CY1001:Thermodynamics

Arti Dua

Department of Chemistry

IIT Madras

!
Lecture 1: Introduction
to Thermodynamics
 Thermodynamics: Introduction

• The science of thermodynamics introduces a new concept

of temperature, which is absent from classical mechanics,
the theory of electricity and magnetism and quantum
mechanics.

• Thermodynamics is an empirical science.

• It describes macroscopic properties of equilibrium
system.
 Thermodynamics: Introduction
• Thermodynamics provides relationship
between physical properties once certain
measurements are made.

! dG = dH - TdS

• Kinetic theory and statistical

thermodynamics enable us to calculate the
magnitudes of these properties.
 Thermodynamics: Introduction

Thermodynamics started as a result of attempts to improve the efficiencies of

steam engines.

Heat Work

The thermodynamic mode of reasoning is applicable to many

different systems from the production of low temperature devices
to information theory.
Types of Systems

Isolated system with (N,V, E) or (N,p,E) constant

Closed system with (N,V,T) or (N,p,T) constant

Open system with (µ, V, T ) or (µ, p, T ) constant

• Describing thermodynamic system requires:

• A few macroscopic properties: P, V, T, n...

• Knowledge if system is homogeneous or heterogeneous.

• Knowledge if system is in equilibrium state

• Knowledge of the number of components.

• Two classes of properties:

• Extensive: depends on the size of the system (mass, volume,
entropy, energy, heat)

• Intensive: independent of the size of the system(temperature,

pressure, chemical potential, density, viscosity...)
 Thermodynamics: Introduction

• It is based on four laws:

• Zeroth law defines temperature (T).

• First law defines energy (U).

• Second law defines entropy (S).

• Third Law gives numerical value to entropy.
Zeroth law of thermodynamics
 Zeroth law of thermodynamics

• It introduces a new property temperature,

which is a state function.

• State function is defined solely by

instantaneous state and is independent of
previous history.

Z T2
dT = T = (T2 T1 )
T1

State Function

T1 T2
 State Function

If T(x, y) is a state function such that the function and their derivatives are
continuous and single valued then

@ 2 T (x, y) @ 2 T (x, y)
=
@x@y @y@x
State functions are exact
differentials

Temperature, Pressure and Volume are state functions.

 Inexact differentials are path functions

@ 2 F (x, y) @ 2 F (x, y)
6=
@y@x @x@y

Work and heat are path functions. They depend on how the
thermodynamic system changes from the initial to final state
Z
dw 6= w
Z
dq 6= q
Path Functions
 Work

force displacement Pex

Work of expansion
l

convention
 Reversible vs. Irreversible Processes

p
p

Reversible process is carried out extremely slowly (quasi-statically) such that

at every instant system departs only infinitesimally from an equilibrium state.

If there are finite departures from equilibrium the process is irreversible

 Reversible and Irreversible transformation
l
Expansion A

Compression

Cyclic Transformation
Irreversible
Total work in single stage
expansion and compression:

Total work in multistage

expansion and compression: Reversible
The First Law of
Thermodynamics
 First Law of Thermodynamics

For infinitesimal change:

For finite change:

For cyclic process:

 The first law of thermodynamics

Clausius statement: The energy of the universe is

conserved
First law of thermodynamics for different processes

Reversible:

Adiabatic:
 The first law of thermodynamics

For fixed n we only need to know two properties (T,V) to describe the system

The task of thermodynamics is to calculate these partial derivatives in terms of

measurable quantities.
 The first law of thermodynamics

Constant Volume:
 ✓ ◆ ✓ ◆ ✓ ◆
@U @T @V
U (T, V ) =) = 1
@T V @V U @U T
Cyclic relation

✓ ◆ ✓ ◆ ✓ ◆
@U @U @T
=
@V T @T V @V U

CV ⌘J Joule Coefficient

obtained from Joule’s experiment on

free expansion of gases

dU = CV dT CV ⌘J dV
⌘J = 0 (ideal gases) =) U (T )

The internal energy of an ideal gas depends only on

temperature U(T) for ideal gases
 Enthalpy

Chemical reactions usually take place at constant pressure. Enthalpy is a useful function of
state under these condition H(T, p).

The change in the enthalpy of a system is equal to the amount of heat exchanged by the
system at constant pressure.
 ✓ ◆ ✓ ◆
@H @H
H(T, p) =) dH = dT + dp
@T p @p T

Cp what is this?

✓ ◆ ✓ ◆ ✓ ◆
@H @T @p
H(T, p) =) = 1
@T p @p U @H T

✓ ◆ ✓ ◆ ✓ ◆
@H @H @T
=
@p T @T p @p U

CV µJT Joule-Thomson Coefficient

Joule-Thomson experiment
estimates this quantity

dH = Cp dT + Cp µJT dp

µJT = 0 (ideal gases) =) H(T )

The enthalpy of an ideal gas depends only on temperature H(T) for ideal gases
Reversible adiabatic expansion of an ideal gas (Homework)
Adiabatic
work

Isothermal
work
A Thermodynamic cycle (Homework)