Chemical Kinetics
Chemical kinetics, also called reaction kinetics, helps us understand the rates of reactions and how
it is influenced by certain conditions.
The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as
proportional to the increase in the concentration of a product per unit time and to the decrease in the
concentration of a reactant per unit time.
Rate of Formations and Disappearances
In any chemical reaction, as the reaction proceeds, the amount of reactants decreases, whereas the
amount of products increases. One has to understand that the rate of the overall reaction depends on
the rate at which reactants are consumed or the rate at which the products are formed.
If a graph is plotted between the concentration of reactants and products and time, the rate of
formation of products and the rate of disappearance of reactants can be easily calculated from the
slope of curves for products and reactants. The overall rate of the reaction may or may not be equal
to the rate of formations and disappearances. Rate of Formations and Disappearances:
(a) Product concentration is zero at time t = 0
(b) at time t = 0, reactants are present.
From the graph, it is noted that the slope of the reactants curve is negative and that for product
curve is positive, indicating the concentration of reactants and products decreases and increases,
respectively.
Zeroth-Order Reactions
A zeroth-order reaction is one whose rate is independent of concentration; its differential rate law is
rate=k.
We refer to these reactions as zeroth order because we could also write their rate in a form such that
the exponent of the reactant in the rate law is 0:
Because rate is independent of reactant concentration, a graph of the concentration of any reactant
as a function of time is a straight line with a slope of −k . The value of k is negative because the
concentration of the reactant decreases with time. Conversely, a graph of the concentration of any
product as a function of time is a straight line with a slope of k , a positive value.
Figure : The graph of a zeroth-order reaction.
The change in concentration of reactant and product with time produces a straight line.
Graph of concentration against time. The reactant is in purple and has a slope of minus k. The
product is in green and has a slope of positive k.
The integrated rate law for a zeroth-order reaction also produces a straight line and has the general
form.
[A]=[A]0−kt
where [A]0 is the initial concentration of reactant A . Equation has the form of the algebraic
equation for a straight line,
y=mx+b,
with y=[A] , mx=−kt , and b=[A]0
Units: In a zeroth-order reaction, the rate constant must have the same units as the reaction rate,
typically moles per liter per second.
First-Order Reactions
In a first-order reaction, the reaction rate is directly proportional to the concentration of one of the
reactants. First-order reactions often have the general form A → products. The differential rate for a
first-order reaction is as follows:
If the concentration of A is doubled, the reaction rate doubles; if the concentration of A is increased
by a factor of 10, the reaction rate increases by a factor of 10, and so forth. Because the units of the
reaction rate are always moles per liter per second, the units of a first-order rate constant are
reciprocal seconds (s−1).
The integrated rate law for a first-order reaction can be written in two different ways: one using
exponents and one using logarithms. The exponential form is as follows:
[A]=[A]0e−kt
where [A]0 is the initial concentration of reactant A at t=0 ; k is the rate constant; and e is the
base of the natural logarithms, which has the value 2.718 to three decimal places. Recall that an
integrated rate law gives the relationship between reactant concentration and time. Equation
predicts that the concentration of A will decrease in a smooth exponential curve over time.
Figure: Graphs of a first-order reaction. The expected shapes of the curves for plots of reactant
concentration versus time (top) and the natural logarithm of reactant concentration versus time
(bottom) for a first-order reaction.
Second-Order Reactions
The simplest kind of second-order reaction is one whose rate is proportional to the square of the
concentration of one reactant. These generally have the form
2A→products
A second kind of second-order reaction has a reaction rate that is proportional to the product of the
concentrations of two reactants. Such reactions generally have the form A + B → products. An
example of the former is a dimerization reaction, in which two smaller molecules, each called a
monomer, combine to form a larger molecule (a dimer).
The differential rate law for the simplest second-order reaction in which 2A → products is as
follows:
Consequently, doubling the concentration of A quadruples the reaction rate. For the units of the
reaction rate to be moles per liter per second (M/s), the units of a second-order rate constant must be
the inverse (M−1·s−1). Because the units of molarity are expressed as mol/L, the unit of the rate
constant can also be written as L(mol·s).
For the reaction 2A → products, the following integrated rate law describes the concentration of the
reactant at a given time:
Because Equation has the form of an algebraic equation for a straight line, y = mx + b, with y = 1/
[A] and b = 1/[A]0, a plot of 1/[A] versus t for a simple second-order reaction is a straight line with
a slope of k and an intercept of 1/[A]0.
