Engineering Chemistry

Module -1
A) Laws of thermodynamics - entropy change (selected processes) –
spontaneity of a chemical reaction and Gibbs free energy - heat
transfer;
B) Kinetics - Concept of activation energy and energy barrier - Arrhenius
equation- effect of catalysts (homo and heterogeneous) – Enzyme
catalysis (Michaelis-Menten Mechanism).
 Part-A
Thermodynamics
 Thermodynamics: Basic Terminologies

the quantity of matter or a region Properties of a system:

Thermodynamic Systems: in space upon which attention is # Intensive Properties:
concentrated in the analysis of a
problem
Everything
external to
the system

# Extensive
Properties
 Thermodynamics: Basic Terminologies

Internal energy (U)

# State function: = Kinetic energy + Potential energy
Depends on the initial state & final state;
independent of the path used to reach from.
It’s a state function & an extensive property of
Example: T (Temperature), P (Pressure), U (Internal
the system.
energy), H (Enthalpy) etc.
Internal energy of a system changes when energy
is transferred into or outside the system in the
form of heat or work

# Path function:
Depends on the path between the initial & final state
Example: W (work done), q (heat transferred) etc.
 Thermodynamics: Basic Terminologies
State of a system
The state of thermodynamic variables such as Work done on/by the system
pressure, temperature, volume, composition W (Work) = F (force) x w (distance moved in the direction of
which describes the system is called state of
the system.
force)
when one/more variables undergo change, the
system is said to have undergone a change of
state

Adiabatic – no heat transferred

Isothermal – constant temperature
Isobaric – constant pressure
Isochoric – constant volume

Gas is heated ⇒ it will expand and pushes the piston, thereby doing work on the piston.
The work done (dw) when the system expands by dV against a pressure Pex: dw =
−PexdV

This is an example of the system doing the work on the surrounding

Reversible Process in Thermodynamics
# Example 1:
A thermodynamic process is Thermal equilibrium of two systems with the same temp.
reversible if the process can be If the temperature of either system is lowered infinitesimally, then
turned back such that both the energy flows into the system with the lower temperature.
system and the surroundings If the temperature of either system at thermal equilibrium is raised
return to their original states, with infinitesimally, then energy flows out of the hotter system
no other change anywhere else in
the universe.
In reality, no such processes as # Example 2:
reversible processes can exist. Reversible expansion:
A change can be reversed by an Suppose a gas is confined by a piston.
infinitesimal modification of a external pressure (Pex) = pressure (P) of the confined gas.
variable. Such a system is in mechanical equilibrium with its surroundings
because an infinitesimal change in the external pressure in either
direction causes changes in volume in the opposite directions.
0th Law of Thermodynamics

According to 0th law:

If two systems are in thermal equilibrium with a third
system, then those two systems are in thermal equilibrium
with each other.

Two physical systems are in thermal

equilibrium if there is no net flow of
heat (thermal energy) between them
when they are connected by a path
permeable to heat.

The 0th law of thermodynamics defines thermal equilibrium and

forms a basis for the definition of temperature.
 1st Law of Thermodynamics

It’s the law of conservation of energy

The energy of an isolated system remains constant. Whenever a quantity of energy (some form)
disappears, an exactly equivalent quantity of energy (some other form) must make an appearance.

Heat (q) and work (w) are equivalent ways of changing the internal energy of a system
Example:
o If a weight has been raised/lowered in the surroundings, transfer of energy happens by doing the work.
o If ice melts in the surroundings, it indicates the transfer of energy as heat.

For a system, if w = work done on a system, q = energy transferred as heat to a system & ΔU = resulting
change in internal energy
The signs of w and q:
+ve if energy is transferred to the system as work/heat
-ve if energy is lost from the system.
 Enthalpy & Heat Capacity

If the change of a system is brought about at Heat capacity (C) of a system b/n any two temperatures –
constant pressure, there will be change in the quantity of heat (q) required to raise the temperature of
volume. the system from the lower temperature (T1) to the higher
temperature (T2) divided by the temperature difference.

