CY11003 

Physical Chemistry 3/13/2023

CY 11003 CHEMISTRY
Sections 3 and 4

Physical  Inorganic Organic 

Chemistry Chemistry Chemistry

Srabani Taraphder Ganesan Mani Kumar Biradha

Physical Chemistry
Teacher Prof. Srabani Taraphder
Office: Room B‐111
(Department of Chemistry, J C Ghosh‐P C Ray Block)
E‐mail: srabani@chem.iitkgp.ac.in
Phone: 83336

• Attendance is mandatory

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Srabani Taraphder Department of 
Chemistry IIT Kharagpur 1
CY11003 Physical Chemistry 3/13/2023

CLASS SCHEDULE

CLASS TIMINGS
Monday     12:00 pm – 12:55 pm 
Tuesday    10:00 am – 11:55 am

©Bill Waterson

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 2
CY11003 Physical Chemistry 3/13/2023

Tutorials

Section Roll No. Section Roll No.

3A+B 22AG‐22EX 4A+B 22AG‐22EX

3C+D 22GG‐22QD 4C+D 22GG‐22QD

Tutorials (Physical Chemistry)
Section Teacher Day & time Venue
3A+B Arpita Poddar Thursday, 09:00‐09:55 NR‐113
3C+D Manisha Khamrai Thursday, 09:00‐09:55 NR‐114

Section Teacher Day & time Venue

4A+B Anusree Mandal Friday, 14:00‐14:55 NR‐113
4C+D Juthi Pal Friday, 14:00‐14:55 NR‐114

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 3
CY11003 Physical Chemistry 3/13/2023

Reading material
Text Book:

Atkin’s Physical Chemistry by P. W. Atkins and others (8th or later edition), Oxford 

University Press 

Reference Books:

Physical Chemistry by Silbey Alberty Bawendi , John Wiley & Sons

Physical Chemistry by I. Levine, McGraw‐Hill
Physical Chemistry by D. W. Ball, Thompson
Heat and Thermodynamics by M. W. Zemansky and R. H. Dittman, McGraw‐Hill

Lecture slides:      Microsoft Teams/Google Drive 

CY 11003 CHEMISTRY

• Principles of Thermodynamics:
• First and Second Law of Thermodynamics
•Concept of Entropy, Helmholtz and Gibbs Free Energy
•Equilibrium and spontaneity conditions for Closed Systems
•Maxwell Relations
•The Chemical Potential; Definition and Concept of Open Systems

• Application of thermodynamics to real world problems
•Phase Equilibria
•Reaction Equilibria
•Electrochemical Equilibria

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 4
CY11003 Physical Chemistry 3/13/2023

Review of
Essential Concepts and Definitions

Image Source:         Google    

Primary Goal of Thermodynamics

• Quantitative description of an equilibrium state of a system

• Determination of the equilibrium state that eventually results when the

system undergoes a change in state

• How and to what extent we can harvest energy from different sources

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 5
CY11003 Physical Chemistry 3/13/2023

Harnessing the Energy

Converting Energy into Useful Work

© imgur.com

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 6
CY11003 Physical Chemistry 3/13/2023

Essential Concepts
System

Change in state  Harnessing energy 
Equilibrium state during change in 
From one equilibrium 
state to another state

How do we maximize the
How do we prepare  How do we carry out the  amount of energy 
the system in an  change in state? extracted to do useful 
equilibrium state? work?

Macroscopic System
• System
A part of the universe whose properties are being investigated

• Surrounding  
Rest of the universe  Surrounding

• Macroscopic dimensions
 Length – 1 meter
 Time – 1 minute
 Number of particles ‐ 𝟔. 𝟎𝟐𝟑 𝟏𝟎𝟐𝟑

• A system in Equilibrium
All measurable properties are independent of time  System

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 7
CY11003 Physical Chemistry 3/13/2023

System, Surrounding and Wall
The system interacts with the surrounding through the wall

Surrounding

Wall

System

Examples

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 8
CY11003 Physical Chemistry 3/13/2023

Thermodynamics
Equilibrium properties of macroscopic systems 

There exist particular states (called equilibrium states) of simple

macroscopic systems that are characterized completely by

three independent variables

Equilibrium State of a Macroscopic System
System:    1 mole of an ideal gas

Isolated system
At equilibrium, the isolated 
system has

Gas • Constant energy, 𝑼
• Constant volume, 𝑽
• Constant number of 
particles, 𝑵
The system cannot exchange  
Wall   energy, 
 adiabatic,   volume or 
 rigid,   matter
 impermeable to the gas with its surroundings

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 9
CY11003 Physical Chemistry 3/13/2023

Thermodynamics
Equilibrium properties of macroscopic systems 
There exist particular states (called equilibrium states) of simple macroscopic
systems that are characterized completely by
three variables.