FACTORS AFFECTING RATE KINETICS
The rate of a reaction can be altered if any of the following parameters are changed. This include:
CONCENTRATION OF REACTANTS
Rate of a reaction is directly proportional to the concentration of reactants.
i.e. rate (r) ∝ cn
r = kcn
where :
c = concentration
n = order of the reaction
k = specific rate
The number of collisions and hence the activated collisions between the reactant molecules increase
with increase in concentration. Therefore, according to the collision theory, the rate of a reaction
should increase with increase in the concentration since the rate is directly proportional to the
collision frequency.
i.e., rate of reaction ∝ collision frequency (Z)
TEMPERATURE
The average kinetic energy increases with increase in absolute temperature. Hence the number of
molecules with energy greater than the threshold energy also increases (see the Maxwell
distribution curves shown below). As a result, the number of effective collisions between reactant
molecules also increases. Therefore, usually it is observed that the rate of reaction increases with
increase in temperature.
Maxwell distribution curves of kinetic energy
However note that increase in temperature also increases the number of collisions and hence the
number of effective collisions are also expected to increase.
Justification: It is known that the collision frequency, Z is proportional to the square root of absolute
temperature, √T of the gas.
Temperature Coefficient: The ratio of rate constants of a reaction at two different temperatures
which differ by 10oC is called temperature coefficient.
temperature coefficient of reaction - ratio of rate constants at different temperatures
NATURE OF REACTANTS
Rate of a reaction depends on the nature of bonding in the reactants. Usually the ionic compounds
react faster than covalent compounds.
The reactions between ionic compounds in water occur very fast as they involve only exchange of
ions, which were already separated in aqueous solutions during their dissolution.
INTENSITY OF LIGHT
The rate of some photochemical reactions, which occur in presence of light, increases with increase
in the intensity of suitable light used. With increase in the intensity, the number of photons in light
also increases. Hence more number of reactant molecules get energy by absorbing more number of
photons and undergo chemical change.
E.g. The rate of photosynthesis is more on brighter days.
However, some photochemical reactions involving the free radicals, generated in a chain process,
are not greatly affected by the intensity of the light. Just one photon is sufficient to trigger the
formation a free radical. This in turn initiate a chain process in which more free radicals are formed
repeatedly in each cycle without the need of extra photons.
CATALYST
Catalyst is a substance which alters the rate of a reaction without being consumed or without
undergoing any chemical change during the reaction.
A catalyst increases the rate of reaction by providing a new path with lower activation energy (Ea’)
for the reaction.
Graph: Effect of catalyst on rate of reaction
In case of reversible reactions, the catalyst lowers the activation energies of both forward and
backward reactions to the same extent and helps in attaining the equilibrium quickly. Note that, as it
is evident from the above diagram, when a catalyst increases the rate of forward reaction, it also
increases the rate of backward reaction.
Some substances may decrease the rate of a reaction. These are generally referred to as negative
catalysts or inhibitors. They interfere with the reaction by forming relatively stable complexes,
which require more energy to breakup. Thus the speed of the reaction is reduced.
Elementary Reaction:
An elementary reaction is a chemical reaction that includes a single sub-step. In these reactions, one
chemical species undergoes a direct change to give the final product in one step. Here, a single
transition state is observed. Experimentally, if we cannot detect any intermediate products during a
chemical reaction, we can categorize that reaction as an elementary reaction.
There are several types of elementary reactions. They are as follows:
Unimolecular Reactions
In this, a single reactant undergoes a reaction such as a decomposition to give the final product(s).
Examples of unimolecular reactions include cis-trans isomerization, ring-opening, racemization,
radioactive decay, etc.
Bimolecular Reactions
Meanwhile, in bimolecular reaction, two particles undergo collision to give the product(s). These
are second-order reactions because the rate of the reaction depends on both reactants. Examples
include nucleophilic substitution reactions.
Trimolecular Reactions
Similarly, in the trimolecular reaction, three particles undergo collision at the same time to give the
product(s). However, this type is rare because it is difficult for three reactants to collide at the same
time.
Non Elementary Reaction
A non-elementary reaction is a chemical reaction that includes multiple sub-steps. That means;
these reactions have a series of steps and different transition states with different intermediates as
well. Therefore, these reactions are very complex in nature.
