MODULE -2

PART - A. THERMODYNAMICS

1
 THERMODYNAMICS: BASIC TERMINOLOGIES
The quantity of matter or a
Properties of a system
Thermodynamic Systems: region in space upon which
attention is concentrated in the # Intensive Properties
analysis of a problem Intensive properties do not
Everything depend on the amount of
external to matter in a sample
the system

# Extensive Properties
Extensive properties
depend on the amount of
matter in a sample

2
 THERMODYNAMICS: BASIC TERMINOLOGIES
# STATE FUNCTION INTERNAL ENERGY (U)
Depends on the initial state & final state;
= Kinetic energy + Potential energy
independent of the path used to reach from.
Example: T (Temperature), P (Pressure), U
(Internal energy), H (Enthalpy) etc. ∙ It’s a state function & an extensive property of
the system.
∙ 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. 3
 THERMODYNAMICS: BASIC TERMINOLOGIES

State of a system Work done on/by the system

➢ The state of thermodynamic variables such as W (Work) = F (force) x w (distance moved
pressure, temperature, volume, composition which in the direction of force)
describes the system 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 push the piston, thereby doing work on the piston.
The work done (dw) when the system expands by dV against a pressure Pex: dw =- PexdV
𝒗
Total work done by the system to expand from volume Vi to Vf: W = − ‫ 𝒙𝒆𝑷 𝒇 𝒗׬‬dv
𝒊

 This is an example of the system doing the work on the surrounding 4

 REVERSIBLE PROCESS IN THERMODYNAMICS
# Example 1:
A thermodynamic process is Thermal equilibrium of two systems with the same temperature
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
system and the surroundings return temperature.
to their original states, with no other ▪ If the temperature of either system at thermal equilibrium is
change anywhere else in the raised infinitesimally, then energy flows out of the hotter
universe. system

In reality, no such processes as # Example 2:

reversible processes can exist. Reversible expansion:
Thus, a more appropriate definition Suppose a gas is confined by a piston
is a reversible change in external pressure (Pex) = pressure (P) of the confined gas.
thermodynamics is A CHANGE THAT ▪ Such a system is in mechanical equilibrium with its
CAN BE REVERSED BY AN surroundings because an infinitesimal change in the
INFINITESIMAL SMALL MODIFICATION external pressure in either direction causes changes in
OF A VARIABLE. volume in the opposite directions.
dw =- 𝑃𝑒𝑥𝑑𝑉 = −𝑝𝑑𝑉
𝑣
W = − ‫𝑝 𝑓 𝑣׬‬dv 5
𝑖
 0TH LAW OF THERMODYNAMICS

According to 0th law:

If two systems are in thermal equilibrium with a third
system, then those two systems are also 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.
6
 1ST LAW OF THERMODYNAMICS

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 appear somewhere
else.
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 has melted in the surroundings, it indicated transfer of energy as heat.

For a system, if w = work done on a system, q = energy transferred as

𝜟𝑼 = 𝒒 + 𝒘
heat to a system & ΔU = resulting change in internal energy

The sign of w and q:

✓ +ve if energy is transferred to the system as work/heat
✓ -ve if energy is lost from the system.
Therefore,
change in internal energy (𝛥𝑈 ) of a system = heat added to the system (q) - the work done by the
system (w)
𝜟𝑼 = 𝒒 − 𝒘 7
 ENTHALPY & HEAT CAPACITY

