CHY-111: Chemical Principles

Dr. Parthapratim Munshi

Department of Chemistry
Office: R-116, first floor, Research Block

E-mail: parthapratim.munshi@snu.edu.in
http://www.snu.edu.in/naturalsciences/parthapratim_munshi_profile.aspx
www.parthapratimmunshi.weebly.com

PhD from:
Solid State and Structural Chemistry Unit (SSCU)
Indian Institute of Science (IISc.), Bangalore, India
Research Experiences in Australia, France and USA

CHY-111: Principles of Chemical Equilibrium and Kinetics

Thermodynamics
Energy
Chemical Kinetics
Chemical Equilibrium
Total 14 lectures; Assignments 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
Carnots 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)

Heat

Dynamite/Power

Greek

Study of transformation of energy via heat and work

Main ingredients/components

has great practical value in

Physics, Chemistry, Biology, Geology and Engineering

System and Surroundings

Surroundings

System:
Surroundings:
Boundary:

System

Boundary

A quantity of
matter or subject
area of a study
Environment outside the system

The separator or surface between the

system and surroundings

Type of System
Isolated system
both, mass and
energy can not cross
the boundary

Hot milk in a
well-insulated
thermo flask

Closed system
only energy can
cross the boundary

Hot milk in a
tightly capped bottle

Open system
both, mass and
energy can cross the
boundary

Hot milk in an
Open glass
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
T = 20 0C
V = 1 m3
STATE -1

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

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:

P1, V1, T1

Property held constant is Pressure

Process path: A

P1 , V 2 , T 3

Isochoric ( or isometric):
Property held constant is Volume
Process path: B

Isothermal:

B
C

Property held constant is Temperature

Process path: C

Cyclic Process
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

3
P2 , V 2 , T 1

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
A

System
B

Thermal Equilibrium

System
C

Thermal Equilibrium

Thermal Equilibrium

Quiz

System
A

System
B

Thermal Equilibrium

System
C

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
Heat evolved or released from a system

+q
q

Work done on the system

Work done by the system

energy increased
energy decreased

+w
w

Work done
Pin

Initial State

Pext

Final State

Pext
h
Pf

Pi

Initial State
Pi > Pext

Final State
Pf = Pext

Pin

Work done by the system

w = Mgh
w=

. h

w = Pext V

w<0

A is area of the piston

V > 0, expansion

work is done by the gas

h
M
Pf = Pext

Pi < Pext

Work is given by
w = Pext V
w > 0,

V < 0, compression

work is done on the gas

P-V diagram
Work done

w = Pext V

If Pext is not constant =

If Pext is constant w = Pext (Vf Vi)

P 1 , V 1 , T1

The PdV work, performed during

the expansion or compression of a

system against a resisting pressure,

is graphically equal to the area

under the P V curve.

P 2 , V 2 , T1

Reversible work
Reversible work for the compression/expansion of an ideal gas
In the case of reversible process Pext = Pgas = nRT/V
2

2
=
1

2
1

Pext

1
=
2
M

For compression V2 < V1, wrev > 0

For expansion V2 > V1, wrev < 0

Final State
Pf = Pext

Pf

P-V diagram
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

w = Pext V

V = -0.5