Difference Between Elementary and Non Elementary Reaction:
The difference between elementary and non elementary reactions depends on the number of sub-
steps of the chemical reaction. Hence, the key difference between elementary and non elementary
reaction is that elementary reactions have a single step while non-elementary reactions have
multiple steps. Therefore, in elementary reactions, there is a single transition state, and there are no
detectable intermediates produced during the reaction. However, in non-elementary reactions, there
is a series of transition states with multiple intermediates we can detect easily.
Collision Theory
The collision theory states that a chemical reaction can only occur between particles when they
collide (hit each other). The collision between reactant particles is necessary but not sufficient for a
reaction to take place. The collisions also have to be effective. It is important to understand the
exact nature of an effective collision since this determines whether particles react with each other
and form new products.
Molecular Collisions
• The more molecules are present, the more collisions will happen.
• Molecules must collide before they can react.
• To effectively initiate a reaction, collisions must be sufficiently energetic (kinetic energy) to bring
about this bond disruption.
• As the temperature rises, molecules move faster and collide more vigorously, greatly increasing
the likelihood of bond cleavages and rearrangements.
• Most reactions involving neutral molecules cannot take place at all until they have acquired the
activation energy needed to stretch, bend, or otherwise distort one or more bonds.
Dependent Variable
A dependent variable is the one which we can test in a scientific experiment, in order to get its
values. The dependent variable is obviously ‘dependent’ on the independent variable.
Controlled variable
Control variables are also called constant or controlled variables.
A controlled variable in an experiment is the one that the researcher holds constant or controls.
Control variables are the variables or elements that researchers strive to keep constant throughout
their research so that they would not influence the outcomes.
Example Temperature, pressure, volume, concentration
Transition state theory (TST)
transition state theory (TST) explains the reaction rates of elementary chemical reactions. The
theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and
activated transition state complexes.
TST is used primarily to understand qualitatively how chemical reactions take place.
The basic ideas behind transition state theory are as follows:
• Rates of reaction can be studied by examining activated complexes near the potential energy
surface. The details of how these complexes are formed are not important. The complex point
itself is called the transition state.
• The activated complexes are in a special equilibrium (quasi-equilibrium) with the reactant
molecules.
• The activated complexes can convert into products, and kinetic theory can be used to calculate the
rate of this conversion.
Transition and intermediates
Intermediate: In a chemical reaction or mechanism, any reacting species which is no longer
starting material or reactant, and has not yet become product, and which is not a transition state. An
intermediate differs from a transition state in that the intermediate has a discrete lifetime (be it a few
nanoseconds or many days), whereas a transition state lasts for just one bond vibration cycle. An
intermediate may be an unstable molecule (a reactive intermediate) or a highly stable molecule.
Exothermic and Endothermic CR
An exothermic process releases heat, causing the temperature of the immediate surroundings to rise.
An endothermic process absorbs heat and cools the surroundings.”
Endothermic reactions: Heat is absorbed.
1) Photosynthesis: Plants absorb heat energy from sunlight to convert carbon dioxide and water into
glucose and oxygen.
6CO2 + 6 H2O + heat ---> C6H12O6 + 6O2
Exothermic reactions: Heat is released.
1) Combustion: The burning of carbon-containing compounds uses oxygen, from air, and produces
carbon dioxide, water, and lots of heat. For example, combustion of methane CH4 + 2(O2) --->
CO2 + 2H2O + heat
2) Rain: Condensation of water vapor into rain releasing energy in the form of heat is an example of
an exothermic process.
Enthalpy of a reaction is defined as the heat energy change (ΔH) that takes place when reactants go
to products. If heat is absorbed during the reaction, ΔH is positive; if heat is released, then ΔH is
negative.
Advancements in Industrial fermenters
The technology of industrial fermentation has been evolving over the years, leading to significant
advancements that have improved the efficiency, sustainability, and versatility of the process.
Continuous fermentation –
One of the primary benefits of continuous fermentation is the ability to better control the
fermentation process and optimize conditions for product production. Through cell recycling and
immobilization, this process reduces capital costs, increases productivity, and yield. Continuous
cultures of bacteria have a higher productivity than batch cultures.
Biosensors –
Furthermore, new techniques for controlling microbial growth are being developed. The creation of
genetic biosensors and other assays can help to speed up the process of optimizing microbial cell
factories.
