CHAPTER 1 SUMMARY

WHAT DO YOU NEED TO KNOW?

SECTION 1.3: How to recognise properties of reactions and the aspects/difficulties of design
related to them
SECTION 1.4: How to apply the ratio of reaction rates and stoichiometric factors
𝑹𝑨 𝑹𝑩 𝑹𝑪 𝑹𝑫 𝑹ሶ 𝑨 𝑹ሶ 𝑩 𝑹ሶ 𝐂 𝑹ሶ 𝐃 𝐫𝑨 𝐫𝑩 𝐫𝐂 𝐫𝐃
𝑹= = = = =⋯ 𝑹ሶ = = = = 𝒓= = = =
𝒔𝑨 𝒔𝑩 𝒔𝑪 𝒔𝑫 𝒔𝑨 𝒔𝑩 𝒔𝑪 𝒔𝑫 𝒔𝑨 𝒔𝑩 𝒔𝑪 𝒔𝑫
How to evaluate units of the rate constant and if a reaction is elementary
SECTION 1.5-1.8: Names of the main reactors, how to sketch the main configurations, how to
select the best reactor, and reactor internals (baffles, agitators, heat
exchangers) according to their main use, advantages and disadvantages.

Agitators
HOMOGENEOUS
Propellers Turbines Wide radius Archimedes

Advantages and uses of Baffles

Jacket
Stirred tank reactor Half-pipe jacket
Heat exchange Isotherm Internal Coil
External heat exchanger
Condenser
Adiabatic
HOMOGENOUS

Operation mode
Batch Semi-batch Continuous

Advantages of the use of packing and baffles

Concentric pipes
Isotherm Tube and shell
Tubular reactor Heat exchange Furnace
Adiabatic

Operation mode
Continuous
REACTORS

(Spray tower
Irrigated bed
Film contactors
Plate tower
Static mixer
FLUID-FLUID
Bubble tower
Bubble contactors Bubble tank
Agitated bubble tank

Monolith
Single packed bed
BIPHASIC SYSTEMS Packed bed Milti-bed
Multitubular isotherm
Tubular or multi-tubular furnace

Fluidised bed Adiabatic/Isotherm/non-isotherm without regeneration

SOLID-FLUID Adiabatic/isotherm/non-isotherm with regeneration
Packed moving bed
Moving bed Fluidised moving bed
Entrained reactor

Other systems Screw or rotary kiln

Suspended solid stirred tank reactor

Mist flow bed

Packed bed solid configurations Bubble flow bed
MULTIPHASIC (G-L-S) Trickle flow bed
Slurry column
Suspended/ebullated solid configurations Agitated slurry
Ebullated bed

WHAT YOU DON’T NEED TO MEMORIZE?

Geometry information for stirred tank reactors including the agitators and baffles.
THREE PIECES OF REACTOR PER WEEK. THE BEST DIET FOR THE CHEMICAL ENGINEER
(EQUATION STEPS TO DEMONSTRATE IN THE EXAM)
EQUATIONS 𝒅𝑵𝑱
Molar balance of component: 𝑭𝑱,𝒊𝒏 − 𝑭𝑱,𝒐𝒖𝒕 + 𝑹ሶ 𝑱 =
GIVEN: 𝒅𝒕
Enthalpy balance: ∆𝑯෡ 𝑹,𝑱 𝑹ሶ 𝑱 𝒅𝑻
Constant pressure,
Constant specific heat capacity 𝒎ሶ 𝒊𝒏 𝒄ො 𝑷,𝒂𝒗 (𝑻𝒊𝒏 − 𝑻∗ ) − 𝒎ሶ 𝒐𝒖𝒕 𝒄ො 𝑷,𝒂𝒗 (𝑻𝒐𝒖𝒕 − 𝑻∗ ) − + 𝑸ሶ = 𝒎ො𝒄𝑷,𝒂𝒗
One reaction, one inlet, one outlet
𝒔𝑱 𝒅𝒕

BATCH STIRRED TANK CONTINUOUS STIRRED TANK TUBULAR REACTOR (TR)

REACTOR (BSTR) REACTOR (CSTR)
Close system Steady state Steady state
(no inlet or outlet) (no accumulation) (no accumulation)
Assumption of operation:

𝐹𝐽,𝑖𝑛 − 𝐹𝐽,𝑜𝑢𝑡 + 𝑅ሶ 𝐽 = 0 𝐹𝐽,𝑖𝑛 − 𝐹𝐽,𝑜𝑢𝑡 + 𝑅ሶ 𝐽 = 0

𝑑𝑁𝐽 ෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻 ෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻
𝑅ሶ 𝐽 = ∗ ∗
𝑚ሶ 𝑖𝑛 𝑐Ƹ𝑃,𝑎𝑣 (𝑇𝑖𝑛 − 𝑇 ) − 𝑚ሶ 𝑜𝑢𝑡 𝑐Ƹ𝑃,𝑎𝑣 (𝑇𝑜𝑢𝑡 − 𝑇 ) − ሶ
+ 𝑄 = 0 𝑚ሶ 𝑖𝑛 𝑐𝑃,𝑎𝑣
Ƹ ∗
(𝑇𝑖𝑛 − 𝑇 ) − 𝑚ሶ 𝑜𝑢𝑡 𝑐𝑃,𝑎𝑣
Ƹ ∗
(𝑇𝑜𝑢𝑡 − 𝑇 ) − + 𝑄ሶ = 0
𝑑𝑡 𝑠𝐽 𝑠𝐽
One inlet an one outlet 𝒎ሶ 𝒊𝒏 = 𝒎ሶ 𝒐𝒖𝒕 = 𝒎ሶ 𝟎 One inlet an one outlet 𝒎ሶ 𝒊𝒏 = 𝒎ሶ 𝒐𝒖𝒕 = 𝒎ሶ 𝟎
Constant specific heat capacity with temperature and conversion Constant specific heat capacity with temperature and conversion
෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻 𝑑𝑇
− + 𝑄ሶ = 𝑚𝑐𝑃,𝑎𝑣
Ƹ
𝑠𝐽 𝑑𝑡
𝑅ሶ𝐽 = ∆𝐹𝐽 𝑅ሶ 𝐽 = 𝐹𝐽,𝑜𝑢𝑡 − 𝐹𝐽,𝑖𝑛

෡𝑅,𝐽 𝑅ሶ𝐽
∆𝐻 ෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻
𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ (𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 ) − + 𝑄ሶ = 0 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ (𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 ) − + 𝑄ሶ = 0
𝑠𝐽 𝑠𝐽

Approach to a perfectly mixed reactor. Approach to a perfectly mixed reactor. Approach to a plug flow reactor:
As the concentration is uniform in the reactor: As the concentration is uniform in the reactor: 𝑹ሶ 𝑱 ≠ 𝐫𝑱 𝑽

𝑹ሶ 𝑱 = 𝒓𝑱 𝑽 𝑹ሶ 𝑱 = 𝐫𝑱 𝑽 We need to apply the mass and energy balance in a shell

Assumption of reactor:

of my reactor, in which:
𝒅𝑹ሶ 𝑱 = 𝐫𝑱 𝒅𝑽
Then I can apply the mass and energy balance I can apply the mass and energy balance in the entire
in the entire volume of reactor volume of reactor
𝑑 𝑅ሶ 𝐽 = 𝐹𝐽 + 𝑑𝐹𝐽 − 𝐹𝐽 = d𝐹𝐽
As the reaction rate changes with time the
heat exchanged is going to change with time: The conditions at the outlet are the same than inside
𝑑𝑄 ෡𝑅,𝐽 𝑑𝑅ሶ𝐽
𝑄ሶ = ∆𝐻
Assumption of reactor:

𝑑𝑡 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ 𝑇 − 𝑇 + 𝑑𝑇 − + 𝑑 𝑄ሶ = 0
𝑠𝐽

𝑑𝑁𝐽
𝑅ሶ 𝐽 = 𝑅ሶ 𝐽 = ∆𝐹𝐽 𝑑 𝑅ሶ𝐽 = d𝐹𝐽
𝑑𝑡
෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻 ෡𝑅,𝐽 𝑑𝑅ሶ 𝐽
∆𝐻
෡𝑅,𝐽 𝑅ሶ 𝐽 𝑑𝑄
∆𝐻 𝑑𝑇 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ (𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 ) − + 𝑄ሶ = 0
− + = 𝑚𝑐𝑃,𝑎𝑣
Ƹ 𝑠𝐽 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ (−𝑑𝑇) − + 𝑑 𝑄ሶ = 0
𝑠𝐽 𝑑𝑡 𝑑𝑡 𝑠𝐽

EQUATIONS We need to convert the differential or increases of molar flow or number of moles into differential or increases of conversion with:

GIVEN: 𝒅𝑵𝑱 = −𝑵𝑱,𝟎 𝒅𝑿𝑱 ∆𝑵𝑱 = −𝑵𝑱,𝟎 ∆𝑿𝑱 𝒅𝑭𝑱 = −𝑭𝑱,𝟎 𝒅𝑿𝑱 ∆𝑭𝑱 = −𝑭𝑱,𝟎 ∆𝑿𝑱

𝑵𝑱,𝟎 𝒅𝑿𝑱
𝑹ሶ 𝑱 = − 𝑹ሶ 𝑱 = −𝑭𝑱,𝟎 ∆𝑿𝑱 𝒅𝑹ሶ 𝑱 = −𝑭𝑱,𝟎 𝒅𝑿𝑱
𝒅𝒕

Combine the generation term of the mass balance with the generation term of the energy balance
෡𝑅,𝐽 𝑵𝑱,𝟎 𝒅𝑿𝑱 𝑑𝑄
∆𝐻 𝑑𝑇 ෡𝑅,𝐽 𝑭𝑱,𝟎 ∆𝑿𝑱
∆𝐻 ෡𝑅,𝐽 𝑭𝑱,𝟎 𝒅𝑿𝑱
∆𝐻
+ = 𝑚𝑐𝑃,𝑎𝑣
Ƹ 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ 𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 + + 𝑄ሶ = 0 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ −𝑑𝑇 + + 𝑑 𝑄ሶ = 0
𝑠𝐽 𝒅𝒕 𝑑𝑡 𝑑𝑡 𝑠𝐽 𝑠𝐽

Substitute the generation term by the reaction rate

Obtaining the parameter of design

(general performance equation)

𝑵𝑱,𝟎 𝒅𝑿𝑱
𝐫𝑱 𝑽 = − 𝐫𝑱 𝑽 = −𝑭𝑱,𝟎 ∆𝑿𝑱 𝐫𝑱 𝒅𝑽 = −𝑭𝑱,𝟎 𝒅𝑿𝑱
𝒅𝒕
from the mass balance

Separate the parameter of design of the reactor in one side of the equation
−𝑵𝑱,𝟎 𝒅𝑿𝑱 −𝑭𝑱,𝟎 ∆𝑿𝑱 −𝑭𝑱,𝟎 𝒅𝑿𝑱
𝒅𝒕 = 𝑽= 𝒅𝑽 =
𝐫𝑱 𝑽 𝐫𝑱 𝐫𝑱

As condition inside the reactor are the same as the conditions at the
Integrate between the limits Integrate between the limits
outlet, 𝐫𝑱 = 𝐫𝑱,𝒐𝒖𝒕

𝒕 𝑿𝑱,𝒆𝒏𝒅 𝑽 𝑿𝑱,𝒐𝒖𝒕 −𝑭
−𝑵𝑱,𝟎 −𝑭𝑱,𝟎 ∆𝑿𝑱 𝑱,𝟎
න 𝒅𝒕 = න 𝒅𝑿𝑱 න 𝒅𝑽 = න 𝒅𝑿𝑱
𝑽= 𝐫𝑱
𝟎 𝑿𝑱,𝒔𝒕𝒂𝒓𝒕 𝐫𝑱 𝑽 𝐫𝑱,𝒐𝒖𝒕 𝟎 𝑿𝑱,𝒊𝒏

𝑿𝑱,𝒆𝒏𝒅 −𝑵 𝑿𝑱,𝒐𝒖𝒕 −𝑭
𝑱,𝟎 −𝑭𝑱,𝟎 ∆𝑿𝑱 𝑱,𝟎
𝒕𝑩𝑷𝑴𝑹 = න 𝒅𝑿𝑱 𝑽𝑪𝑷𝑴𝑹 = 𝑽𝑷𝑭𝑹 = න 𝒅𝑿𝑱
𝑿𝑱,𝒔𝒕𝒂𝒓𝒕 𝐫𝑱 𝑽 𝐫𝑱,𝒐𝒖𝒕 𝑿𝑱,𝒊𝒏 𝐫𝑱

෡𝑅,𝐽 𝑁𝐽,0 𝑑𝑋𝐽

∆𝐻 ෡𝑅,𝐽 𝐹𝐽,0 ∆𝑋𝐽
∆𝐻 ෡𝑅,𝐽 𝐹𝐽,0 𝑑𝑋𝐽
∆𝐻
USE OF THE ENERGY BALANCE TO OBTAIN THE

+ 𝑑 𝑄ሶ = 0
PARAMETER RELATED TO THE THERMAL CONDITIONS

+ 𝑑𝑄 = 𝑚𝑐𝑃Ƹ 𝑑𝑇 𝑚ሶ 0 𝑐𝑃Ƹ 𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 + + 𝑄ሶ = 0 𝑚ሶ 0 𝑐𝑃Ƹ −𝑑𝑇 +

𝑠𝐽 𝑠𝐽 𝑠𝐽

෡𝑅,𝐽 𝑁𝐽,0
∆𝐻 ෡𝑅,𝐽 𝐹𝐽,0
ISOTHERM (dT = 0)

∆𝐻
𝑑𝑄 = − 𝑑𝑋𝐽 𝑑𝑄ሶ = − 𝑑𝑋𝐽
heat exchanged?

