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).

1
 Part-A
Thermodynamics

2
 Thermodynamics: Basic Terminologies

the quantity of matter or a Properties of a system:

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

# Extensive
Properties

3
 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
Example: T (Temperature), P (Pressure), U of the system.
(Internal 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 4
Example: W (work done), q (heat transferred) etc.
 Thermodynamics: Basic Terminologies
State of a system
⮚ The state of thermodynamic variables
Work done on/by the system
such as pressure, temperature, volume, W (Work) = F (force) x w (distance moved in the direction of
composition which describes the system
force)
is called state of the system.
⮚ 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 5

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

6
 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.

7
 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.

8
 Enthalpy & Heat Capacity

⮚ If the change of a system is brought ❑ Heat capacity (C) of a system b/n any two
about at constant pressure, there will be temperatures – the quantity of heat (q) required to
change in volume. raise the temperature of 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’
C
❑ 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
or ΔH = ΔU + PΔV @ constant volume w = 0 & ΔU = q
, 9
 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,

10
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
work done inversely proportional 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
expansion is reversible or irreversible. flows out of the system to the
11
surrounding.
 Application of 1st Law to the Expansion Work

 Reversible isothermal expansion:

w = dv = dv (as PV = nRT)
throughout the expansion, Pex = P as the expansion is reversible)

 Work done by the n moles of gas can be

evaluated as:
w= =

(since = in an isothermal expansion of a perfect gas)

 The work done by a perfect gas when it

 Relations for Irreversible Isothermal expansion expands reversibly and isothermally is
equal to the area under the isotherm p =
a) Free expansion (expansion in vacuum) nRT/V.
w = -dv =0  The work done during the irreversible
b) Volume of the gas expands against a constant expansion against the same final
pressure. pressure is equal to the rectangular area
w = -dv = -Pex (Vf – Vi) shown slightly darker. Note that the
reversible work done is greater than
12
the irreversible work done.
 Application of 1st Law to the Expansion Work
 Adiabatic process (constant heat)  Reversible adiabatic expansion
 no heat is added/ removed from a  Relation between T, V and P
system.

( )( )
𝛾−1
 1st law of thermodynamics: 𝑇𝑖 𝑉𝑓
= Þ ln
ΔU = wthe system, q
(as no heat is allowed to enter/leave 𝑇𝑓 𝑉𝑖
= 0) 𝐶𝑝
 Example: A gas expanding so quickly that no heat Þ ln [𝑎𝑠 ,𝛾= ]
can be transferred. Due to the expansion work, 𝐶𝑣
temperature drops. This is exactly what happens ln
with a carbon dioxide fire extinguisher, with the Þ ― = R]
gas coming out at high pressure and cooling as it
expands at atmos.wpressure ln
® Expansion: = ― ve, = ― ve; Þ
So, T of the system falls
Þ Work is done by the system at the expense of  Irreversible adiabatic expansion
its internal energy
 Free expansion (Pex = 0) :
 w = = (for 1 mole of gas)  Expansion against a constant pressure:
 (for 1 mole of gas)
13
 Application of 1st Law to the Expansion Work
 Isobaric process (constant pressure)  Isochoric process (constant volume)

 the pressure is kept constant.  the volume is kept constant

 The work done by the system in an isobaric  The work done is zero in an isochoric
process is simply the pressure multiplied by the process
change in volume  . Example of an isochoric system: A gas in a
 Example of an isobaric system: A gas, being box with fixed walls
slowly heated or cooled, confined by a piston in a
cylinder.

14
 Some Special Forms of First Law of Thermodynamics

Mathematical statement of the First law of Thermodynamics is

ΔU = q – w

Case 1 : Cyclic process & isothermal process

ΔU = 0 ∴ q = w

Case 2 : isochoric process

w = 0 ∴ ΔU = qv

Case 3 : adiabatic process

q = 0 ∴ ΔU = – w

Case 4 : isobaric process

15
ΔU = q – w or ΔU = q – PΔV
 Numerical from of 1st Law

Find ΔU, q and w if 2 moles of hydrogen at 3 atm pressure expand

isothermally at 50 ºC and reversibly to a pressure of 1 atm. Calculate
energy in cal.
Ans: q = w ; q = – 1410 cals

16
 Numerical from of s1st Law

1) 1g of water at 373 K is converted into steam at the same temperature.

The volume of water becomes 1671 ml on boiling. Calculate the change
in the internal energy of the system if the heat of vaporisation is 540 cal/g
(Bahl & Arun Bahl, pg. 251). Ans: ΔU = 499 cal/g

2) Calculate the maximum work done when pressure on 10 g of hydrogen

is reduced from 20 to one atmosphere at a constant temperature of 273
K. The gas behaves ideally. Will there be any change in internal energy ?
Also calculate ‘q’.
Ans: q = w = – 8126.65 cals.