If change in a system is brought about at Heat capacity (C) of a system between any two
constant pressure, there will be change in temperatures – the quantity of heat (q) required to
volume. raise the temperature of the system from the lower
temperature (T1) to the higher temperature (T2)
Vi = volume of initial state, Vf = volume of final divided by the temperature difference.
state. 𝒒
Work done by the system, 𝑤 = 𝑃 (𝑉𝑓 − 𝑉𝑖 ) 𝑪=
𝑻𝟐 − 𝑻𝟏
ΔU = q - w
or, ΔU = q - P (𝑉𝑓 − 𝑉𝑖 ) ☻ If mass of the system is 1 g, the heat capacity is
 𝑈𝑓 − 𝑈𝑖 = q – P 𝑉𝑓 − 𝑉𝑖 called the specific heat of the system
 (𝑈𝑓 + 𝑃𝑉𝑓 ) − 𝑈𝑖 + 𝑃𝑉𝑖 = 𝑞 ☻ For 1 mol of substance, the heat capacity is
termed as ‘molar heat capacity’
❑ The quantity (U + PV) is called the
𝑑𝑞
enthalpy (H) of the system C=
𝑑𝑇
 𝐻𝑓 − 𝐻𝑖 = 𝑞
➢ Molar heat capacity varies with temperature
ΔU = ΔH – PΔV ❑ Molar heat capacity at constant volume
𝜕𝑈
or, ΔH = ΔU + PΔV 𝐶𝑣 =
@ constant volume w = 0 & ΔU = q 8
𝜕𝑇 𝑣
 Heat Capacity
Molar heat capacity at constant pressure (Cp)
ΔU = q - w
@ constant pressure, 𝝏𝑯
ΔU = q – P (𝑉𝑓 − 𝑉𝑖 ) As quantity (U+PV) is the
there is change in  𝑪𝒑 =
or, q = ΔU + pΔV enthalpy (H) of the system 𝝏𝑻
volume & some work is 𝒑
done
❑ Relationship between Cp & Cv ▪ For ideal gas, PV = RT (for 1 mole)
Δ(PV) = R ΔT
For a system, ΔH = ΔU + Δ(PV)
ΔH ΔU Δ(PV) RΔ(T)
or, = + 𝐶𝑝 = 𝐶𝑣 +
ΔT ΔT ΔT ΔT or, 𝐶𝑝 = 𝐶𝑣 + R
Δ(PV) or, 𝑪𝒑 ― 𝑪𝒗 = R
or, 𝐶𝑝 = 𝐶𝑣 +
ΔT
CV = 3/2 R (For monoatomic ideal gas)
CP = 5/2 R (For monoatomic ideal gas)
𝑪𝒑
Heat capacity ratio, 𝜸 = 𝑪𝒗
= 5/3 for a monoatomic ideal gas
9
APPLICATION OF 1ST LAW TO THE EXPANSION WORK

Isothermal Process (constant temperature)

In an isothermal process,
the temperature stays
constant, so the pressure
work done and volume are inversely
proportional to one
another
For an ideal gas,
The internal energy (U) ∝ Temperature (T)
if T = fixed, ΔU = 0 (according to 1 st law, which deals with ΔU)

Pressure-volume diagram ▪ If the system does work, the energy

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
surrounding. 10
 APPLICATION OF 1ST LAW TO THE EXPANSION WORK

➢ Reversible isothermal expansion:

𝑣 𝑣 𝑛𝑅𝑇
w = ‫𝑃 𝑓 𝑣׬‬dv = ‫𝑓 𝑣׬‬ dv (as PV = nRT)
𝑖 𝑖 𝑉
(throughout the expansion, Pex = P as the expansion is reversible)
▪ Work done by the n moles of gas can be
evaluated as: 𝑉𝑓 𝑃
w = 𝑛𝑅𝑇 ln = 𝑛𝑅𝑇 ln 𝑖
𝑉𝑖 𝑃𝑓
𝑉𝑓 𝑃𝑖
(since = in an isothermal expansion of a perfect gas)
𝑉𝑖 𝑃𝑓
➢ 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.
𝑣
w = ‫ 𝑥𝑒𝑃 𝑓 𝑣׬‬dv =0 ➢ The work done during the irreversible
𝑖
a) Volume of the gas expands against a constant expansion against the same final
pressure. pressure is equal to the rectangular area
𝑣 shown slightly darker. NOTE THAT THE
w = ‫ 𝑥𝑒𝑃 𝑓 𝑣׬‬dv = Pex (Vf – Vi)
𝑖
REVERSIBLE WORK DONE IS GREATER THAN
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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 system. ▪ Relation between T, V and P
▪ 1st law of thermodynamics: 𝛾−1
ΔU = - w 𝑇𝑖 𝑉𝑓
= 𝑇𝑖 𝑉𝑓
𝑇𝑓 𝑉𝑖  ln = 𝛾 − 1 𝑙𝑛
(as no heat is allowed to enter/leave the system, q = 0) 𝑇𝑓 𝑉𝑖

