CHY-111: Principles of Chemical Equilibrium and Kinetics

UNIT - 3

• Thermodynamics
• Energy
• Chemical Kinetics

Total 9 lectures and 1 exam

Text Book:
1. Physical Chemistry – A molecular Approach by Donald A. McQuarrie and John D. Simon
2. Physical Chemistry - by Peter Atkins and Julio Paula
Thermodynamics
TOPICS
• Thermodynamic System & Surroundings
• Laws of Thermodynamics
• Zeroth Law
• First Law
• Thermal Process
• Thermal Process using an ideal gas
• Specific Heat capacities
• Second Law
• Heat Engines
• Carnot’s Principle and the Carnot Engine
• Refrigerators and Air Conditioners
• Entropy
• Third Law of Thermodynamics
Thermodynamics

Lecture - 1
What is Thermodynamics?
Thermodynamic System & Surroundings
Laws of Thermodynamics
Zeroth Law
First Law
What is Thermodynamics?

THERMODYNAMICS
Greek (Therme) (Dynamis) Greek

Heat Dynamite/Power

Study of transformation of energy via heat and work

Main ingredients
has great practical value in
Physics, Chemistry, Biology, Geology and Engineering
System and Surroundings

Surroundings System Boundary

Environment A quantity of The separator or

outside the matter or surface between
system subject area the system and
of a study surroundings
Type of System
Isolated system Closed system Open system
both, mass and only energy can both, mass and
energy can not cross cross the boundary energy can cross the
the boundary boundary

Hot milk in a Hot milk in a Hot milk in an

well-insulated tightly capped bottle Open glass
thermo flask
Pictures from Google search
Properties of System

Properties of a system is measured by its characteristic

Properties:
Pressure (P), Volume (V), Temperature (T), Mass (m), Energy (E) etc.

Specific Properties:
Properties per unit mass e.g. specific volume (v) = V/m; another example ?

To understand a thermodynamic system it is very important to know the

• State,
• Equilibrium conditions
• Process
State

State:
Set of properties that completely describes the conditions of a system
e.g. m, V, T

m = 1 kg
m = 1 kg T = 20 0C
T = 20 0C V = 2 m3
V = 1 m3

STATE -1 STATE -2
Equilibrium & Process
Equilibrium:
Maintaining balance in a system

Thermal Equilibrium– No Temperature gradient

Mechanical Equilibrium – No Pressure gradient

Phase Equilibrium – for system with multiple phase

but each phase with same mass
Chemical Equilibrium – No changes in Chemical composition
(No reaction occurs)

Process:
Change in a system from one equilibrium state to another
Thermodynamic Processes
Isobaric: P 1 , V 1 , T1 A P 1 , V 2 , T3
Property held constant is Pressure 1 2
Process path: A
P
Isochoric ( or isometric):
Property held constant is Volume B
Process path: B
C
Isothermal:
Property held constant is Temperature 3
Process path: C
P 2 , V 2 , T1
Cyclic Process
V
Reversible Process: e.g. swing of a frictionless pendulum
Irreversible Process: e.g. A glass of hot milk
Adiabatic Process: no heat transfer into or out of the system
e.g. perfectly insulated system
Summary

• What is Thermodynamics? (heat and work are the main ingredients)

• Thermodynamic System, Surroundings and Boundary

• Isolated system, Closed system, Open system

• Properties, Specific properties

• State, Equilibrium and Process

• Thermodynamic Processes

• Isobaric, Isochoric, Isothermal, Reversible, Irreversible, Adiabatic….

Thermodynamics

Laws of Thermodynamics
Zeroth Law
First Law
Zeroth Law of Thermodynamics
- Law of thermal equilibrium

If two bodies are in thermal equilibrium with a third body, they

are also in thermal equilibrium with each other

System System System

A B C

Thermal Equilibrium Thermal Equilibrium

Thermal Equilibrium
Quiz

System System System

A B C
Thermal Equilibrium Thermal Equilibrium
a) C is at a lower temperature than A
b) C is at a higher temperature than A
c) C and A are at the same temperature and there will be no heat flow
if they are connected
d) There is not enough information to answer the question

• Heat is something that flows and temperature is what makes heat flow.
• A difference in temperature causes heat to flow.
First Law of Thermodynamics
- Law of conservation of energy

Energy can neither be created nor destroyed, but transformed

from one state to another

heat (q) and work (w)

- mode of energy transfer between a system and its surrounding

Sign conventions:
Heat added to a system +q
Heat evolved or released from a system –q

Work done on the system +w energy increased

Work done by the system –w energy decreased
Work done
Pin Initial State Final State
Pext
Pext
h
Pf h
M M M
Pi M

Initial State Final State Pin

Pi > Pext Pf = Pext Pi < Pext Pf = Pext

Work done by the system Work is given by

w =  Mgh w =  Pext V V < 0, compression
𝑴𝒈
w= . 𝑨h A is area of the piston w > 0, work is done on the gas
𝑨

w =  Pext V V > 0, expansion

w<0 work is done by the gas
P-V diagram
Work done w =  Pext V
𝑣𝑓
If Pext is not constant 𝑤 = − න 𝑃𝑒𝑥𝑡 𝑑𝑉 If Pext is constant w =  Pext (Vf – Vi)
𝑣𝑖

P 1 , V 1 , T1
1
The PdV work, performed during
P
the expansion or compression of a
system against a resisting pressure,
is graphically equal to the area
P2, V2, T1
under the P – V curve.
2

V
Reversible work

Reversible work for the compression/expansion of an ideal gas

In the case of reversible process Pext = Pgas = nRT/V

2 2 2
𝑛𝑅𝑇 𝑑𝑉 𝑑𝑉
𝑤𝑟𝑒𝑣 = − න 𝑃𝑔𝑎𝑠 𝑑𝑉 = − න
𝑉
𝑑𝑉 = −𝑛𝑅𝑇 න ‫𝑉 ׬‬ = lnV
1 1 1 𝑉

Pext
𝑉2 For compression V2 < V1, wrev > 0
𝑤𝑟𝑒𝑣 = −𝑛𝑅𝑇 𝑙𝑛
𝑉1
For expansion V2 > V1, wrev < 0
M Pf
𝑃1
𝑤𝑟𝑒𝑣 = −𝑛𝑅𝑇 𝑙𝑛
𝑃2
𝑃1𝑉1 = 𝑃2𝑉2
Final State
Pf = Pext
P-V Problem

Consider an ideal gas that occupies 1.00 dm3 at a pressure of 2.00 atm. If the gas
is compressed isothermally at a constant external pressure, Pext , so that the final
volume is 0.500 dm3, what is the smallest value Pext can have? Calculate the work
involved using this value Pext.

PiVi = PfVf 2x1 = Pextx 0.5 Pext = 4 atm

V = -0.5 dm3

w =  Pext V = 2 dm3 atm