17
 Numerical from of 1st Law

Calculate the pressure-volume work done when a system containing a

gas expands from 1.0 litre to 2.0 litres against a constant external
pressure of 10 atmospheres. Express the answer in calories and joules.
Ans = -242 cal & 1012.528 J

18
 Numerical from of 1st Law

2) One mole of an ideal gas at 25ºC is allowed to expand reversibly at

constant temperature from a volume of 10 litres to 20 litres. Calculate the
work done by the gas in joules and calories.
Ans = – 410.46 cal

Find the work done when one mole of the gas is expanded reversibly and
isothermally from 5 atm to 1 atm at 25ºC.
Ans = – 3.988 kJ

19
 Numerical from of 1st Law

2) Calculate the value of ΔU and ΔH on heating 64.0 g of oxygen from

0ºC to 100ºC. Cv and Cp on an average are 5.0 and 7.0 cal mol–1degree–1

Ans: ΔU = 2000 cals ΔH = 2800 cals

20
 Numerical from of 1st Law

2) Calculate the amount of heat necessary to raise 213.5 g of water from

25º to 100ºC. Molar heat capacity of water is 18 cal mol–1 K–1.
Ans: q = 16,012 cals

21
 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
22
 Numerical from of 1st Law
 Example 3: 1 mole of an ideal monoatomic gas at 27 C expands reversibly and adiabatically from a
volume of 10 dm3 to a volume of 20 dm3. Calculate q, U, W and H. Given

Solution:
Since the process is adiabatic, q = 0 Since for an adiabatic process, q =0,
hence ΔU = w = – 1384 J
Þ ΔH = ΔU + ΔPV = ΔU + ΔnRT
Þ Tf = 189K = ΔU + nR(Tf- Ti)

𝐶 𝑣=( )
𝜕𝑈
𝜕𝑇 𝑣
Þ ® (1 mol)

ΔH = – 1384 J – 923 J = – 2307 J

For a finite change in n moles,
# Note: ΔH can also be calculated by
= (1 mol) using the relation
= – 1384 J
 Example 4: 10 moles of an ideal gas expands reversibly and isothermally from a pressure of 10 atm to
2 atm at 300 K. Calculate the work done.
Solution: w = = (10 mol) = 40.15 103J 23
 2nd Law of Thermodynamics

 1st law of thermodynamics states - one form of energy can change into
another form but the total amount of energy remains the same.

 Once we specify a particular process or change, this law helps us to

balance the internal energy, heat released and work done in the
process.

 But 1st law says nothing about whether the process specified occur
and if so in which direction.

 This question concerns the second law of thermodynamics.

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 2nd Law of Thermodynamics

 Spontaneous process or
natural process: A process
which proceeds of its own,
without any outside assistance.

 Nonspontaneous process or
unnatural process – A process
which does not proceed on its
own.

 Tendency of a process to occur

naturally is called spontaneity.
25
 CRITERIA OF SPONTANEITY

 A spontaneous change is one-way or unidirectional. For reverse

change to occur, work has to be done.

 For a spontaneous change to occur, time is no factor. A spontaneous

reaction may take place rapidly or very slowly.

 If the system is not in equilibrium state, a spontaneous change is

inevitable. The change will continue till the system attains the state of
equilibrium.

 Once a system is in equilibrium state, it does not undergo any

further spontaneous change if left undisturbed. To take system away
from equilibrium, some external work must be done on system.
26
 CRITERIA OF SPONTANEITY

 A spontaneous change is accompanied by decrease of internal

energy or enthalpy (ΔH). It implies that only such reactions will occur
which are exothermic.

 But melting of ice & evaporation of rain water are endothermic

processes which proceed spontaneously.

 Clearly, there is some other factor in addition to ΔH which governs

spontaneity.

 Second law of thermodynamics introduces new factor Entropy to explain

this.
27
CRITERIA OF SPONTANEITY

28
 ENTROPY

 Entropy - measure of randomness or disorder of the molecules of the

system. Symbol of entropy is S

 Change in disorder accompanying a process from start to completion is

represented by ΔS.

 Entropy of a system is a state function and depends only on the initial

and final states of the system.

