CY11003 

Physical Chemistry 3/13/2023

Fundamental Concepts of 
Thermodynamics

CY 11003 CHEMISTRY
Spring 2022‐2023

The Equilibrium States 
System Wall Equilibrium
state

Isolated Adiabatic Rigid Impermeable 𝑼, 𝑽, 𝑵

Closed Diathermal Rigid Impermeable 𝑻, 𝑽, 𝑵

𝑻, 𝒑, 𝑵
Diathermal Flexible Impermeable
Open Diathermal Rigid Permeable 𝑻, 𝑽, 𝝁

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

The Equilibrium States 
System Wall Equilibrium
state

Isolated Adiabatic Rigid Impermeable 𝑼, 𝑽, 𝑵

Closed Diathermal Rigid Impermeable 𝑻, 𝑽, 𝑵

𝑻, 𝒑, 𝑵
Diathermal Flexible Impermeable
Open Diathermal Rigid Permeable 𝑻, 𝑽, 𝝁

Equation of State
This is a mathematical relationship between appropriate
thermodynamic variables of a system at equilibrium
e.g. 𝒇 𝒑, 𝑽, 𝑻 𝟎

Example
• Ideal gas equation of state

𝒑𝑽 𝒏𝑹𝑻

• van der Waals equation of state

𝒂𝒏𝟐
𝒑 𝑽 𝒏𝒃 𝒏𝑹𝑻
𝑽𝟐

http://hyperphysics.phy‐astr.gsu.edu/hbase/Kinetic/idegas.html

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

Thermodynamic Processes in a closed system
From an initial equilibrium state to a final equilibrium state

• Isothermal (constant T), 

• Isobaric (constant p), 

• Isochoric (constant V)

• Adiabatic (no heat transfer)

• Exothermic & Endothermic 

• Cyclic

• Reversible & Irreversible

Reversible and Irreversible Processes
Reversible processes Irreversible processes
• Occur in  infinite number of  • Occur rapidly in a single step
steps and slowly pass 
through successive stages of 
infinitesimal quantities
• Do not remain in 
• Virtual thermodynamic  thermodynamic equilibrium
equilibrium at each of the  while passing from initial to 
small stages final state
• Backward changes of the  • Forward and backward 
thermodynamic quantities at  changes of the 
every stage is the same as in 
thermodynamic quantities 
the forward direction but 
opposite in sign are unequal

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

Reversible and Irreversible Processes
Initial state

Final state Final state

The Laws of Thermodynamics

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

First Law of Thermodynamics
•There exists an extensive state function 𝑼 such that for any 
closed system, 
∆𝑼 𝒒 𝒘

Process Sign convention

Transfer of heat to the system  𝒒 𝟎
from the surrounding
Transfer of heat from the system  𝒒 𝟎
to the surrounding
Expansion of system against an  𝒘 𝟎
external pressure
Compression of system by an  𝒘 𝟎
external pressure

First Law of Thermodynamics

• For an infinitesimal change in state, 
d𝑼 ð𝒒 ð𝒘

• For an isolated system    ð𝒒 ð𝒘 𝟎 ⇒ 𝒅𝑼 𝟎

• For an adiabatic process ð𝒒 𝟎 ⇒ 𝒅𝑼 ð𝒘

• For a cyclic process            ∆𝑼 ∮ 𝒅𝑼 𝟎⇒ 𝒒 𝒘 𝟎

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

Work and Heat
 For an isochoric process, 
insert the locking pin so the 
volume cannot change.

 For an isothermal process, 
keep the thin bottom in 
thermal contact with the 
flame or the ice.

 For an adiabatic process, 
add insulation beneath the 
cylinder, so no heat is 
transferred in or out. 

Work
Pressure‐volume work
work of expansion (or compression)

pex = external pressure
A = piston area
dz = displacement
dV = A dz =volume change for the gas

Work is required to move an object a distance dz against an 
opposing force F. Total work done,
Vf Vf

w    F dz    ( p ex A )dz    p ex dV    pdV Only for reversible process

Vi Vi

dV  change in the volume of the system

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

Work

Other types of work –
not considered in the present discussion

Heat
• Heat is transferred between a
system and surrounding by
virtue of a temperature
difference only.

• Heat is not a state function

(path dependent).

• Heat can be transferred

reversibly or irreversibly. A
reversible transfer of heat
requires the temperature
difference between two bodies
to be infinitesimal.

