N2 =31.0 SO3= 78.0
Thermal calculation on reactor systems
Temperature rise accompanying adiabatic oxidation of SO2 in a tubular reactor operating at steady state.
Example The feed to the reactor has the following composition in mole percentages: SO2 = 9.0, O2= 12.0 and N2, =
79.0. The feed temperature is 750 K and the reactor pressure is close to l atmosphere. If the outlet
conversion of SO2 (moles of SO2 reacted per mole of SO2 in the feed) is 0.60, what is the temperature of
the product stream?
Data: The oxidation reaction will be written in the form S0₂ + (1/2)02 → SO3
the enthalpy of reaction at 750 K being ∆HR =-89 300 J per mole of S0₂ consumed
The mean molar specific heats (in J mol-1K-1) over the temperature range of interest are taken to be as
follows:

Solution .
adiabatic, ∆Q=0 Q= 𝐹𝐴0 ∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ]+ σ 𝐹𝑖 𝐶𝑝𝑚𝑖 𝑑𝑇 = 0

𝑏𝑎𝑡𝑐ℎ 𝑏𝑎𝑡𝑐ℎ
𝐻𝑓𝑖𝑛𝑎𝑙 − 𝐻𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = ∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ]+ ෍ 𝐶𝑝𝑚𝑖 𝑑𝑇 = 𝑄 = 0

σ 𝐶𝑝𝑚𝑖 = (0.4)𝐶𝑝𝑚𝑆𝑂2+ (43 − 0.5 × 0.6)𝐶𝑝𝑚𝑂2+ + (799)𝐶𝑝𝑚𝑁2 + (1 × 0.6)𝐶𝑝𝑚𝑆𝑂3 = 374 J K-1

−(∆𝐻𝑅,𝐴 (𝑇0) [𝑋𝐴 ])
𝑑𝑇= σ 𝐶𝑝𝑚𝑖
= 143 𝐾 ∴ 𝑇 𝑜𝑢𝑡𝑙𝑒𝑡 = 750 + 143 = 893 𝐾