𝑠𝐽 𝑠𝐽
෡𝑅,𝐽 𝐹𝐽,0 ∆𝑋𝐽
∆𝐻
𝑄ሶ = 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ 𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 −
𝑄 ෡𝑅,𝐽 𝑁𝐽,0
∆𝐻 𝑋𝐽,𝑒𝑛𝑑 𝑠𝐽 𝑄ሶ ෡𝑅,𝐽 𝐹𝐽,0
∆𝐻 𝑋𝐽,𝑜𝑢𝑡
න 𝑑𝑄 = − න 𝑑𝑋𝐽 න 𝑑𝑄ሶ = − න 𝑑𝑋𝐽
0 𝑠𝐽 𝑋𝐽,𝑠𝑡𝑎𝑟𝑡 𝑠𝐽
0 𝑋𝐽,𝑖𝑛

෡ 𝑹,𝑱 𝑵𝑱,𝟎
∆𝑯 ෡ 𝑹,𝑱 𝑭𝑱,𝟎 ∆𝑿𝑱
∆𝑯 ෡ 𝑹,𝑱 𝑭𝑱,𝟎
∆𝑯
𝑸=− ∆𝑿𝑱 𝑸ሶ = 𝒎ሶ 𝟎 𝒄ො 𝑷,𝒂𝒗 𝑻𝒐𝒖𝒕 − 𝑻𝒊𝒏 − 𝑸ሶ = − ∆𝑿𝑱
𝒔𝑱 𝒔𝑱 𝒔𝑱
Outlet temperature?

෡𝑅,𝐽 𝑁𝐽,0 ෡𝑅,𝐽 𝐹𝐽,0 𝑑𝑋𝐽

∆𝐻
∆𝐻 ෡𝑅,𝐽 𝐹𝐽,0 ∆𝑋𝐽
∆𝐻 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ −𝑑𝑇 + =0
𝑑𝑋𝐽 = 𝑚𝑐𝑃,𝑎𝑣
Ƹ 𝑑𝑇
ADIABATIC (Q = 0)

𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ 𝑇𝑖𝑛 − 𝑇𝑜𝑢𝑡 + =0 𝑠𝐽
𝑠𝐽 𝑠𝐽

𝑇𝑒𝑛𝑑 ෡𝑅,𝐽 𝑁𝐽,0 𝑋𝐽,𝑒𝑛𝑑

𝑇𝑜𝑢𝑡 ෡𝑅,𝐽 𝐹𝐽,0 𝑋𝐽,𝑜𝑢𝑡
∆𝐻
∆𝐻 𝑚ሶ 0 𝑐𝑃,𝑎𝑣
Ƹ න 𝑑𝑇 = න 𝑑𝑋𝐽
𝑚𝑐𝑃,𝑎𝑣
Ƹ න 𝑑𝑇 = න 𝑑𝑋𝐽 𝑠𝐽
𝑇𝑠𝑡𝑎𝑟𝑡 𝑠𝐽 𝑋𝐽,𝑠𝑡𝑎𝑟𝑡
𝑇𝑖𝑛 𝑋𝐽,𝑖𝑛