Example: A gas expanding so quickly that no heat can be 𝑇𝑖 𝑪𝒑 𝑉𝑓 𝐶𝑝

transferred. Due to the expansion work, temperature  ln = − 1 𝑙𝑛 [𝑎𝑠, 𝛾 = ]
𝑇𝑓 𝑪𝒗 𝑉𝑖 𝐶𝑣
drops. This is exactly what happens with a carbon dioxide
𝑇𝑖 𝑹 𝑉𝑓
fire extinguisher, with the gas coming out at high pressure  ln = 𝑙𝑛 [𝑎𝑠, 𝐶𝑝 ― 𝐶𝑣 = R]
𝑇𝑓 𝑪𝒗 𝑉𝑖
and cooling as it expands at atmos. pressure
𝑻𝒊 𝑽𝒇
Expansion: w = +ve, ∆𝑼 = ― ve;  𝑪𝒗 ln = 𝑹 𝒍𝒏
𝑻𝒇 𝑽𝒊
So, T of the system falls
 Work is done by the system at the expense of ➢ Irreversible adiabatic expansion
its internal energy ▪ Free expansion (Pex = 0) : ∆𝑇 = 0, 𝑊 = 0, ∆𝐻 = 0
▪ w = ∆𝑈 = 𝑪𝒗 𝚫𝑻 (for 1 mole of gas) ▪ Expansion against a constant pressure:
𝑇𝑖 𝑃𝑓 − 𝑇𝑓 𝑃𝑖
▪ ∆𝐻 = 𝑪𝒑𝚫𝑻 (for 1 mole of gas) 𝐶𝑣 𝑇𝑓 − 𝑇𝑖 = 𝑅 𝑃𝑒𝑥
𝑃𝑖 𝑃𝑓 12
 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
process is simply the pressure multiplied by the ✓ Example of an isochoric system: A gas in a
change in volume box with fixed walls
✓ Example of an isobaric system: A gas, being
slowly heated or cooled, confined by a piston in a
cylinder.

13
 NUMERICAL FROM OF 1ST LAW
Example 1: Calculate w and ∆𝑈 for the conversion of 1 Example 2: 1 mole of an ideal gas expands
mole of water at 100 ℃ to steam at 1 atm pressure. against a constant external pressure of 1 atm
Heat of vaporisation of water at 100 ℃ is 40670 Jmol-1 from a volume of 10 dm3 to a volume of 30 dm3.
Assume ideal gas behaviour Calculate the work done by the gas in Joules.

Solution: Solution:
P = 1 atm 𝑤 = 𝑃𝑒𝑥𝛥𝑉
Vi = vol. of 1 mole of liquid water at 1 atm pressure = 1 𝑎𝑡𝑚 30 𝑑𝑚3 − 10𝑑𝑚3
= 18 ml = 18 × 10-3 L = 20 𝑑𝑚3 𝑎𝑡𝑚
Vf = nRT/P = 1 x .0821 x 373/1 = 30.6 L
w = P (Vf - Vi) 1 atm dm3 = 101.325 J
= 1 (30.6 -0.018) = 30.582 L atm = 30.582 x 101. 35 Therefore,
= 3099.48 J 𝑤 = 20 𝑑𝑚3 𝑎𝑡𝑚
Since, conversion of water to steam is
accompanied by increase in volume, work is done w= 20 𝑑𝑚3 × 101.325 = 2026.5 J
by the system on the surroundings.
Hence, w = 3099 Jmol-1
Since, ΔU = q-W = 40,670-3099.48 = 37,571 Jmol-1
14
 NUMERICAL FROM OF 1ST LAW
Example 3: 1 mole of an ideal monoatomic gas at 27 C expands reversibly and adiabatically from a
𝐶 3
volume of 10 dm3 to a volume of 20 dm3. Calculate q, ∆U, W and ∆H. Given 𝑣 =
𝑅 2
Solution:
Since the process is adiabatic, q = 0 Since for an adiabatic process, q =0,
𝑇𝑓 𝑉 hence ΔU = w = 1384 J
𝐶𝑣 ln = 𝑅 ln 𝑖
𝑇𝑖 𝑉𝑓
3 𝑇𝑓 10 𝑑𝑚3 ΔH can also be calculated by using the relation 𝑑𝐻 =
 ln = ln( )  Tf = 189K 𝐶𝑝 𝑑𝑇
2 300 20 𝑑𝑚3
𝜕𝑈 For a finite change in n moles,
𝐶𝑣 =  𝑑𝑈 = 𝐶𝑣 𝑑𝑇
𝜕𝑇 𝑣 ∆𝑈 = 𝑛𝐶𝑝∆𝑇
5
For a finite change in n moles, = (1 mol) × 8.314 𝐽 𝑚𝑜𝑙−1 𝐾 −1 (189 − 300)𝐾
2
∆𝑈 = 𝑛𝐶𝑣 ∆𝑇 = – 2307 J
3
= (1 mol) × 8.314 𝐽 𝑚𝑜𝑙−1 𝐾 −1 (189 − 300)𝐾
2
= – 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.
𝑃𝑖 10 𝑎𝑡𝑚
Solution: w = 𝑛𝑅𝑇 ln =(10 mol) 8.314 𝐽 𝑚𝑜𝑙−1 𝐾 −1 300 𝐾 ln = 40.15 × 103J 15
𝑃𝑓 2 𝑎𝑡𝑚
 Entropy
The 1st law & the 2nd law of thermodynamics were summed up by German Physicist Rudolf Clausius as
below:
THE ENERGY OF THE UNIVERSE REMAINS CONSTANT; THE ENTROPY OF THE UNIVERSE TENDS
TOWARDS A MAXIMUM
➢ Heat engine
▪ Its a device which transforms heat into work
▪ This happens in a cyclic process
▪ Heat engines require a hot reservoir to supply energy (QH) and
a cold reservoir to take in the excess energy (QC)
– QH is defined as positive, QC is defined as negative