In an isolated system, the equilibrium state is defined in terms of

 Internal energy, U
 Volume, V
 Number of particles, N

For multi‐component systems, instead of N, one uses numbers of each species, 
𝑵𝟏 , 𝑵𝟐 , … …

Equilibrium State of a Macroscopic System
System:    1 mol of an ideal gas Closed system

Equilibrium state of 
this system

Gas 𝑻, 𝑽, 𝑵

Thermostat At equilibrium, the system has

Wall  • Constant temperature, 𝑻
 diathermal,  • Constant volume, 𝑽
 rigid,  • Constant number of 
 impermeable to the gas particles, 𝑵

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 10
CY11003 Physical Chemistry 3/13/2023

Equilibrium State of a Macroscopic System
System:    1 mol of an ideal gas Closed system

Equilibrium state of 
this system
Volume
𝑻, 𝒑, 𝑵
Gas

At equilibrium, the system has
Thermostat

Wall  • Constant temperature, 𝑻
 diathermal,  • Constant pressure, 𝑽
 Flexible/movable,  • Constant number of 
 impermeable to the gas particles, 𝑵

Equilibrium State of a Macroscopic System
System:    1 mol of an ideal gas Open system

Equilibrium state of 
this system

Gas 𝑻, 𝑽, 𝝁

Thermostat At equilibrium, the system has

Wall  • Constant temperature, 𝑻
 diathermal,  • Constant volume, 𝑽
 rigid,  • Constant chemical potential, 𝝁
 permeable to the gas

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 11
CY11003 Physical Chemistry 3/13/2023

System and its Interaction with the Surroundings

System Wall Equilibrium

state
Open Diathermal Rigid Permeable 𝑻, 𝑽, 𝝁

Closed Diathermal Rigid Impermeable 𝑻, 𝑽, 𝑵

Diathermal Flexible Impermeable 𝑻, 𝒑, 𝑵

Isolated Adiabatic Rigid Impermeable 𝑼, 𝑽, 𝑵

Understanding the Change in State
Experiment: System is brought in thermal contact with a hot thermostat to 
make the system undergo a change in state from its initial equilibrium state

𝑻, 𝑽, 𝑵 𝑻 , 𝑽, 𝑵

Initial equilibrium state Final equilibrium state

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 12
CY11003 Physical Chemistry 3/13/2023

Thermal Equilibrium Mechanical Equilibrium Material Equilibrium

Porous wall for matter 
flow

Equal chemical potential

Thermodynamics of systems in contact with reservoir(s)

Reservoir type Thermodynamic state  of  Condition of equilibrium

system

Thermostat T, 𝑽, 𝑵 𝑻𝒔𝒚𝒔𝒕𝒆𝒎 𝑻𝒓𝒆𝒔𝒆𝒓𝒗𝒐𝒊𝒓

Thermostat+ Barostat T, 𝒑, 𝑵 𝑻𝒔𝒚𝒔𝒕𝒆𝒎 𝑻𝒓𝒆𝒔𝒆𝒓𝒗𝒐𝒊𝒓

𝒑𝒔𝒚𝒔𝒕𝒆𝒎 𝒑𝒓𝒆𝒔𝒆𝒓𝒗𝒐𝒊𝒓

Srabani Taraphder Department of 
Chemistry IIT Kharagpur 13
CY11003 Physical Chemistry 3/13/2023

A molecular‐level machine can be defined as “an

assembly of a distinct number of molecular
components that are designed to perform
machinelike movements (output) as a result of an A rotaxane consists of a 
crown ether threaded on a 
appropriate external stimulation (input)”. dumbbell‐shaped structure 
Furthermore, a machine requires a supply of (top). When light shines on it 
(model, bottom) the crown 
energy for its operation, and can be driven by ether moves along the 
dumbbell 
suitable energy sources.
www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/ Credit: COURTESY OF ALBERTO CREDI, 
UNIVERSITY OF BOLOGNA
advanced‐chemistryprize2016.pdf

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