Fundamentals of chemical

reaction engineering
BT2041 Biological Rate Processes
Instructor: Vignesh Muthuvijayan

Chemical species
• Any chemical compound, element, or living
organism with a given identity
• Identity of a chemical species is determined by
kind, number, and configuration
• E.g. – Penicillin is made up of a fixed number of
specific elements in a definite configuration

Image from Wikimedia Commons

2
 Chemical species
• Isomers – Same stoichiometric formula, but different
configurations
• Have different chemical and physical properties
• Treated as different chemical species

Image from Shijie Liu, Bioprocess Engineering: Kinetics, Sustainability,

and Reactor Design, 1st Edition, 2012, Elsevier

Chemical species
• Chemical species are commonly represented by
elemental formula
• Elemental formula normalized by carbon
• E.g. – E. coli is CH1.70O0.424N0.25

4
 Chemical reaction
• A detectable number of molecules of one or more
species have lost their identity and assumed a new
form
• Change can be in kind or number of atoms and/or
change in structure or configuration of these atoms
• Total mass is neither created nor destroyed during
this process
• For individual species, generation and consumption
rates can be measured

Chemical reaction
• Decomposition

• Combination

• Isomerization

glucose (D-glucopyranose) fructose (D-fructofuranose)

6
 Classification of chemical reactions
• Based on directionality
• Irreversible: 𝐴 ⟶ 𝐵
• Reversible: 𝐴 ⇄ 𝐵
• Based on phases
• Homogeneous: Reactions happening in one phase
• Heterogeneous: Reactions that require at least two
phases

Classification of chemical reactions

Table from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

8
 Variables affecting reaction rates
• Factors for all reactions
• Temperature
• Pressure
• Composition
• More complex for heterogeneous reactions
• Rate at which material moves from one phase to
another (mass transfer)
• Rate at which heat is dissipated (heat transfer)
• Mass or heat transfer can be rate limiting if these
are much slower than the reaction rates

Stoichiometry
• Consider the following reaction
𝑁2 + 𝑂2 → 2𝑁𝑂
• This can be written as
𝐴 + 𝐵 → 2𝐶
• This reaction can be written in the following algebraic form

−𝐴 − 𝐵 + 2𝐶 = 0
• Since alphabets are limited in number, we can use subscripts, i.e., species j can
be represented as Aj
−𝐴1 − 𝐴2 + 2𝐴3 = 0
• The generalized single reaction becomes
𝑁𝑆

෍ 𝜈𝑗 𝐴𝑗 = 0
𝑗=1

10
 Stoichiometry
• Most processes involve multiple reactions
• Consider the following reaction system
𝑁2 + 𝑂2 → 2𝑁𝑂
2𝑁𝑂 + 𝑂2 → 2𝑁𝑂2
• This can be written as
−𝐴1 − 𝐴2 + 2𝐴3 = 0
−2𝐴3 − 𝐴2 + 2𝐴4 = 0
• This can be generalized as
𝑁𝑆

෍ 𝜈𝑖𝑗 𝐴𝑗 = 0, 𝑖 = 0, 1, 2, … , 𝑁𝑅
𝑗=1

11

Stoichiometric matrix

Image from Shijie Liu, Bioprocess Engineering: Kinetics, Sustainability,

and Reactor Design, 1st Edition, 2012, Elsevier

12
 Rate of reaction
• Represented as 𝑟𝑗 , which is the rate of formation of
species j
• If species j is a reactant, the numerical value of 𝑟𝑗 is
negative
• If species j is a product, the numerical value of 𝑟𝑗 is
positive
• Many meaningful and useful definitions that give
interrelated rates of reaction

13

Rate of reaction
• Rate of change in the number of moles of a species j is given as
𝑑𝑁𝑗 /𝑑𝑡
• Rate of reaction can be defined based on
1 𝑑𝑁𝑗
• unit volume of reacting fluid 𝑟𝑗 =
𝑉 𝑑𝑡
1 𝑑𝑁𝑗
• unit mass of catalyst or enzyme 𝑟𝑗′ =
𝑚 𝑑𝑡
1 𝑑𝑁𝑗
• unit mass of solid in fluid-solid systems 𝑟𝑗′′ =
𝑊 𝑑𝑡
1 𝑑𝑁𝑗
• unit interfacial surface in two-fluid or gas-solid systems 𝑟𝑗′′′ =
𝑆 𝑑𝑡
1 𝑑𝑁𝑗
• unit volume of solid in gas-solid systems 𝑟𝑗′′′′ =
𝑉𝑠 𝑑𝑡
1 𝑑𝑁𝑗
• unit volume of reactor, if different from volume of reacting fluid 𝑟𝑗′′′′′ =
𝑉𝑅 𝑑𝑡

14
 Rate of reaction
• Assume a single-phase reaction
𝑎𝐴 + 𝑏𝐵 → 𝑟𝑅 + 𝑠𝑆
• Reaction rate of reactant A is given as

• Reaction rates of all materials are related by

−𝑟𝐴 −𝑟𝐵 𝑟𝑅 𝑟𝑆
= = =
𝑎 𝑏 𝑟 𝑠
Equation from Octave Levenspiel, Chemical Reaction Engineering,
3rd Edition, 2006, Wiley

15

Rate of reaction
• Reactions occur at varied speeds

Figure from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

16
 Example #1
• A rocket engine burns a stoichiometric mixture of fuel
(liquid hydrogen) in oxidant (liquid oxygen). The combustion
chamber is cylindrical, 75 cm long and 60 cm in diameter,
and the combustion process produces 108 kg/s of exhaust
gases. If combustion is complete, find the rate of reaction of
hydrogen and oxygen.

Problem from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

17

18
19

Example #2
• A human being (75 kg) consumes about 6000 kJ of
food per day. Assume that the food is all glucose
and that the overall reaction is
C6H12O6 + 6O2 → 6CO2 + 6H2O, −Δ𝐻𝑟 = 2816 𝑘𝐽
• Find the man’s metabolic rate in terms of moles of
oxygen used per m3 of person per second.

Problem from Octave Levenspiel, Chemical Reaction Engineering,

3rd Edition, 2006, Wiley

20
21

Rate of reaction
• Mathematical definition of rate of reaction can cause
confusion
• Stems from lab-scale experiments used for collecting
reaction rate data
• Batch-type → constant volume
• Reactants are mixed at time t = 0
• Concentration of one of the reactants (𝐶𝐴 ) is measured at various
times t
• Rate of reaction is determined from the slope of a plot of 𝐶𝐴 vs t
𝑑𝐶𝐴
• Rate of reaction is reported as 𝑟𝐴 =
𝑑𝑡

22
 Rate of reaction
𝑑𝐶𝐴
𝑟𝐴 =
𝑑𝑡
• This definition is not accurate
• It is a mole balance valid only for a constant volume batch system
• Will not apply for continuous-flow reactors operated at steady state
• For continuous-flow reactors at steady state,
𝑑𝐶𝐴
• concentration doesn’t change with time → =0
𝑑𝑡
• reactants are consumed and products are generated ⇒ 𝑟𝐴 ≠ 0
𝑑𝐶𝑗
• 𝑟𝑗 = is not the definition of rate of reaction
𝑑𝑡
• 𝑟𝑗 is the rate of formation of species j per unit volume

23