➢ Carnot Cycle
▪ A Carnot cycle (named after the French engineer Sadi Carnot)
consists of four reversible stages in which a gas (the working
substance) is either expanded/compressed in various ways
▪ To demonstrate the maximum convertibility of heat into work
▪ The system consists of 1 mole of an ideal gas which is
subjected to four strokes 16
 CARNOT CYCLE

➢ Four stages of Carnot Cycle: A. 1st stroke:

Curve AB: A→B: Isothermal expansion at Th
Work done by the gas
 The gas is placed in thermal contact with QH (at Th) and
undergoes reversible isothermal expansion from A to B.
 The entropy change is qh/Th ( qh = the energy supplied to
the system as heat from the hot source)
𝑽𝑩
𝒒𝒉 = −𝒘𝟏 = 𝑹𝑻𝒉 𝒍𝒏
𝑽𝑨
B. 2nd stroke:
Curve BC (B → C): Adiabatic expansion,
Work done by the gas

 Contact with QH is broken & the gas undergoes

reversible adiabatic expansion from B to C.
Since  No energy leaves the system as heat, ΔS = 0
 The expansion is carried on until the temperature
𝜕𝑈 of the gas falls from Th to Tc (the temperature of Qc)
𝐶𝑣 =
𝜕𝑇 18
𝑣 −𝒘𝟐 = −𝑪𝒗 (𝑻𝒉 − 𝑻𝒄)
CARNOT CYCLE
C. 3rd stroke:
Curve CD (C → D): Isothermal compression at TC,
Work done on the gas.
▪ The gas is placed in contact with the cold sink (Qc) and undergoes a
reversible isothermal compression from C to D at Tc.
▪ Energy is released as heat to the cold sink; the entropy change of
the system = qc/Tc, where qc is negative.
𝑉𝐷
−𝑞𝑐 = 𝑤3 = 𝑅𝑇𝑐 ln
𝑉𝐶
D. 4th stroke:
Curve DA (D → A): Adiabatic compression
Work done on the gas
▪ Contact with Qc is broken and the gas
undergoes reversible adiabatic compression
from D to A such that the final temperature is Th.
▪ No energy enters the system as heat, so the q is
zero.
▪ Hence, ΔU = -w
𝑤4 = 𝐶𝑣 (𝑇ℎ − 𝑇𝑐 ) 19
 CARNOT CYCLE
The area enclosed by the four curves represents the net
work done by the engine in one cycle
Total workdone W = w1 + w2 + w3 + w4
= R Th ln (VB/VA) – RTc(VC/VD)
Since VB/VA = VC/VD, W = R(Th-Tc) ln (VB/VA)
W/qh = (Th-Tc)/Th
Efficiency = (Th-Tc)/Th = 1- Tc/Th
In addition to this, w = qh-qc