෡ 𝑹,𝑱 𝑵𝑱,𝟎 ∆𝑿𝑱

∆𝑯 ෡ 𝑹,𝑱 𝑭𝑱,𝟎 ∆𝑿𝑱
∆𝑯 ෡ 𝑹,𝑱 𝑭𝑱,𝟎 ∆𝑿𝑱
∆𝑯
𝑻𝒆𝒏𝒅 = 𝑻𝒔𝒕𝒂𝒓𝒕 + 𝑻𝒐𝒖𝒕 = 𝑻𝒊𝒏 + 𝑻𝒐𝒖𝒕 = 𝑻𝒊𝒏 +
𝒎ො𝒄𝑷,𝒂𝒗 𝒔𝑱 𝒎ሶ 𝟎 𝒄ො 𝑷,𝒂𝒗 𝒔𝑱 𝒎ሶ 𝟎 𝒄ො 𝑷,𝒂𝒗 𝒔𝑱
 SPECIFIC PERFORMANCE EQUATIONS AND OTHER EQUATIONS
PROVIDED IN THE EXAM (CHAPTER 2 Part II and 3)
MOLAR BALANCE: NOMENCLATURE:
𝑑𝑁𝐽 𝐶𝐽,0 Concentration of J in the reference point (where XJ is considered nil).
ሶ
𝐹𝐽,𝑖𝑛 − 𝐹𝐽,𝑜𝑢𝑡 + 𝑅𝐽 = 𝐶𝐽 Concentration of J.
𝑑𝑡
𝑐𝑃,𝑎𝑣
Ƹ Specific heat capacity.
∆𝑁𝐴 = −𝑁𝐴,0 ∆𝑋𝐴 𝑑𝑁𝐴 = −𝑁𝐴,0 𝑑𝑋𝐴 𝜀𝐴 Compressibility factor
𝐹𝐽,0 Molar flow J at the reference point (where XJ is considered nil).
∆𝐹𝐴 = −𝐹𝐴,0 ∆𝑋𝐴 𝑑𝐹𝐴 = −𝐹𝐴,0 𝑑𝑋𝐴 ෡𝑅,𝐽
∆𝐻 Enthalpy of reaction.
𝑘2 Rate constant for the Michaelis-Menten enzymatic kinetic
𝑅ሶ 𝐴 = 𝑟𝐴 𝑉 𝑘𝐴 Rate constant
ENERGY BALANCE: Constant pressure, one inlet, one outlet, 𝐾 Equilibrium constant
𝐾𝑀 Michaelis constant
constant specific heat capacity, one reaction. 𝑚 Mass of reaction.
𝑚ሶ 𝑖𝑛 Mass flow inlet.
෡𝑅,𝐽 𝑅ሶ 𝐽
∆𝐻 𝑑𝑇
𝑚ሶ 𝑖𝑛 𝑐𝑃,𝑎𝑣
Ƹ (𝑇𝑖𝑛 − 𝑇∗) − 𝑚ሶ 𝑜𝑢𝑡 𝑐𝑃,𝑎𝑣
Ƹ (𝑇𝑜𝑢𝑡 − 𝑇 ∗) − + 𝑄ሶ = 𝑚𝑐𝑃Ƹ 𝑚ሶ 𝑜𝑢𝑡 Mass flow outlet.
𝑠𝐽 𝑑𝑡 𝑁𝐽,0 Moles of J in the reference point (where XJ is considered nil).
𝑁𝐽 Moles of J.
𝑄ሶ Heat flow..
𝑞0 Volumetric flow at the reference point (where XJ is considered nil).
𝑞𝑋=0 Volumetric flow at conversion fed in the reactor.
𝑞𝑋=1 Volumetric flow at total conversion.
𝑟𝐽 Reaction rate of J.
𝑅ሶ 𝐽 Generation of J.
S Ratio of concentrations CJ,0/CA,0
𝑡𝐵𝑃𝑀𝑅 Time of reaction for a batch perfectly mixed reactor.
𝜏𝐶𝑃𝑀𝑅 Space time of a continuous perfectly mixed reactor
𝜏𝑃F𝑅 Space time of a plug flow reactor
𝑇∗ Temperature of in a reference state
𝑇𝑖𝑛 Temperature at the inlet or initial temperature
𝑇𝑜𝑢𝑡 Temperature at the outlet or final temperature
𝑠𝐽 Stoichiometric factor of j (negative if it is a reactant, positive if it is product).
V Volume of reaction.
V0 Volume of reference (where XJ is considered nil).
𝑉𝑋=1 Volume at total conversion.
𝑉𝑋=0 Volume at conversion zero.
𝑋𝐽,𝑒 Conversion of J at in equilibrium conditions.
𝑋𝐽,𝑒𝑛𝑑 Conversion of J at the end of a reaction performed in batch mode.
𝑋𝐽,𝑖𝑛 Conversion of J at the inlet stream of a continuous mode reactor.
𝑋𝐽,𝑜𝑢𝑡 Conversion of J at the outlet of a continuous mode reactor.
𝑋𝐽,𝑠𝑡𝑎𝑟𝑡 Conversion of J at the start of a reaction performed in batch mode.

𝑉𝑋=1 − 𝑉𝑋=0 𝑞𝑋=1 − 𝑞𝑋=0 σ 𝑠𝐽 𝑁𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡,0 σ 𝑠𝐽 𝐹𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡,0

𝜀𝐴 = 𝜀𝐴 = 𝜀𝐴 = 𝜀𝐴 =
𝑉𝑋=0 𝑞𝑋=0 −s𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑁𝑡𝑜𝑡𝑎𝑙,0 −s𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝐹𝑡𝑜𝑡𝑎𝑙,0

SPECIFIC PERFORMANCE EQUATIONS FOR ISOTHERM CONDITIONS OR CONSTANT VALUE OF kA

BATCH STIRRED TANK REACTOR CONTINUOUS STIRRED TANK TUBULAR REACTOR
(time for BPMR in batch) REACTOR (space time for CPMR) (space time for PFR)
KINETIC

0th 𝐶𝐴.0 ∆𝑋𝐴 𝐶𝐴.0 ∆𝑋𝐴 𝐶𝐴.0 ∆𝑋𝐴

𝑡𝐵𝑃𝑀𝑅 = 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 =
𝑟𝐴 = −𝑘𝐴 𝑘𝐴 𝑘𝐴 𝑘𝐴