If mass of the system is 1 g, the heat capacity is called

the specific heat of the system.
For 1 mol of substance, the heat capacity is termed as
‘molar heat capacity’

The quantity (U + PV) is called the

enthalpy (H) of the system Molar heat capacity varies with temperature

Molar heat capacity at constant volume

ΔU = ΔH – PΔV
o ΔH = ΔU + PΔV @ constant volume w = 0 & ΔU = q
r,
 Heat Capacity
Molar heat capacity at constant pressure (Cp)
ΔU = q - w
@ constant pressure,
there is change in As quantity (U+PV) is the
volume & some work is enthalpy (H) of the system
done

Relationship between Cp & Cv For ideal gas, PV = RT (for 1 mole)

Δ(PV) = R ΔT

Heat capacity ratio,

Application of 1st Law to the Expansion Work

Isothermal Process (constant temperature)

In an isothermal process, the
temperature stays constant,
so the pressure and volume
are inversely proportional
work done to one another.

For an ideal gas,

The internal energy (U) ∝ Temperature (T)
if T = fixed, ΔU = 0 (according to 1st law, which deals with ΔU)

If the system does work, the energy

Pressure-volume diagram comes from heat flowing into the system
from the surrounding
# Magnitude of w depends on whether the If work is done on the system, heat flows
expansion is reversible or irreversible. out of the system to the surrounding.
Application of 1st Law to the Expansion Work

Reversible isothermal expansion:

(as PV = nRT)

Work done by the n moles of gas can be evaluated as:

in an isothermal expansion of a perfect gas)

Relations for Irreversible Isothermal The work done by a perfect gas when it expands
expansion reversibly and isothermally is equal to the area under
the isotherm p = nRT/V.
The work done during the irreversible expansion
against the same final pressure is equal to the
rectangular area shown slightly darker. Note that the
reversible work done is greater than the
irreversible work done.
 Numerical from of 1st Law

Example 2: 1 mole of an ideal gas expands against

a constant external pressure of 1 atm from a
volume of 10 dm3 to a volume of 30 dm3. Calculate
the work done by the gas in Joules.

Since, conversion of water to steam is accompanied

by increase in volume, work is done by the system
on the surroundings.
Hence, w = – 3100 Jmol-1
 2nd Law of Thermodynamics
Why we need for the 2nd law of thermodynamics? The 1st law uses the internal energy to identify
The 1st law of thermodynamics does not tell us anything permissible changes
about the direction of change. The direction of The 2nd law uses the entropy to identify which
spontaneous change of a process is defined by the 2nd law of these permissible changes are spontaneous.
of thermodynamics A spontaneous process points towards the
direction in which the total entropy increases.
2nd law of thermodynamics Entropy (S) is a state function.
Heat does not flow spontaneously from a cool body
to a hotter body.
The entropy (S) of an isolated system increases in
the course of a spontaneous change. Thermodynamic definition of entropy
ΔStot > 0 The thermodynamic definition of entropy
concentrates on the change in entropy (dS)
Where, Stot = S + Ssur
that occurs as the result of a physical or
S = the entropy of the system of interest, &
chemical process.
Ssur = the entropy of the surroundings
dqrev is the energy transferred as heat
# Note: when considering applications of the 2nd law – it is a reversibly to the system at the absolute
statement about the total entropy of the overall isolated temperature T.
system (the ‘universe’), not just about the entropy of the
system of interest.
 Entrop
y
Process that leads to an increase in entropy (ΔS > 0)
Entropy change for the system of an isothermal
expansion of a perfect gas

Notice the increasing disorder in above processes

 Entrop
y
Total Entropy change in irreversible (spontaneous) Isothermal Reversible expansion
process of a perfect gas
example: Isothermal expansion of an ideal gas at
constant temperature into vacuum

Clausius inequality

All spontaneous process occurring in Nature are

irreversible and entropy of the universe is
increasing continuously.
 Spontaneity of a Chemical Reaction

A spontaneous reaction is a reaction that favors the formation of products at the conditions under which
the reaction is occurring. Spontaneous processes may be fast or slow, but they occur without outside
intervention.
Ex. i) Conversion of graphite to diamond is slow;
ii) A burning fire is relatively a fast reaction.
"In any spontaneous process there is always an increase in the entropy of the universe“
For a given change to be spontaneous, ΔSuniverse must be positive.

Gibbs Free Energy

Free energy is energy that is available to do work. The free energy change of a reaction is a
mathematical combination of the enthalpy change and the entropy change.

The change in enthalpy, change in entropy and change in free energy of a reaction are the driving forces behind
all chemical reactions.
 Conditions for Spontaneity of a Chemical Reaction (Changes in Enthalpy (ΔH),
Entropy (ΔS), and Free Energy (ΔG))
A spontaneous reaction is one that releases free energy, and so the sign of ΔG must be negative. Since both
ΔH and ΔS can be either positive or negative, depending on the characteristics of the particular reaction,
there are four different possible combinations as shown in the table below.