 Change in entropy, ΔS, for any process is given by equation,

ΔS = Sfinal – Sinitial

When Sfinal > Sinitial, ΔS is positive. 29

 ENTROPY

 A process accompanied by an increase in entropy tends to be

spontaneous

30
 2nd Law of Thermodynamics
▪ Why we need for the 2nd law of thermodynamics? ⮚ The 1st law uses the internal energy to
→ The 1st law of thermodynamics does not tell us identify permissible changes
anything about the direction of change. The⮚ The 2nd law uses the entropy to identify
direction of spontaneous change of a process is which of these permissible changes are
defined by the 2nd law of thermodynamics spontaneous.
❑ 2nd law of thermodynamics → A spontaneous process points towards
the direction in which the total entropy
▪ Heat does not flow spontaneously from a cool increases.
body to a hotter body.
⮚ Entropy (S) is a state function.
▪ The entropy (S) of an isolated system
increases in the course of a spontaneous ⮚ Thermodynamic definition of entropy
change. ΔS > 0 → The thermodynamic definition of entropy
tot

Where, Stot = S + Ssur concentrates on the change in entropy

(dS) that occurs as the result of a
S = the entropy of the system of interest, &
physical or chemical process.
Ssur = the entropy of the surroundings
→ dqrev is the energy transferred as heat
# Note: when considering applications of the 2nd law – it
reversibly to the system at the absolute
is a statement about the total entropy of the overall
temperature T.
isolated system (the ‘universe’), not just about the
entropy of the system of interest. 31
 Entropy

▪ 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 32

 Entropy
⮚ Total Entropy change in irreversible ⮚ Isothermal Reversible expansion
(spontaneous) 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. 33
 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.
34
 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

Negative at higher temperatures, positive at

Positive Positive
lower temperatures

Negative at lower temperatures, positive at

Negative Negative
higher temperatures

Positive Negative Always positive

35
 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
⮚ In an endothermic reaction:
the decrease in enthalpy.
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
36
 Free Energy

 In an exothermic reactions

 commonly spontaneous  At chemical equilibrium,

because dH < 0 & then dG < 0 provided TdS is not
so negative that it outweighs the decrease in  dG = 0
enthalpy.  Free energy change with
temperature and pressure:

37
 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.
38
 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

Negative at higher temperatures, positive at

Positive Positive
lower temperatures

Negative at lower temperatures, positive at

Negative Negative
higher temperatures

Positive Negative Always positive

39
 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
Substanc So (J/K.
e mol) Ans: From the absolute entropies of substances, we can calculate the
H2 (g) 131.0 entropy change by

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

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.

40
 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.
41
 Numerical from 2nd Law of Thermodynamics
 Example 1: Calculate the efficiency of  Example 3: Heat supplied to a Carnot engine is 1897.8 kJ.
a certain power station operates with How much useful work can be done by the engine which
superheated steam at 300 (Th = 573 works between 0 ∘C and 100 ∘C.
K) and discharges the waste heat into Solution:
the environment at 20 (T = 293 K).
Tc​= 0 + 273 = 273 K, Th ​= 100 + 273 = 373 K
Solution: Tc= (1 − η)Th qh = 1897.8 kJ
 η = 1 – (Tc /Th) w
Theoretical efficiency (η) = 1 – (293K/573K) = 1897.8 kJ
= 0.489 = 508.7 kJ
= 48.9 %  Work done by the engine is 508.7 kJ
# In practice, there are other losses due to
mechanical friction and the fact that
turbines do not operate reversibly.
 Example 2: Calculate the maximum efficiency of a heat engine operating between 100 ∘C and 25 ∘C
Solution: = 1 – (298 K/373 K)
Tc​= 25 + 273 = 298K Tc= (1 − η)Th
For engines, we = 0.201
have Th​= 100 + 273 = 373 K  η = 1 – (Tc /Th) = 20.1 % 42
 Numerical from 2nd Law of Thermodynamics

 Example 4: 5 mole of an ideal gas  Example 5: Calculate the change in entropy

expands reversibly from a volume of 8 accompanying the heating of 1 mole of Helium gas
dm3 to 80 dm3 at a temperature of 27 ∘C. (assumed ideal) from a temperature of 298 K to a
Calculate the change in entropy. temperature of 1000 K at constant pressure. Assume
Solution: Cv =3/2 R As
Solution:
)  Cp =
Given that = 2, = 80 dm3 𝑇𝑓
∆ 𝑆𝑃 =𝐶 𝑝 ln
𝑇𝑖 = 25.17
= (5 mol) (8.314 J K-1mol-1) (80 dm3/8 dm3)
= 95.73 JK-1
 Example 6: 1 mol of an ideal gas expands reversibly from a volume of 10 dm3 and 298 K to a volume
of 20 dm3 and temperature 250 K. Assuming Cv =3/2 R, calculate the entropy change for the process.
Solution
:
= 1.5 ( + ( ln (20 dm3/10 dm3)
= 3.57 JK-1mol-1

43
 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 ⇒ if the value zero is ascribed to the entropies of elements
or the total number of ways a in their perfect crystalline form at T = 0, then all perfect
molecular state can be crystalline compounds also have zero entropy at T = 0
distributed 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. 44
 Module 1

Part-B
Chemical Kinetics

45
 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

46
 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.

47
 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:

48
 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.

49
 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.

50
 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.

51
 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)
52
 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,

53
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.