Efficiency of a heat engine

The thermal efficiency of a heat engine is

𝑤𝑜𝑟𝑘 𝑝𝑒𝑟𝑓𝑜𝑟𝑚𝑒𝑑 𝑊
𝜂 = ℎ𝑒𝑎𝑡 𝑎𝑏𝑜𝑠𝑟𝑏𝑒𝑑 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 ℎ𝑜𝑡 𝑠𝑜𝑢𝑟𝑐𝑒 = 𝑞 = 1 − 𝑞𝑐 /𝑞ℎ = 1 − 𝑇𝑐 /𝑇ℎ
ℎ

• Another statement of the 2nd Law:

➢ The “engine” statement of the 2nd Law:
– It is impossible for any process to have as its
– it is impossible for any system to have an
sole result the transfer of heat from a cooler
efficiency of 100% (𝜂 = 1)[Kelvin’s statement] object to a warmer[Clausius’s
object statement]20
 APPLICATION OF THE CARNOT CYCLE

• Energy efficiency of the

Carnot cycle is independent
of its working substance.
• Any cyclic process that
absorbs heat at one
temperature and rejects
heat at another temperature
and is reversible has the
energy efficiency of a
Carnot cycle.

Thermal devices or thermal machines are one of

the applications of this cycle.
✓ The heat pumps to produce heating, Refrigeration, Air conditioners & Heat pumps
✓ The refrigerators to produce cooling, ● These appliances are heat engines operating
✓ The steam turbines used in the ships, in reverse.
✓ The combustion engines of the combustion ● By doing work, heat is extracted from the cold
vehicles reservoir & exhausted to the hot reservoir
21
✓ The reaction turbines of the aircraft
 NUMERICAL
Example 1: Calculate the efficiency of a Example 3: Heat supplied to a Carnot engine is 1897.8 kJ.
certain power station operates with How much useful work can be done by the engine which works
superheated steam at 300 ℃ (Th = 573 K) between 0 ∘C and 100 ∘C.
and discharges the waste heat into the
environment at 20 ℃ (T = 293 K). Solution:
Tc​= 0 + 273 = 273 K, Th ​= 100 + 273 = 373 K
Solution: Tc= (1 − η)Th qh = 1897.8 kJ
 η = 1 – (Tc /Th) 𝑇
w = 𝑞ℎ × (1 − 𝑐 )
𝑇ℎ
Theoretical efficiency (η) = 1 – (293K/573K) = 1897.8 kJ × (1 −
273 𝐾
)
= 0.489 373 𝐾
= 48.9 % = 508.7 kJ
 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: 𝜂 = 1 – (298 K/373 K)
Tc​ = 25 + 273 = 298K Tc= (1 − η)Th
= 0.201
For engines, we have Th​ = 100 + 273 = 373 K  η = 1 – (Tc /Th) = 20.1 % 22
 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 permissible changes
anything about the direction of change. The direction ➢ the 2nd law uses the entropy to identify which
of spontaneous change of a process is defined by of these permissible changes are
the 2nd law of thermodynamics spontaneous.
• A spontaneous process points towards the
❑ 2nd law of thermodynamics direction in which the total entropy
increases.
▪ Heat does not flow spontaneously from a cool ➢ Entropy (S) is a state function
body to a hotter body
▪ The entropy (S) of an isolated system increases in Thermodynamic definition of entropy
the course of a spontaneous change. → The thermodynamic definition of entropy
ΔStot > 0 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 reversibly to the system at the absolute
a statement about the total entropy of the overall isolated temperature T.
system (the ‘universe’), not just about the entropy of the
𝒇 𝒅𝒒
system of interest. 𝒅𝑺 = 𝒅𝒒𝒓𝒆𝒗ൗ𝑻, 𝜟𝑺 = ‫ 𝒊׬‬23𝒓𝒆𝒗
𝑻
 ENTROPY
Process that lead to an increase in entropy (ΔS > 0) Entropy change for the system - isothermal
expansion of a perfect gas