ΔH◦ ΔS◦ ΔG◦

Negative Positive Always negative

Positive Positive Negative at higher temperatures, positive at lower temperatures

Negative Negative Negative at lower temperatures, positive at higher temperatures

Positive Negative Always positive

 Change in Free Energy @ different conditions
In an exothermic reactions At chemical equilibrium,
commonly spontaneous dG = 0
because dH < 0 & then dG < 0 provided TdS
is not so negative that it outweighs the
decrease in enthalpy. In an endothermic reaction:
dH > 0
but if such a reaction is to be spontaneous at constant
temperature and pressure, G must decrease.

as dG = dH − TdS
it is possible for dG to be
negative provided that the
entropy of the system increases
so much that TdS outweighs dH.

Endothermic reactions are

therefore driven by the
increase of entropy of the
system
 Solved problem-1
Q. How can you say that the following reaction is spontaneous or not? Justify the answer using
the standard entropy values given in the table.

Standard Entropy Values at 25°C

Substance So (J/K. mol)
131.0
Ans: From the absolute entropies of substances, we can calculate the entropy
H2 (g) change by

O2 (g) 205.0 So of Products – So of Reactants

H2O (l) 69.9

The entropy change for this reaction is highly negative because three gaseous molecules are being converted
into two liquid molecules. According to the drive towards higher entropy, the formation of water from
hydrogen and oxygen is an unfavorable reaction. In this case, the reaction is highly exothermic and the drive
towards a decrease in energy allows the reaction to occur.
 Solved problem-2
Q.2. What is ΔG for the melting of ice at -10 ◦C if the H = 6.01 kJ/mol and S = 0.022 kJ K-1mol-1

T= −10∘C + 273 = 263 K

Thus, we see that at −10 ∘C, the Gibbs free energy change ΔG is
positive for the melting of water. Therefore, we would predict that the
reaction is not spontaneous at −10 ∘C.
 3rd Law of Thermodynamics
At T = 0, all energy of thermal motion has been
quenched and in a perfect crystal all the
atoms/ions are in a regular, uniform array.
The localization of matter and the absence of
thermal motion suggest that such materials also
have zero entropy.

Statistical or microscopic definition of entropy:

S = k ln W
When T = 0, W = 1
where, S = the entropy, ∴ S = k lnW
k = Boltzmann constant, =0
W = the number of microstates or ⇒ if the value zero is ascribed to the entropies of elements in
the total number of ways a their perfect crystalline form at T = 0, then all perfect crystalline
molecular state can be distributed compounds also have zero entropy at T = 0
over the energy states for a specific
value of total energy.
Third law of thermodynamics:
The entropy of all perfect crystalline substances is zero at T = 0.
 Module 1

Part-B
Chemical Kinetics
 What is Chemical kinetics?
Chemical kinetics is the branch of chemistry which deals with the study of rates (or
fastness) of chemical reactions, the factors affecting it and the mechanism by which
the reactions proceed.

The rate of a chemical reaction might depend on variables such as

pressure,
temperature, and
the presence of a catalyst,

It is to be contrasted with thermodynamics, which deals with the direction in which a process
occurs but in itself tells nothing about its rate
 The rates of reactions
The change in concentration of reactants or products per unit time.
Here, the instantaneous rate of disappearance of one of the reactants (A or B)
at a given time, t (at constant volume) is −d[R]/dt. Similarly, the rate of
formation of one of the products is d[P]/dt. (Note the change in the sign)

The negative sign indicates that the concentration is decreasing with time.
 The rates of reactions

Consider a general reaction,

A+B→C

The rate of reaction will be:

Consider another general reaction:

aA + bB → cC +
dD where a, b, c d are stoichiometric coefficients

The rate of reaction will be:

 The rates of reactions

Sample Questions:
Write rate expressions for the following reactions:

1. NO2 (g) + CO (g) → NO (g) + CO2 (g)

2. 2HI (g) → H2 (g) + I2 (g)

Solution:

1
.
2.
 Rate laws and rate constants

The rate law is the relationship between the rate and the concentration, which are
related by a proportionality constant k, known as rate constant.
aA + bB → cC + dD

rate = k [A]m[B]n
where m and n are order of reaction in A and B, respectively k is the rate constant.

This above equation is called the rate law of the reaction.