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

Expansion against constant pressure
Vf

w    p ex dV   p ex (V f  Vi )   p ex  V
Vi

Expansion against constant final pressure:

w   p f (V f  Vi )

Free expansion: 
Expansion against zero opposing force
w = 0

Expansion, i.e., Vf > Vi , w < 0 (work done by the system on surrounding)

Compression, i.e., Vf < Vi , w > 0 (work done on the system by surrounding)

Pressure‐Volume Work 
by/on
an Ideal Gas

𝟐
𝒘 𝒑𝒆𝒙𝒕 𝒅𝑽 𝒑𝑽 𝒏𝑹𝑻
𝟏

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

Work done by Isothermal expansion of an ideal gas 
Reversible isothermal change:  𝒑𝒆𝒙𝒕 𝒑 at every stage
𝟐 𝑽𝟐 𝑽𝟐
𝒏𝑹𝑻 𝒅𝑽 𝑽𝟐
𝒘𝒓𝒆𝒗 𝒑𝒅𝑽 𝒅𝑽 𝒏𝑹𝑻 𝒏𝑹𝑻 𝐥𝐧
𝟏 𝑽𝟏 𝑽 𝑽𝟏 𝑽 𝑽𝟏

At higher T, work done is more for 
same expansion of volume.

Irreversible isothermal change:
Work against a constant pressure 
𝒑𝒆𝒙𝒕 𝒑𝒇
𝟐 𝟐
𝒘𝒊𝒓𝒓𝒆𝒗 𝒑𝒆𝒙𝒕 𝒅𝑽 𝒑𝒇 𝒅𝑽 𝒑𝒇 𝑽𝟐 𝑽𝟏
𝟏 𝟏

Maximum work is done by the system during reversible expansion
𝒘𝒓𝒆𝒗 𝒘𝒊𝒓𝒓𝒆𝒗

Work done by adiabatic expansion of an Ideal Gas 
d𝑼 ð𝒒 ð𝒘,  ð𝒒 𝟎 ⇒ ð𝒘 𝒅𝑼 𝒏 𝑪𝑽 𝒅𝑻
𝟐
𝒘 𝒑
𝟏 𝒆𝒙𝒕
𝒅𝑽 𝒏 𝑪𝑽 𝑻𝟐 𝑻𝟏

Reversible adiabatic expansion
Obtain 𝑻𝟐 using any of the following
𝒑𝑽𝜸 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 or   𝐓𝑽𝜸 𝟏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 or  𝑻𝜸 𝑷𝟏 𝜸 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Irreversible adiabatic expansion against a constant pressure    𝒑𝒆𝒙𝒕 𝒑𝟐
Obtain 𝑻𝟐 as follows
𝒏𝑹𝑻𝟐 𝒏𝑹𝑻𝟏
𝒏 𝑪𝑽 𝑻𝟐 𝑻𝟏 𝒑𝒆𝒙𝒕 𝑽𝟐 𝑽𝟏 𝒑𝟐
𝒑𝟐 𝒑𝟏
𝑪𝑽 𝒑𝟐
𝑹 𝒑𝟏
∴ 𝑻𝟐 𝑻𝟏
𝑪𝑽
𝟏
𝑹

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

Experiment for 
an irreversible adiabatic expansion of an ideal gas 

𝒑𝟐
Stops are withdrawn
rapidly without any Movable Frictionless Piston
𝒑𝟐 exchange of energy
Stop

Movable Frictionless Piston
𝒑𝟐

Adiabatic, rigid, 
Gas Gas
𝒑𝟏 impermeable walls

𝒑𝟏 𝒑𝟐
Initial equilibrium state Final equilibrium state

Show that work is path dependent
Ideal gas, closed system, reversible process
Calculate    wf and wb

The reversible work wrev

• depends on the path used to go from 1 to 2
• can have any positive or negative value for
a given change of state

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

A practice problem

A sample consisting of 65.0 g of Xe is confined in a container at 
2.0 atm and 298 K.

Calculate the work done if the gas undergoes expansion under 
isothermal/adiabatic condition

(i) reversibly to a pressure of 1.0 atm
(ii) against a constant external pressure of 1.0 atm. 