1st 1 1 − 𝑋𝐴,𝑒𝑛𝑑 ∆𝑋𝐴 1 1 − 𝑋𝐴,𝑜𝑢𝑡

𝑡𝐵𝑃𝑀𝑅 = − × 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 = − × 𝑙𝑛
𝑟𝐴 = −𝑘𝐴 𝐶𝐴 𝑘𝐴 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑘𝐴 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 1 − 𝑋𝐴,𝑖𝑛

2nd (1 reactant) 1 ∆𝑋𝐴 ∆𝑋𝐴 1 ∆𝑋𝐴

𝑡𝐵𝑃𝑀𝑅 = 𝜏𝐶𝑃𝑀𝑅 = 2 𝜏𝑃𝐹𝑅 =
𝑟𝐴 = −𝑘𝐴 𝐶𝐴2 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑒𝑛𝑑 )(1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 ) 𝑘𝐴 𝐶𝐴,0 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑜𝑢𝑡 )(1 − 𝑋𝐴,𝑖𝑛 )
𝑠𝐵 𝑠𝐵 𝑠𝐵
If S value is different to the value of : If S value is different to the value of : If S value is different to the value of :
𝑠𝐴 𝑠𝐴 𝑠𝐴
)

𝑠 ∆𝑋𝐴 𝑠𝐵
1 𝑆 − 𝑠𝐵 𝑋𝐴,𝑒𝑛𝑑 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝜏𝐶𝑃𝑀𝑅 = 𝑆− 𝑋 1 − 𝑋𝐴,𝑖𝑛
𝐴 𝑠 1 𝑠𝐴 𝐴,𝑜𝑢𝑡
𝑡𝐵𝑃𝑀𝑅 =
𝑠𝐵
× 𝑙𝑛
𝑠𝐵 𝑘𝐴 𝐶𝐴,0 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑆 − 𝑠𝐵 𝑋𝐴,𝑜𝑢𝑡 𝜏𝑃𝐹𝑅 = × 𝑙𝑛
2nd (2 reactants) 𝐴 𝑠 𝑠
CONSTANT DENSITY OR CONSTANT VOLUME (

𝑘𝐴 𝐶𝐴,0 𝑆 − 𝑆− 𝑋 1 − 𝑋𝐴,𝑒𝑛𝑑 𝑘𝐴 𝐶𝐴,0 𝑆− 𝐵 𝑆 − 𝐵 𝑋𝐴,𝑖𝑛 1 − 𝑋𝐴,𝑜𝑢𝑡

𝑠𝐴 𝑠𝐴 𝐴,𝑠𝑡𝑎𝑟𝑡 𝑠𝐴 𝑠𝐴
𝑟𝐴 = −𝑘𝐴 𝐶𝐴 𝐶𝐵
𝑠𝐵
𝑆 = 𝐶𝐵,0 /𝐶𝐴,0 𝑠𝐵
If S value equals the value of :
𝑠𝐴 𝑠𝐵
If S value equals the value of : If S value equals the value of :
𝑠𝐴 𝑠𝐴
∆𝑋𝐴
1 ∆𝑋𝐴 𝜏𝐶𝑃𝑀𝑅 = 2
𝑡𝐵𝑃𝑀𝑅 = 𝑆 𝑘𝐴 𝐶𝐴,0 1 − 𝑋𝐴,𝑜𝑢𝑡 1 ∆𝑋𝐴
𝑆 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑒𝑛𝑑 )(1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 ) 𝜏𝑃𝐹𝑅 =
𝑆 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑜𝑢𝑡 )(1 − 𝑋𝐴,𝑖𝑛 )
Pseudo-1st 1 1 − 𝑋𝐴,𝑒𝑛𝑑 ∆𝑋𝐴 1 1 − 𝑋𝐴,𝑜𝑢𝑡
𝑡𝐵𝑃𝑀𝑅 = − × 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 = − × 𝑙𝑛
𝑟𝐴 = −𝑘𝐴 𝐶𝐵,0 𝐶𝐴 𝑘𝐴 𝐶𝐵,𝑂 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑘𝐴 𝐶𝐵,𝑂 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 𝐶𝐵,𝑂 1 − 𝑋𝐴,𝑖𝑛