Downstream processing –
Finally, advances in downstream processing (DSP) are contributing significantly to the
advancement of industrial fermentation. DSP, as an integral part of the entire manufacturing
process, is influenced by a variety of factors, including the raw materials used and the bioprocess
itself. New DSP methods have changed the game in industrial fermentation. The application of new
membrane technologies, crystallization, chromatography, and even nanobiocatalysts enables more
efficient and cost-effective separation and purification of the final product.
Bioreactors are used to grow organisms in large volumes, thereby enabling the production of
mass quantities of the target product. These reactors can be batch reactors, which contain all of the
components needed for cell growth, or continuous reactors, which have inlet and outlet ports
allowing for the addition of fresh growth media and the removal of cell waste.
Batch type bioreactor/ fermenter
It refers to a technique in which microbial cells grow and multiply to convert substrates into
products. Batch fermentation is performed using the stirred tank fermentor.
Batch fermentation itself clears that it involves batch-wise fermentation of the specific media.
Microbial cells harness the added nutrients. Thereafter, they ferment raw materials into desired
products within a predetermined fermentation time.
The factors affecting the fermentation time and rate include:
Type of substrate you are adding
Environmental conditions
Inoculum concentration
The product of interest
Batch culture depends upon the closed system fermentation. The culture volume remains the same.
Note: There is no addition or elimination of any content during the process.
Principle
Batch culture follows a closed system fermentation. You should add all the required materials
before the fermentation starts. The incubation of culture media proceeds for a specific fermentation
period.
During this period, you can neither add fresh media nor discard spent media. Batch culture
fermentation involves the commercial production of various products. This process takes place in
separate batches.
Here, other factors become limiting, as we supply limited nutrients for microbial growth. As a
result, the bacteria show a sigmoid growth curve with four distinct phases.
Typical diagram of an ideal batch / fed batch type bioreactor
The agitator allows uniform mixing of the culture broth. Also, it maintains a constant temperature.
The foam sensor senses the froth formed in the bioreactor. And, to break the froth, we can add
antifoaming agents.
Preconditions for designing:
The design of a bioreactor should take into account several physicochemical conditions: agitation
and aeration, rheology, hydrodynamic stresses, temperature, biochemical kinetics, form of feeding,
pH, concentration of microbes, and chemical species (oxygen, salt, alcohol).
Material balance for batch and Fed batch
see lecture notes / note book
CSTR
A continuous stirred tank bioreactor consists of a cylindrical vessel with motor driven central
shaft that supports one or more agitators (impellers). The shaft is fitted at the bottom of the
bioreactor. The number of impellers is variable and depends on the size of the bioreactor i.e.,
height to diameter ratio, referred to as aspect ratio. The aspect ratio of a stirred tank
bioreactor is usually between 3-5.
A continuous stirred tank bioreactor is made up of a cylindrical vessel with a central shaft controlled
by a motor that supports one or more agitators (impellers).
The sparger, in combination with impellers (agitators), allows for improved gas distribution
throughout the vessel.
A stirred tank bioreactor can be operated continuously in the fermentor, temperature control is
effortless, construction is cheap, easy to operate, resulting in low labor cost, and it is easy to clean.
It is the most common type of bioreactor used in industry.
Material balance for CSTR
see lecture notes / note book
A fluidized bed reactor (FBR) is a type of reactor that can perform a wide range of
multiphase chemical processes. In this reactor, a fluid (gas or liquid) is transported at high enough
speeds through a solid granular material (typically a catalyst) to suspend the solid and force it to
behave like a fluid.
The FBR can be provided in an aerobic, anoxic, or anaerobic configuration:
Aerobic systems: The FBR system is supplied with air or oxygen to promote aerobic metabolism,
where the organic contaminants entering the system serve as a growth and energy providing
substrate.
Anoxic systems: A growth substrate (e.g., acetic acid. ethanol, methanol, etc.) and a phosphorus
nutrient are supplied to the fluidized bed bioreactor, which promotes metabolism by the attached
microorganisms of all the dissolved oxygen, nitrate, nitrite, perchlorate, selenium and other metals.
Anaerobic systems: More recalcitrant organic contaminants are supplied as a growth and energy
substrate without the presence of oxygen. Metabolism of these organics occurs and methane gas is
formed. This gas can be flared or captured for beneficial reuse.