 Rate laws and rate constants

Important points about rate laws and rate constant:

Rate law is a result of experimental observation. You CANNOT look at the
stoichiometry of the reaction and predict the rate law (unless the reaction is
an elementary reaction).
The rate law is not limited to reactants. It can have a product term, For
example: rate = k[A]m[B]n[C]c
The rate constant is independent of the concentrations but depends on the
temperature.
The units for k vary. Determine units for k by considering units for rate and
for concentration.
 Order of a reaction

A+B→C

For rate = k[A]m[B]n

Where, m is the order of reaction in A, n is the order of reaction in B. m and n can be
integers, fractions, negative or positive.

The overall reaction order is the sum of the exponents in the rate law.
m=0 (Zero order k[A]0)
m=1 (First order k[A]1)
m=2 (Second order k[A]2)

Examples:
H2 + Cl2 → 2HCl. Rate = k[H2]0 [Cl2]0 (Zero order)
SO2Cl2(g) → SO2(g) + Cl2(g) Rate = k[SO2Cl2]1
(First order)
NO2 → 2 NO + O2 Rate = k[NO2]2 (Second order)
2NO(g) + 2H2(g) → 2N2 (g) + 2H2O (g) Rate = k[NO]2 [H2]1 (Third order)
CH3COOC2H5 + H2O → CH3COOH + C2H5OH Rate = [CH3COOC2H5]1[H2O]0 (pseudo-first-order)
 Integrated rate laws
Since rate laws are in differential form, we must integrate them to find out the concentration as a
function of time.

Integrated first-order rate law:

A→
B
Rate =

Separate concentration and time terms

Integrating over the limits [A]0 to [A]t and 0 to t,

Continue….
 Integrated rate laws
Straight line equation (y = mx+c)

If we plot ln [A]t versus time, then we will get a straight line having negative slope (-
k). Rate constants can be determined from experiment by plotting data in this
manner.
 Pseudo First Order Reaction
A pseudo first-order reaction can be defined as a second-order or bimolecular reaction that
is made to behave like a first-order reaction.
This reaction occurs when one reacting material is present in great excess or is maintained
at a constant concentration compared with the other substance.
A+B→
C
So, if component B is in large excess and the concentration of B is very high as compared to that
of A, the reaction is considered to be a pseudo-first-order reaction with respect to A and if
component A is in large excess and the concentration of A is very high as compared to that of B,
the reaction is considered to be pseudo-first order with respect to B.

For example:
CH3COOC2H5 + H2O → CH3COOH + C2H5OH

Rate = k
[CH3COOC2H5]
The concentration of water is very high and thus does not change much during the
course of the reaction.
 Temperature dependence of reaction rates
The rate constant of most reactions increases with increase in the temperature.

Arrhenius equation

where, A is the pre-exponential factor and Ea is the activation energy.

A plot of ln k against 1/T is a straight line when the reaction follows the behavior described by the
Arrhenius equation.
The higher the activation energy, the stronger the temperature dependence of the rate constant (i.e.,
the steeper the slope).
If a reaction has zero activation energy, its rate is independent of temperature.

If we plot the graph ln k vs 1/T, we will get the value of A

from the intercept at infinite T (i.e.; 1/T=0) and the value of
Ea from the slope.
Energy barrier: interpretation of Arrhenius parameters

One can rewrite the above equation as:

To interpret Ea, lets us consider the collision between molecules of reactants A and
B:

Collision
theory:
1. The rate of a reaction is proportional to the rate of reactant collisions:
2. The reacting species must collide in an orientation that allows contact between
the atoms that will become bonded together in the product.
3. The collision must occur with adequate energy to permit mutual penetration of
the reacting species’ valence shells so that the electrons can rearrange and form
new bonds (and new chemical species).
 Collision theory

But all the collision will not lead to the product. Only the molecules which are
having sufficient energy (E ≥ Ea) can cross the energy barrier.
The minimum energy necessary to form a product during a collision between
reactants is called the activation energy (Ea).
The kinetic energy of reactant molecules plays an important role in a reaction
because the energy necessary to form a product is provided by a collision of a
reactant molecule with another reactant molecule.
If the activation energy is much larger than the average kinetic energy of the
molecules, the reaction will occur slowly: Only a few fast-moving molecules will
have enough energy to react.
If the activation energy is much smaller than the average kinetic energy of the
molecules, the fraction of molecules possessing the necessary kinetic energy will
be large; most collisions between molecules will result in reaction, and the reaction
will occur rapidly.
 Collision theory