Initial equilibrium state   
𝒏 𝟎. 𝟒𝟗𝟓 𝒎𝒐𝒍 𝒑𝟏 𝟐. 𝟎 𝒂𝒕𝒎 𝑻𝟏 𝟐𝟗𝟖 𝑲
Nature of ideal gas  Final equilibrium  Work done
expansion state
Expression Value (J)

Isothermal reversible 𝒑𝟐 𝟏. 𝟎 𝒂𝒕𝒎

Isothermal irreversible 𝒏𝑹𝑻𝟏

𝑽𝟐
𝒑𝟐
𝒏𝑹𝑻𝟏
𝑽𝟐
𝒑𝟏
Adiabatic reversible 𝑻𝟐 𝟐𝟐𝟓. 𝟖𝟒 𝑲

Adiabatic irreversible 𝑻𝟐 𝟐𝟑𝟖. 𝟒 𝑲

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

Initial equilibrium state   
𝒏 𝟎. 𝟒𝟗𝟓 𝒎𝒐𝒍 𝒑𝟏 𝟐. 𝟎 𝒂𝒕𝒎 𝑻𝟏 𝟐𝟗𝟖 𝑲
Nature of ideal gas  Final equilibrium  Work done
expansion state
Expression Value (J)

Isothermal reversible 𝒑𝟐 𝟏. 𝟎 𝒂𝒕𝒎 𝒑𝟏

𝒘 𝒏𝑹𝑻 𝒍𝒏
𝒑𝟐
Isothermal irreversible 𝒏𝑹𝑻𝟏 𝒘 𝒑𝟐 𝑽𝟐 𝑽𝟏
𝑽𝟐
𝒑𝟐
𝒏𝑹𝑻𝟏 𝒑𝒆𝒙𝒕 𝒑𝟐 𝟏. 𝟎 𝒂𝒕𝒎
𝑽𝟐
𝒑𝟏
Adiabatic reversible 𝑻𝟐 𝟐𝟐𝟓. 𝟖𝟒 𝑲 𝒘 𝒏𝑪𝑽 𝑻𝟐 𝑻𝟏

Adiabatic irreversible 𝑻𝟐 𝟐𝟑𝟖. 𝟒 𝑲 𝒘 𝒏𝑪𝑽 𝑻𝟐 𝑻𝟏

Initial equilibrium state   
𝒏 𝟎. 𝟒𝟗𝟓 𝒎𝒐𝒍 𝒑𝟏 𝟐. 𝟎 𝒂𝒕𝒎 𝑻𝟏 𝟐𝟗𝟖 𝑲
Nature of ideal gas  Final equilibrium  Work done
expansion state
Expression Value (J)

Isothermal reversible 𝒑𝟐 𝟏. 𝟎 𝒂𝒕𝒎 𝒑𝟏 ‐850.1

𝒘 𝒏𝑹𝑻 𝒍𝒏
𝒑𝟐
Isothermal irreversible 𝒏𝑹𝑻𝟏 𝒘 𝒑𝟐 𝑽𝟐 𝑽𝟏 ‐613.2
𝑽𝟐
𝒑𝟐
𝒏𝑹𝑻𝟏 𝒑𝒆𝒙𝒕 𝒑𝟐 𝟏. 𝟎 𝒂𝒕𝒎
𝑽𝟐
𝒑𝟏
Adiabatic reversible 𝑻𝟐 𝟐𝟐𝟓. 𝟖𝟒 𝑲 𝒘 𝒏𝑪𝑽 𝑻𝟐 𝑻𝟏 ‐445.5

Adiabatic irreversible 𝑻𝟐 𝟐𝟑𝟖. 𝟒 𝑲 𝒘 𝒏𝑪𝑽 𝑻𝟐 𝑻𝟏 ‐367.9

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

First Law of Thermodynamics
• First law introduces the concept of internal energy, 𝑼

• Equilibrium state of an isolated system        𝑼, 𝑽, 𝑵

• Internal energy, 𝑼 cannot be measured

• Change in internal energy can be measured during  a 
change in state 

Process Initial  Final equilibrium  Change in 

equilibrium state state internal energy
Infinitesimal 𝑼 𝑼 𝒅𝑼 𝒅𝑼
Finite 𝑼𝟏 𝑼𝟐 ∆𝑼 𝑼𝟐 𝑼𝟏

First Law of Thermodynamics

• For an infinitesimal change in state, 

d𝑼 ð𝒒 ð𝒘

• For a finite change in state,

∆𝑼 𝒒 𝒘

Srabani Taraphder Department of Chemistry 
IIT Kharagpur 13