Biochemical Reaction

• Biochemical reactions are characterized by the use of enzymes or

whole cells (micro-organisms) to carry out specific conversions
• Example:
• Fermentation of fruit juices to make alcohol
• Subsequent oxidation to vinegar

• Living organisms are capable of carrying out a wide range of

transformations which can often be manipulated by controlling their
environment or by changing genetic constitution. The primary interest
of organism is to replicate themselves
Application
 Applications of biological processes will considering systematics,
genetics, biochemistry and physiology.
 Outline of a biological process:
Biochemical Reaction
• Important aspects to reactors:
• Nature and processing of raw materials
• Choice and manipulation of the catalysts
• Control of reaction process from which the product must be
recovered.

• Bioprocesses are autocatalytic reactions. Cells is a group of proteins

that have catalytic properties (Enzymes).

• Enzymes, similar to inorganic catalyst in some ways and very powerful

catalysts that capable to enhance the overall rate of reactions.
Biochemical Reaction
 Enzymes are water-soluble but are frequently bound to membranes
within the cells or retained in the microbe by the cell walls.

 Enzymes usually retain their catalytic activity when isolated from the
cell.

 Bioreactors as an alternatives to conventional chemical reactors, e.g in

pharmaceutical industry, micro-organism & enzymes can be used to
produce specific streo-isomers selectivity.
 Rates & Kinetics of Biological
Processes
 Kinetics of reproduction
 Bio-Reactors & mass balance
 Mass transfer in biological system
 Enzyme kinetics
Rates & Kinetics of Biological
Processes
A  nS S  n A A  n p P
 A = biological species (organism, cells)
 S = substrate (nutrient conc – cell or organism
metabolizes to reproduce)
 P = metabolic product
Rates & Kinetics of Biological
Processes
 Kinetics of Reproduction
 In ideal environment, cells begin to reproduce with the existence of
nutrients in the mode of exponential growth.
 In biological systems, food supply is consumes while organism
grows (reproduces).
A  S  2A  P, r  kCACS (metabolic products ignored)

dC A
 In excess nutrients, Cs = Cs0,  kCS 0C A , C A  C A0 exp(kCS 0 t ) (batch
dt reactor)

 Exponential growth is “natural” tendency of any living system

because it wants to reproduce itself. It is inherently unstable growth
mode because the system will inevitably increase until food supply
exceeded.
Rates & Kinetics of Biological
Processes
 Kinetics of Reproduction
 Suffer death model:
dC A
 r b  rd  k bC A  k d C A2 kb = kCS0
dt

 Reverse reaction represent death as 2nd order kinetics

kb
 At steady state, C As 
kd
 CA increase with time if CA0<CS
 CA decrease with time if CA0>CAS
Rates & Kinetics of Biological
Processes
 Metabolism
 If organism A is not reproducing,

A  S  A  P, r  kCACS

 If CA is constant at CA0, mass balance of nutrient S in a batch

reactor is:
dCS
 kCA0CS , CS  CS 0 exp(kCA0t )
dt

CP  CS 0  CS
Rates & Kinetics of Biological
Processes
 Biological reactor
 Modeled as batch or flow – similar with nonbiological reactors, but
more complicated.
 Most of the reactor is semibatch – nutrients are fed continuously.
 Batch system:-
 Small amounts of material
 Time variant reaction conditions (Slow reaction, longer residence time.)
 Discontinuous production – high cost of product.
 Easy to analyze.
 Downtime for cleaning and filling
Bioreactors
 Advantages
 high selectivity
 Feasible for multistage separation in purification
 Reduced potential pollution
 Increased energy recovery and reduced greenhouse
emissions
 Lower long-term maintenance cost

 Disadvantages
 Product may formed in dilute aqueous solution
 Low rates
 Rheological properties that difficult to handle
 Low interfacial tensions – difficulties in physical
separation of product
Biological Reactor
 The operating characteristic of various reactor modes

Mode of Advantages Disadvantages

operation
Batch Simple. Suitable for small Downtime for loading and
production cleaning. Reaction conditions
change with time.
Continuous High production. Better product Requires flow control. Culture
quality due to constant maybe unstable over long
conditions. Good for kinetic periods.
studies.
Fed Batch Control environment conditions Requires feeding strategy to
e.g. substrate concentration obtain desired concentration.
Biological Reactor
 Kinetic considerations for reactor choice