The potential energy rises to a maximum and the

cluster of atoms that corresponds to the region
close to the maximum is called the activated
complex.
After the maximum, the potential energy falls as
the atoms rearrange in the cluster and reaches a
value characteristic of the products.
The peak of the potential energy corresponds to
the activation energy Ea..This crucial configuration
is called the transition state of the reaction.
The pre-exponential factor is a measure of the rate
at which collisions occur irrespective of their
energy. Hence, the product of A and the
exponential factor, e−Ea/RT, gives the rate of
successful collisions.
A potential energy profile for an
exothermic reaction. The height
of the barrier between the
reactants and products is the
activation energy of the
reaction.
 Collision theory

Both postulates of the collision theory of reaction rates are accommodated in the
Arrhenius equation. The frequency factor A is related to the rate at which
collisions having the correct orientation occur. The exponential term is related to
the fraction of collisions providing adequate energy to overcome the activation
barrier of the reaction.
 Collision theory
Quantitatively, for two reactions at the same temperature

The reaction with the higher activation energy has the lower rate constant and the slower rate.

The larger value of Ea results in a smaller value for reflecting the smaller fraction of

molecules with enough energy to react.

The reaction with the smaller Ea has a larger fraction of molecules with enough energy to

react. This will be reflected as a larger value of , a larger rate constant, and a faster rate

for the reaction.

(a) As the activation energy of a reaction decreases, the number of molecules with at least this much energy increases, as shown by the
shaded areas.
(b) At a higher temperature, T2, more molecules have kinetic energies greater than E a, as shown by the yellow shaded area.
 Catalysi
s is of great significance as it affects our daily
The science and technology of catalysis
life. Four major sectors of the world economy; petroleum and energy production,
chemicals and polymer production, food industry and pollution control, involve
catalytic processes.
 Definition of
Catalysis
“A catalyst is a chemical entity which by virtue of its presence in a
reacting system increases or decreases the rate of the reaction, itself
remaining unchanged in chemical properties or mass at the end of a
reaction.”
The phenomenon of alteration of the rate of a reaction by a catalyst is
known catalysis.

The term catalysis, proposed in 1835 by Jöns Jakob Berzelius (1779-

1848), comes from the Greek words kata meaning down and lyein
meaning loosen.

The economic significance of the catalyst industry is enormous. The

catalytic processes contribute greater than 30-40% of global GDP. The
global catalyst market size was estimated at USD 34.0 billion in 2019 and
is expected to reach USD 35.1 billion in 2020.
Characteristics of
Catalysts

(1) The catalyst remains unchanged (in mass and chemical

composition) in the reaction.
(2) A small quantity of the catalyst is required.
(3) The catalyst does not change the equilibrium constant but the
equilibrium approaches earlier.
 Catalytic reactions

Catalysts work by providing alternative mechanism involving a

different transition state of lower energy. Thereby, the activation
energy* of the catalytic reaction is lowered compared to the
uncatalyzed reaction as shown in Figure below:

Figure: Schematic diagram to illustrate the effect of catalyst on activation energy of

 Types of catalysis

Following are the main types of

catalysis:
1. Heterogeneous catalysis
2. Homogeneous catalysis
3. Enzyme catalysis
1. Heterogeneous catalysis
If the catalyst is present in a different phase than the reactants is
called heterogeneous catalyst and the phenomenon is known
heterogeneous catalysis.
In heterogeneous catalysis the reactions take place at the interface of
two phases. The catalyst is, often a solid and adsorbs a liquid or a
gas. This type of catalysis is of great importance in many industrial
processes.

Figure: Schematic diagram to illustrate the heterogeneous catalysis.

 Examples of Heterogeneous catalyst
(a) Manufacture of ammonia by the Haber process. Iron (Fe) acts as catalyst.

N2 (g) + 3H3 (g) → 2NH3 (g)

(b) Manufacture of sulphuric acid by the Contact process. Vanadium pentoxide
(V2O5) or platinum are catalysts for the production of SO3 (g) from SO2 (g) and
O2 (g).

2SO2 (g) + O2 (g) → 2SO3 (g)

(c) Catalysts used in many reactions in the petroleum and polymer industries. There
are cases of heterogeneous catalysis where a reaction in the liquid phase is
catalysed by a substance in the solid state. An example is the decomposition of
H2O2 (aqueous) by MnO2 (s).