Reversible 1st
𝑟𝐴 = −𝑘𝐴 𝐶𝐴 + 𝑘𝑃 𝐶𝑃 𝑠𝑃 𝑠𝑃 𝑠𝑃
𝑆− 𝑋 𝑋𝐴,e − 𝑋𝐴,𝑒𝑛𝑑 𝑋 − 𝑆 ∆𝑋𝐴 𝑆− 𝑋 𝑋𝐴,e − 𝑋𝐴,𝑜𝑢𝑡
𝑠𝐴 𝐴,e 𝑠𝐴 𝐴,e 𝑠𝐴 𝐴,e
𝑠 𝑡𝐵𝑃𝑀𝑅 = × 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 = × 𝑙𝑛
(𝑆 − 𝑃 𝑋𝐴,𝑒 ) 𝑠𝑃 𝑋𝐴,e − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑠𝑃 𝑠𝑃 𝑋𝐴,e − 𝑋𝐴,in
𝑠𝐴 𝑘𝐴 −𝑆 𝑘𝐴 −𝑆 𝑋𝐴,e − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 −𝑆
𝑠𝐴 𝑠𝐴 𝑠𝐴
𝐾𝐶 =
1 − 𝑋𝐴,𝑒
Autocatalytic 𝑠𝑃 𝑠𝑃
1 𝑆− 𝑋 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 ∆𝑋𝐴 1 𝑆− 𝑋 1 − 𝑋𝐴,𝑖𝑛
𝑟𝐴 = −𝑘𝐴 𝐶𝐴 𝐶𝑃 𝑠𝐴 𝐴,𝑒𝑛𝑑 𝜏𝐶𝑃𝑀𝑅 = 𝑠𝐴 𝐴,𝑜𝑢𝑡
𝑡𝐵𝑃𝑀𝑅 = × 𝑙𝑛 𝑠 𝜏𝑃𝐹𝑅 = × 𝑙𝑛
𝑘𝐴 𝐶𝐴,0 𝑆 + 1 𝑠 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑜𝑢𝑡 )(𝑆 − 𝑠𝑃 𝑋𝐴,𝑜𝑢𝑡 ) 𝑘𝐴 𝐶𝐴,0 𝑆 + 1 𝑠
𝑆 − 𝑃 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 1 − 𝑋𝐴,𝑒𝑛𝑑 𝐴 𝑆 − 𝑃 𝑋𝐴,𝑖𝑛 1 − 𝑋𝐴,𝑜𝑢𝑡
𝑆 = 𝐶𝑃,0 /𝐶𝐴,0 𝑠𝐴 𝑠𝐴

1 1 − 𝑋𝑆,𝑠𝑡𝑎𝑟𝑡 ∆𝑋𝑆 𝐾𝑀 1 1 − 𝑋𝑆,𝑖𝑛

Michaelis – Menten 𝑡𝐵𝑃𝑀𝑅 = 𝐾𝑀 × ln + 𝐶S,0 ∆𝑋𝑆 𝜏𝐶𝑃𝑀𝑅 = + 𝐶S,0 𝜏𝑃𝐹𝑅 = 𝐾𝑀 × ln + 𝐶S,0 ∆𝑋𝑆
𝑘2 𝐶E,0 1 − 𝑋𝑆,𝑒𝑛𝑑 𝑘2 𝐶E,0 1 − 𝑋𝑆,𝑜𝑢𝑡 𝑘2 𝐶E,0 1 − 𝑋𝑆,𝑜𝑢𝑡

0th 𝐶𝐴,0 1 + 𝜀𝐴 𝑋𝐴,𝑒𝑛𝑑 𝐶𝐴.0 ∆𝑋𝐴 𝐶𝐴.0 ∆𝑋𝐴

𝑡𝐵𝑃𝑀𝑅 = × 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 =
)

𝑟𝐴 = −𝑘𝐴 𝑘𝐴 𝜀𝐴 1 + 𝜀𝐴 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑘𝐴 𝑘𝐴
VARIABLE DENSITY (

1st 1 1 − 𝑋𝐴,𝑒𝑛𝑑 ∆𝑋𝐴 1 + 𝜀𝐴 𝑋𝐴,𝑜𝑢𝑡 1 1 − 𝑋𝐴,𝑜𝑢𝑡

𝑡𝐵𝑃𝑀𝑅 = − × 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 𝜏𝑃𝐹𝑅 = − 𝜀𝐴 ∆𝑋𝐴 + 1 + 𝜀𝐴 𝑙𝑛
𝑟𝐴 = −𝑘𝐴 𝐶𝐴 𝑘𝐴 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑘𝐴 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 1 − 𝑋𝐴,𝑖𝑛