Reaction kinetics Batch Continuous Fed Batch

Tank
Zero order OK OK Low conversion
First order Best Low conversion OK
only
Substrate Low initial Best Best
inhibition concentration
Product inhibition Best Low conversion Low conversion
only only
Production OK for Not suitable Best for
triggered by shift in temperature shift concentration
environment shift
Rates & Kinetics of Biological
Processes
 Material balance
 CSTR
C A  C A0
 r  kCACS

 If Cs = Cs0,
C A0
CA 
1  kCS 0

Plot of concentration CA versus time

in growth of A+S  2A+P for different
values of nutrient concentration CS0
Rates & Kinetics of Biological
Processes
 Material balance
 PFR
dC A
 kCACS
d

 If Cs = Cs0,

C A  C A0 expkCS 0 

Plot of concentration CA versus time

in growth of A+S  2A+P for different
values of nutrient concentration CS0
Rates & Kinetics of Biological
Processes
 What is the rate reaction with mass transfer of
organism A with nutrient S?

 Answer: Read chapter 1 - Topic mass transfer

Rates & Kinetics of Biological
Processes
 Material balance
 CSTR gives a higher conversion than a PFTR in autocatalytic
reaction such as growth of living systems.
 Production of organism A is higher in the CSTR than in PFTR.
 CA increase exponentially in PFTR, BUT it does not increase as fast
as in CSTR.
Enzymatic Reactions
 Enzymes
 Proteins that act as biological catalyst.
 Provide a pathway for the substrate to proceed at a faster rate.

 Characters similar with catalyst

 Present in small quantity
 Not consumed during the course of reaction
 Do not effect the chemical reaction equilibrium

 A given enzyme can only catalyze one type of reaction – therefore

unwanted products are easily controlled in enzyme catalyzed
reactions.
Pseudo-Steady-State Hypothesis (PSSH)
 Theory of active intermediates - decomposition of intermediate does
not occur instantaneously after internal activation of the molecule;
rather there is time lag, although infinitesimally small, during the
species remains activated.
 A reactive intermediate reacts virtually as fast as it is formed.
Therefore, the net rate formation of active intermediate is zero.

𝑛
 𝑟𝐴∗ = 𝑖=1 𝑟𝑖𝐴∗ =0
Enzyme Kinetics
 Kinetics is the study of the rated of chemical reactions.

 The rates of biological reactions are greatly increased by enzyme

catalysts.

 Enzyme kinetics is based upon the elementary kinetics.

 The mechanism of enzymes reactions are similar as catalytic reactions.

Substrate (S) adsorb reversibly on the Enzyme (E), and then reacts to
form product (P) and leaves a free enzyme site for further reaction.

 The rate reaction catalyzed by enzyme can usually be described by the

Michaelis-Menten kinetic equation.
Example of Enzymatic Reaction and
Derivation of Enzyme Kinetic
Enzyme Kinetics
 Mechanisms
(Net rate of disappearance
S  E  E S  rS  k1[S][E ]  k 2 [E  S] of substrate)
E S W  P  E rP  k 3 [E  S][W ]

 Mass balance of [E·S]:

rES  k1[S][E ]  k 2 [E  S]  k 3 [E  S][W ]

 Using Pseudo Steady State (PSS) Hypothesis to express [E·S], rE·S = 0,

k1 [E ][S ]
[E  S ] 
k 2  k 3 [W ]

k1k 3 [E ][S ][W ]

 Thus, rate of disappearance of substrate is  rS   
k 2  k 3 [W ]
Enzyme Kinetics
 Total enzyme concentration: [E 0 ]  [E ]  [E  S]

 Substituting for [E] and solving for [E], the rate law for disappearance of
substrate, S is:
k1k 3 [W ][S ][E 0 ]
 rS   
k1[S ]  k 2  k 3 [W ]

 Let k cat  k 3 [W ] Therefore,

k cat  k 2 k cat [E 0 ][S ] Vmax [S ] (Michaelis-Menten
KM   rS    
k1 [S ]  K M K M  [S ] equation)
Vmax  k cat [E 0 ]

rate of ES breakdow n to S or P
KM 
rate of ES formation
Enzyme Kinetics
1 K 1 1
 M 
rs Vmax [S ] Vmax

Michaelis-Menten plot – reaction rate Lineweaver-Burk plot

versus substrate concentration
References
 Schmidt, L.D. (2005). The Engineering of Chemical
Reactions, 2nd edition, New York: Oxford University Press.
 Fogler, H.S. (2006). Elements of Chemical Reaction
Engineering, 4th Edition, New Jersey: Prentice Hall.
 Levenspiel, O. (1999). Chemical Reaction Engineering, 3rd
Edition, New York: John Wiley.

CPE624 FACULTY OF CHEMICAL ENGINEERING 36