54
 Integrated rate laws
Other forms:

ln
At  kt
A0
At  e  kt
A0
At  A0 e  kt
Integrated first order rate law

The exponential decay of the reactant in a first-order

reaction. The larger the rate constant, the more rapid
the decay.

55
 Integrated rate laws
Question: The variation in the partial pressure of azomethane with time was followed at 600 K, with
the results given below. Confirm that the decomposition is first-order in azomethane, and find the rate
constant at 600 K.

CH3N2CH3 (g) → CH3CH3 (g) + N2 (g)

Solution: To confirm that a reaction is first-order, plot ln([A] t/[A]0) against

time and expect a straight line. Because the partial pressure of a gas is
proportional to its concentration, an equivalent procedure is to plot ln(p/p0)
against t.
First, convert p into ln(p/p0) and draw the graph. The plot is straight,
confirming a first-order reaction, and its slope is -3.610-4.
Therefore, k = 3.6 10-4 s-1.

56
 First-order Half-life
Half-life is the time it takes for the original concentration to be reduced by half.
From above:

ln
At  kt
A0
 A0 
 
 2 
ln  kt t / 2
A0
1
ln   ktt / 2
2
 0.693  kt t / 2
t t / 2  0.693 / k
It is clear from the result that the half-life of a reactant is independent of its initial concentration for a
first-order reaction. Therefore, if the concentration of A at some arbitrary stage of the reaction is [A],
then it will have fallen to 1/2[A] after a further interval of (ln 1/2)/k.

57
 First-order Half-life

Question:

1. The half-life of a first-order reaction was found to be 10 min at a certain temperature. What is its
rate constant?

Solution: k= 0.693/600s = 0.00115s-1

58
 First-order Half-life
Question:
2. If 3.0 g of substance A decomposes for 36 minutes the mass of unreacted A remaining is found to
be 0.375 g. What is the half-life of this reaction if it follows first-order kinetics?

Solution:

59
 First-order Half-life
Question:
2. If 3.0 g of substance A decomposes for 36 minutes the mass of unreacted A remaining is found to
be 0.375 g. What is the half-life of this reaction if it follows first-order kinetics?

Solution:

ln
At  kt
A0

ln
At / t  k
A0
0.375 g
ln
3g
k
36 min

k =0.0578 min-1

ln 2 0.693
t1 / 2    12 min
k 0.0578
60
 Integrated second-order rate law
A→B

d A
 k A
2

dt

d A
 kdt
A2
1 1
  kt
At A0

Integrated zero-order rate law

A→ B

d A
 k A
0

dt

At  A0  kt

61
 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.

62
 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.
63
 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.

64
 Temperature dependence of reaction rates
Questions:
1. The rate of the second-order decomposition of acetaldehyde (CH 3CHO) was
measured over the temperature range 700–1000 K, and the rate constants are reported
below. Find Ea and A.

Solution: First convert T in (103) and k into ln k. Now, plot ln k against 1/T. You will
obtain the following graph having slope = -22.7 and intercept 27.7.

Now, Ea = 22.7 × (8.3145 J K−1 mol−1) × 103 K = 189 kJ mol−1

A = e27.7 dm3 mol−1s−1 = 1.1 × 1012 dm3 mol−1 s−1

65
 Temperature dependence of reaction rates

2. The values of rate constants for a reaction are 9.51x10 -9 L/mol.s and 1.10x10-5 L/mol.s at
temperatures 500K and 600 K respectively. Calculate the activation energy.

Solution: k2 E 1 1
ln  a   
k1 R  T2 T1 
1
k 1 1
Ea   R ln 2   
k1  T2 T1 

After substituting the given values and calculating,

Ea= 176 kJ/mol

66
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).
67
 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.

68
 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.
A potential energy profile for
❖ The pre-exponential factor is a measure of the
rate at which collisions occur irrespective of an exothermic reaction. The
their energy. Hence, the product of A and the height of the barrier between
exponential factor, e−Ea/RT, gives the rate of the reactants and products is
successful collisions. the activation energy of the
reaction.
69
 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.

70
 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. 71
 Catalysis
The science and technology of catalysis is of great significance as it affects our daily
life. Four major sectors of the world economy; petroleum and energy production,
chemicals and polymer production, food industry and pollution control, involve
catalytic processes.

72
 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. 73
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.

74
 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 75

 Types of catalysis

Following are the main types of catalysis:

1. Heterogeneous catalysis

2. Homogeneous catalysis

3. Enzyme catalysis

76
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. 77

 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 78
solid phase. The decomposition of KClO is catalysed by solid MnO .
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 79

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)
80
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 sugar) (glucose) (fructose)

81
Enzyme catalysis
Michaelis-Menton mechanism

82
 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)
H2O2 → H2O + O2
Molecular structure of
Reaction catalysed by the enzyme, Catalase
catalase
83
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.

84
 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

85
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.

86
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]

87