ΔU = 0, q = w  𝑞𝑟𝑒𝑣 = 𝑤𝑟𝑒𝑣
as, wrev = nRT ln (𝑉𝑓 /𝑉𝑖)
[from the expression of work done in a reversible
isothermal expression]
 𝑞𝑟𝑒𝑣 = 𝑛𝑅𝑇𝑙𝑛(𝑉𝑓/𝑉𝑖)

as 𝑑𝑆 = 𝑑𝑞𝑟𝑒𝑣ൗ𝑇

 Δ𝑆 = 𝑛𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖)

Δ𝑆𝑚 = 𝑛𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖)

☻ Notice the increasing disorder in above processes 24

 ENTROPY
Total Entropy change in irreversible (spontaneous) Isothermal Reversible expansion
process of a perfect gas w = −𝑝Δ𝑉 & qrev = 𝑝Δ𝑉
Example: Isothermal expansion of an ideal gas at 𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 +
constant temperature into vacuum 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔
𝑞𝑟𝑒𝑣 𝑞𝑟𝑒𝑣
= + −
As, w = 0, 𝛥𝑈 = 0  𝑞 = 0 [from 1st
law] 𝑇 𝑇
 no heat is absorbed by =0
or removed from the surrounding, ▪ In an isolated system, there is no heat transfer
Hence, Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 0 and 𝑑𝑞 = 0 , thus dS ≥ 0
Δ𝑆𝑚 = 𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖) All natural processes are spontaneous &
As, 𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 irreversible.
 Δ 𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 ▪ Reversible process:
= 𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖) + 0 𝑑𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑠𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = 0
= 𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖)
▪ Irreversible process
As Vf > 𝑉𝑖, this spontaneous (irreversible) 𝑑𝑆𝑡𝑜𝑡𝑎𝑙 > 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑠𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 > 0
isothermal expansion of a gas is accompanied
All spontaneous process occurring in
by the increase in entropy.
Nature is irreversible, entropy of the
universe is increasing continuously 25
 Entropy

▪ The 1st law & the 2nd law of thermodynamics were summed up by German Physicist Rudolf Clausius as
below:
The energy of the universe remains constant; the entropy of the universe tends towards a
maximum

Entropy change during different processes

▪ For an ideal gas (1 mole) with variable T
&V
𝑇𝑓 𝑉𝑓
∆𝑆 = 𝐶𝑣 ln + 𝑅 ln
𝑇𝑖 𝑉𝑖
▪ For an ideal gas with variable P & T
𝑇𝑓 𝑃𝑓
∆𝑆 = 𝐶𝑝 ln − 𝑅 ln
𝑇𝑖 𝑃𝑖
▪ For an ideal gas in an isothermal process
𝑉𝑓 𝑃𝑓
∆𝑆𝑇 = 𝑅 ln = − 𝑅 ln
𝑉𝑖 𝑃𝑖
▪ For an ideal gas in an isobaric process
𝑇𝑓
∆𝑆𝑃 = 𝐶𝑝 ln
𝑇𝑖
▪ For an ideal gas in an isochoric process
𝑇𝑓
∆𝑆𝑣 = 𝐶𝑣 ln
𝑇𝑖 26
 Numerical from 2nd Law of Thermodynamics

Example 4: 5 mole of an ideal gas expands Example 5: Calculate the change in entropy
reversibly from a volume of 8 dm3 to 80 accompanying the heating of 1 mole of Helium gas
dm3 at a temperature of 27 ∘C. Calculate (assumed ideal) from a temperature of 298 K to a
the change in entropy. temperature of 1000 K at constant pressure. Assume Cv
Solution: =3/2 R
Δ𝑆 = 𝑛𝑅𝑙𝑛(𝑉𝑓/𝑉𝑖) Solution: As 𝐶𝑝 − 𝐶𝑣 = 𝑅
 Cp =𝐶𝑣 + 𝑅 = 2.5 𝑅
Given that 𝑛 = 5, 𝑉𝑓 = 80 dm , 𝑉𝑖 = 8 dm
3 3
𝑇𝑓
∆𝑆𝑃 = 𝐶𝑝 ln = 2.5 × 8.314 𝐽𝑚𝑜𝑙−1 𝐾 −1 ln 1000𝐾
Δ𝑆 = (5 mol) (8.314 J K-1mol-1) 𝑙𝑛(80 dm3/8 dm3) 𝑇𝑖 298𝐾
= 25.17 𝐽𝑚𝑜𝑙 −1 𝐾 −1
= 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: 𝑇𝑓 𝑉𝑓
∆𝑆 = 𝐶𝑣 ln + 𝑅 ln
𝑇𝑖 𝑉𝑖
250 𝐾
= 1.5(8.314 𝐽𝑚𝑜𝑙−1 𝐾 −1 ) ln + (8.314 𝐽𝑚𝑜𝑙−1 𝐾 −1 ) ln (20 dm3/10
298𝐾
dm3)
= 3.57 JK-1mol-1 27
 FREE ENERGY