2H2O2 (aq) → 2 H2O (l) + O2 (g)

(d) Examples of reactions in which both the reactant and the catalyst are in the
solid phase. The decomposition of KClO3 is catalysed by solid MnO2.
2 KClO3 (s) → 2KCl (s) + 3O2 (g)
2. Homogeneous catalysis
In a reaction, if the catalyst is present in the same phase as the
reactants, it is called a homogeneous catalyst and the phenomenon
is homogeneous catalysis. Such catalysis can take place in gaseous
reaction or reactions in solution.
These chemicals help in attaining the equilibrium more quickly by
increasing the rates of both the forward and reverse reactions to an
extent.

Figure: Schematic diagram to illustrate the homogeneous catalysis.

Examples of homogeneous catalysis in the gas phase

(a) Oxidation of sulphur dioxide, SO2, by oxygen to sulphur trioxide,

SO3, in presence of nitric oxide, NO, in the Chamber Process for
sulphuric acid manufacture.
2SO2 (g) + O2 (g) → 2SO3 (g)
here, NO acts as a catalyst.
(b) The following reaction in the gas phase is catalyzed by traces of
chlorine gas, particularly in presence of light.
2N2O (g) → 2N2 (g) + O2 (g)
In presence of light chlorine forms chlorine radicals, which react with
N2O forming the intermediate radical ClO*. The proposed mechanism
is:
Step 1: N2O (g) + Cl* (g) → N2 (g) + ClO*(g)
Step 2: 2ClO*(g) → Cl2 (g) + O2 (g)
Examples of homogeneous catalysis in the solution phase

(a) Hydrolysis of ester in the presence of acid and alkali:

CH3COOC2H5 (l) + H2O (l) → CH3COOH (aq) + C2H5OH (aq)

(b) Hydrolysis of sucrose (cane sugar) into glucose and fructose in
presence of minerals acids acting as catalysts:

C12H22O11 (aq) + H2O (l) → C6H12O6 (aq) + C6H12O6 (aq)

(cane (glucose (fructose
sugar) ) )
Enzyme catalysis
Michaelis-Menton mechanism
 Enzymes
Enzymes are protein-based molecules that can process certain
chemical reactions

These reactions occur at a localized site, called the active site,

at the rate much faster than a normal chemical reaction.

Substrate is the molecule that fits into the active site of the
enzyme and undergoes transformation to a product.

Example of an enzyme catalysed reaction is catalase that

converts hydrogen peroxide to water and oxygen. It is an
important enzyme protecting the cell from oxidative damage by
reactive oxygen species (ROS)

H2 O2 → H 2 O + O 2
Molecular structure of Catalase
Reaction catalysed by the enzyme, catalase
Mechanism of enzyme-catalyzed reactions
Enzyme-catalyzed reactions work in
a lock and key fashion.

The substrate uniquely fits like a

key into the active site of the
enzyme, forming a lock-key
complex.

The substrate is converted into the

product by the enzyme at the active
site.

The product is then released from

the active site.
 Enzymes’ effect on the activation energy
Enzymes lower the activation energy for reactions. The
lower the activation energy, the faster the rate of the
reactions.

For example: the enzyme catalase reduces the activation

energy for the decomposition of hydrogen peroxide to 8
kJ mol-1, corresponding to an acceleration of the reaction
by a factor of 1015 at 298 K.

A generic equation for the complex formation is as

follows:

E+S ES P+E
Michaelis-Menten equation
Michaelis-Menten equation is a commonly used model that assumes that the concentration of the enzyme
remains constant.

The enzyme reacts with the substrate for form an enzyme-substrate complex, which leads to the synthesis of
the product and the release of the enzyme

ka kb
E +S ES P+E
ka ’

Where, ka is the rate of formation of ES, ka’ is the rate of dissociation of ES, and kb is the rate of formation
of P from ES.
Michaelis-Menten Mechanism
One of the earliest descriptions of the action of enzymes is the Michaelis-Menten mechanism. The proposed
mechanism, with all species in an aqueous environment, is as follows.

Step 1: The bimolecular formation of a combination, ES, of the enzyme E and the substrate S:
E + S → ES Rate of formation of ES = ka[E][S]

Step 2: Unimolecular decomposition of the complex:

ES → E + S Rate of decomposition of ES = ka’[ES]

Step 3: The unimolecular formation of products P and the release of the enzyme from its combination
with the substrate:

ES → P + E Rate of decomposition of ES = ka’[ES]

Rate of decomposition of ES = ka’[ES]