Principle behind fluidized bed reactor
In a fluidized bed reactor, the solid substrate material (the catalytic material upon which chemical
species react) is often supported by a porous plate known as a distributor. The fluid is then driven up
through the solid material via the distributor. The solids stay in place while the fluid travels through
the voids in the material at lower fluid velocities.
In the fluidized bed reactor, the effluent is vented on a regular basis. A properly built aeration
system produces fine bubble ventilation. Microorganisms receive oxygen as a result, and the
reactor's entire contents are combined. Compressed air is produced by a blower. The microbes are
attached to microscopic plastic.
Advantages of Fluidized Beds Reactors
1: Uniform particle mixing: Fluidized beds do not suffer from poor mixing like packed beds do
because of the solid material's inherent fluid-like nature. This thorough mixing ensures a consistent
result, which can be difficult to obtain in other reactor designs. Elimination of radial and axial
concentration gradients improve fluid-solid contact. It is critical for reaction efficiency and quality.
2: Temperature gradients that are consistent: Many chemical reactions necessitate the addition or
removal of heat. Localized hot or cold areas inside the reaction bed, which are common in packed
beds, are avoided in a fluidized environment like an FBR. Local temperature fluctuations,
particularly hotspots, can cause product degradation in other reactor types. As a result, FBRs are
ideal for exothermic processes. Researchers discovered that FBRs have significant bed-to-surface
heat transfer coefficients.
3: Continual operation of reactor: The fluidized bed allows for continuous product withdrawal and
introduction of new reactants into the reaction vessel. Due to the elimination of start-up
circumstances in batch processes, manufacturers may create their various goods more effectively
when they operate in a continuous process mode.
4: Maintenance is very low: FBP requires maintenance once or twice a year to ensure proper
operation.
5: Proven system: FBP is a scientifically proven sophisticated sewage treatment technology.
Disadvantages of FBRs
If the fluidization is not optimal, it can cause problems such as defluidization, channeling, or
entrainment of the particles. FBRs also require a careful design and operation to prevent erosion,
corrosion, or fouling of the reactor walls and the gas distributor.
Plug flow reactor
Plug-flow reactors (PFR) consist of tubes or pipes through which the reagents or reactants enter
through one inlet pipe and are mixed well for a specific time and flow rate before escaping through
the outlet.
It is called as variable type bioreactor due to change in volume of inlet and outlet slurry.
Fluid going through a plug flow reactor is modeled as flowing through the reactor as a series of
infinitely thin coherent “plugs”, each having a uniform composition and its semipermeable property.
The plugs travel in the axial direction of the reactor, with each plug having a different composition
from the ones before and after it.
The plug flow reactor model (PFR, sometimes called variable volume continuous tubular reactor,
CTR, or piston flow reactors) is a model used to describe chemical reactions in continuous, flowing
unmixed systems of horizontal geometry.
Plug flow reactors have a wide variety of applications in either gas or liquid phase systems.
Common industrial uses of tubular reactors are in gasoline production, oil cracking, synthesis of
ammonia from its elements, and the oxidation of sulfur dioxide to sulfur trioxide.
Airlift bioreactor
An airlift bioreactor works by agitating the contents of the bioreactor pneumatically using gas. The
gas used for agitation can act to either, introduce new molecules to the mixture inside of the
bioreactor, or remove specific metabolic molecules produced by microorganisms. Airlift bioreactors
have a built-in bubble column designed to release gas into the bioreactor. Gas is usually injected
into the bubble column at the bottom of the bioreactor. Mixing occurs as the bubbles rise through
the bubble column to the top of the bioreactor.
Simple diagram of an airlift bioreactor
The pattern of fluid circulation inside airlift bioreactors can be customized through the design of its
bubble column and shape. There are two separate channels within an airlift bioreactor: one channel
for gas/liquid up-flow and one channel for gas/liquid down-flow. Both channels create a closed gas/
liquid circuit. The mechanism for removing gaseous substances at the top of the bioreactor is called
the gas separator.
The two types of airlift bioreactors
There are two types of airlift bioreactors: external loop vessels and baffled vessels. External loop
vessels have distinct and separate conduits for circulation of gases and liquids. Baffled vessels draw
upon spider diffraction techniques to customize gas and liquid through the bioreactor flow by
including channels, vanes, and/or other methods of obstruction. Baffled vessels allow for greater
control of gas and liquid circulation patterns within