➢ Free energy and the spontaneity

As, Δ 𝑆𝑡𝑜𝑡𝑎𝑙 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔
and Δ 𝑆𝑡𝑜𝑡𝑎𝑙 is a criterion for the spontaneity/feasibility of a process.
▪ It is not always easy to know the entropy change of both system and the surrounding
▪ We can express this in terms of G (the free energy function) and thus can device a
criterion of spontaneity in terms of the state function of the system.
There are few assumptions:
Assumption no 1:
The system is in thermal equilibrium with its surroundings at a temperature T.
Assumption no 2:
Heat transfer between the system and the surrounding happens at constant volume
Assumption no 3:
Heat transfer between the system and the surrounding happens at constant pressure.
28
 FREE ENERGY
Under the Assumption 1 & Assumption 2 The criterion of spontaneity in terms of Gibbs Free
𝑑𝑈 energy change (dG) and Helmholtz energy (dA)
Clausius inequality becomes: dS − ≥0
𝑇
𝑑𝐺 ≤ 0 & 𝑑𝐴 ≤ 0
[we get this by applying the 1st law &
In an endothermic reaction:
the 𝑑 𝑞𝑣 = 𝑑𝑈]  TdS ≥ dU
dH > 0
dA=dU−TdS [A = Helmholtz free but if such a reaction is to be spontaneous at constant
energy] temperature and pressure, G must decrease.
 A=U−TS
as ∆G = ∆ H − T ∆ S
it is possible for ∆G to be
Under the Assumption 1 & Assumption 3
𝑑𝐻 negative provided that the
Clausius inequality becomes: dS − ≥ 0 entropy of the system
𝑇
[constant P, no additional work]  TdS ≥ dH increases so much that T ∆ S
outweighs ∆ H.
dG = dH−TdS [G = Gibbs free energy] Endothermic reactions are
therefore driven by the
 G=H−TS increase of entropy of the
system 29
 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:
𝑃2
∆𝐺 = 𝑛𝑅𝑇 ln
𝑃1
𝑉1
= 𝑛𝑅𝑇 ln
𝑉2

30
 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 the
total number of ways a molecular state If the value zero is ascribed to the entropies of elements in
can be distributed over the energy their perfect crystalline form at T = 0, then all perfect
states for a specific value of total crystalline compounds also have zero entropy at T = 0
energy.
Third law of thermodynamics:
The entropy of all perfect crystalline substances is zero at T = 0.
31
 Module 2

B. CHEMICAL KINETICS

32
 What is Chemical kinetics?
Chemical kinetics is the branch of chemistry which deals with the study
of rates (velocity) 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
33
 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.

34
 The rates of reactions

Consider a general reaction,

A+B→C
d A d B  d C 
The rate of reaction will be: −
dt
=−
dt
=
dt

Consider another general reaction: aA + bB → cC + dD

where a, b, c d are stoichiometric coefficients

− 1 d A 1 d B  1 d C  1 d D 
The rate of reaction will be: a dt = − = =
b dt c dt d dt

35
 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:

d NO2  d CO d NO d CO2 

1. − =− = =
dt dt dt dt

1 d HI  d H 2  d I 2 
2. − = =
2 dt dt dt

36
 Rate Laws and Rate Constants
The rate law is the relationship between the rate and 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 and k is the

rate constant.

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

37
 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).