2nd (1 reactant) 1 (1 + 𝜀𝐴 )∆𝑋𝐴 1 − 𝑋𝐴,𝑒𝑛𝑑 ∆𝑋𝐴 1 + 𝜀𝐴 𝑋𝐴,𝑜𝑢𝑡

2
1 1 + 𝜀𝐴 2 ∆𝑋𝐴 1 − 𝑋𝐴,𝑜𝑢𝑡
𝑡𝐵𝑃𝑀𝑅 = + 𝜀𝐴 𝑙𝑛 𝜏𝐶𝑃𝑀𝑅 = 2
𝜏𝑃𝐹𝑅 = + 𝜀𝐴2 ∆𝑋𝐴 + 2𝜀𝐴 1 + 𝜀𝐴 𝑙𝑛
𝑟𝐴 = −𝑘𝐴 𝐶𝐴2 𝑘𝐴 𝐶𝐴,0 (1 − 𝑋𝐴,𝑒𝑛𝑑 )(1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 ) 1 − 𝑋𝐴,𝑠𝑡𝑎𝑟𝑡 𝑘𝐴 𝐶𝐴,0 1 − 𝑋𝐴,𝑜𝑢𝑡 𝑘𝐴 𝐶𝐴,0 1 − 𝑋𝐴,𝑜𝑢𝑡 1 − 𝑋𝐴,𝑖𝑛 1 − 𝑋𝐴,𝑖𝑛
 KEY INFORMATION TO REMEMBER OR
PROVIDED IN THE EXAM FOR CHAPTER 4
EQUATIONS PROVIDED
Selectivity towards a reaction, SN/i (where N is the reaction 1, 2, … and I is the reactant A,
B,…) 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑁 𝑅𝑖,𝑁 𝑅ሶ 𝑖,𝑁
𝑆𝑁/𝑖 = × 100 = × 100 = × 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑖 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑅𝑖 𝑅ሶ 𝑖
Selectivity towards a product, SJ (where J is the product P, Q,…)
𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐽 𝑅𝐽 𝑅ሶ 𝐽
𝑆𝐽 = × 100 = × 100 = × 100
𝑚𝑜𝑙𝑎𝑟 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖 −𝑅𝑖 −𝑅𝑖 ሶ
Selectivity as a distribution of products, SJ (where J is the product P, Q,…)
𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐽 𝑅𝐽 𝑅ሶ 𝐽
𝑆𝐽% = × 100 = × 100 = × 100
𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑎𝑙𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝐽 σ 𝑅𝐽 σ 𝑅ሶ 𝐽
Selectivity ratio of product, SJ/K (J is the desired product, and K is the unwanted
product/s) 𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐽 𝑅𝐽 𝑅ሶ𝐽
𝑆𝐽/𝐾 = = =
𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑢𝑛𝑤𝑎𝑛𝑡𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝐾 𝑅𝐾 𝑅ሶ 𝐾
Yield of reaction, YN/i (where J is the desired product P, Q,…)
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑁 𝑅𝑖,𝑁 𝑅ሶ 𝑖,𝑁
𝑌𝑁/𝑖 = × 100 = × 100 = × 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖 𝑓𝑒𝑑 −𝑁𝑖,0 −𝐹𝑖,0
Yield of product, YJ (where J is the desired product P, Q,…and i is the limiting reactant)
𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐽 𝑅𝐽 𝑅ሶ 𝐽
𝑌𝐽 = × 100 = × 100 = × 100
𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖 𝑓𝑒𝑑 𝑁𝑖,0 𝐹𝑖,0
Yield of desired product over the ideal, YJ% (where J is the desired product P, Q,: I is
the limiting reactant, and N is the reaction in which the desired product if formed such
as 1, 2,…) 𝑛𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝐽
𝑌𝐽% = × 100
𝑚𝑜𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐽 𝑖𝑓 𝑛𝑜 𝑠𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 𝑜𝑐𝑐𝑢𝑟𝑟𝑒𝑑 𝑎𝑛𝑑
ሶ 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑤𝑎𝑠 100%
𝑅𝐽 𝑅𝐽
𝑌𝐽% = 𝑠𝐽,𝑁 × 100 = 𝑠 × 100
𝐽
− × 𝑁𝑖,0 − × 𝐹𝑖,0
𝑠𝑖,𝑁 𝑠𝑖

WHAT DO YOU NEED TO KNOW?

➢ HOW TO APPLY THE RULES AND SELECT THE BEST REACTOR
Rule 1. RULE OF THE TEMPERATURE
The increase of temperature favours the reaction rate with higher activation
energy.

Rule 2. RULE OF THE CONCENTRATION

High concentrations of a specie j promotes the reaction rate with higher kinetic
order with respect this specie j.

Rule 3. RULE OF MIXING

To favour intermediates of reaction, we need to avoid mixing
streams with different fluids at different concentrations.

Rule 4. RULE OF SERIES-PARALLEL

Analyse the reactants separately and apply rules 3 for the
appropriate reactant.

➢ WHEN TO APPLY THE RULES

RULE 1
RULE 2 PARALLEL
SERIES
RULE 3 SERIES-PARALLEL
RULE 4
➢ RELATIONS BETWEEN SELECTIVITIES AND YIELDS
Which selectivities add to 100% and which not.
What is the meaning of the values obtained
If there is any relation between some selectivities and yields