✓ Rate = k[A]m[B]n

✓ 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. 38
 Molecularity
Kinetics of the elementary step depends only on the number of reactant
molecules in that step.
Molecularity - the number of reactant molecules that participate in
elementary steps
 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)

40
 Order of a Reaction

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)

41
 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
d  A
Rate = − dt = k A
Separate concentration and time terms
d A
= −kdt
A
Integrating over the limits [A]0 to [A]t and 0 to t,
d A
 A = −k  dt
d A
[ A ]t t


[ A ]0
 A
= − k 
0
dt

ln At − ln A0 = −kt 42

Continue….
 INTEGRATED RATE LAWS
ln At = −kt + ln A0 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.

43
 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.
44
 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. 45
 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 = −ktt / 2
A0
1
ln = −ktt / 2
2
− 0.693 = −ktt / 2
tt / 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 2)/k. 46
 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

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? 0.375 g
ln
At = − kt ln
At / t = −k ln
3g
Solution: A0 A0 k =−
36 min

k =0.0578 min-1
ln 2 0.693
t1 / 2 = = = 12 min
k 0.0578
47
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

48
 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. 49
 TEMPERATURE DEPENDENCE OF REACTION RATES
The rate constant of most reactions increases with increase in the temperature.
Ea
Arrhenius equation ln k = ln A −
RT
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. 50
 Temperature dependence of reaction rates
Questions:
1. The rate of the second-order decomposition of acetaldehyde (CH3CHO) 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
51
 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 500 K and 600 K respectively. Calculate the activation

energy.
Solution: ln k2 = − Ea  1 − 1 
 
k 1 R T T 2 1 
−1
k 1 1
Ea = − R ln 2  − 
k1  T2 T1 

After substituting the given values and calculating,

Ea= 176 kJ/mol

52
ENERGY BARRIER: INTERPRETATION OF ARRHENIUS PARAMETERS
Ea
ln k = ln A −
RT
One can rewrite the above equation as:
Ea
−
k = Ae RT

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
53
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.
54
 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
❖The pre-exponential factor is a measure of the rate at for an exothermic
reaction. The height of
which collisions occur irrespective of their energy.
the barrier between the
Hence, the product of A and the exponential factor, reactants and products is
e−Ea/RT, gives the rate of successful collisions. the activation energy of
the reaction. 55
 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.

56
 COLLISION THEORY
Quantitatively, for two reactions at the same temperature
✓ The reaction with the higher activation energy has the lower rate constant and the
E
slower rate. The larger value of Ea results in a smaller value for e − RT reflecting the
a

smaller fraction of molecules with enough energy to react.

✓ The reaction with the smaller Ea has a larger fraction of molecules with enough energy
E
to react. This will be reflected as a larger value of e − RT , a larger rate constant, and a
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
Ea, as shown by the yellow shaded area. 57
MODULE 2

C. CATALYSIS

58
 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.

59
60
 DEFINITION OF CATALYSIS
“A catalyst is a chemical entity which by virtue of its presence in a
reaction 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.

61
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.

62
 CHARACTERISTICS OF CATALYSTS

✓ The catalyst remains unchanged (in mass and chemical composition)

in the reaction.

✓ A small quantity of the catalyst is required.

✓ The catalyst does not change the equilibrium constant but the
equilibrium approaches earlier.

63
 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:
diagram to illustrate the

activation energy of
effect of catalyst on
Figure: Schematic

reactions.

64
 TYPES OF CATALYSIS
Following are the main types of catalysis:

1. Heterogeneous catalysis

2. Homogeneous catalysis

3. Enzyme catalysis

65
1. HETEROGENEOUS CATALYSIS
If the catalyst is present in a different phase than the reactants it 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.

66
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)

67
 EXAMPLES OF HETEROGENEOUS CATALYST

(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)

68
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.

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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)
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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:
(cane sugar) (glucose) (fructose)
C12H22O11 (aq) + H2O (l) → C6H12O6 (aq) + C6H12O6 (aq)

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 D. ENZYME CATALYSIS
MICHAELIS-MENTON MECHANISM

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 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. Molecular structure of Catalase

❑ Example of an enzyme catalysed reaction is H2O2 → H2O + O2

catalase that converts hydrogen peroxide to
water and oxygen. It is an important enzyme Reaction catalysed by the
protecting the cell from oxidative damage by enzyme, catalase
reactive oxygen species (ROS) 73
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.
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 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
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