Prelude to Thermodynamics

Lecture 1: Fundamental Concepts

 Prelude to Thermodynamics

What is Thermo - Dynamics?

The branch of science that studies
dynamics of thermal energy or simply heat.
 What is Thermodynamics All About?

Happens:
Butter melts in a hot pan

Never Happens:
Molten butter freezes back

? ? ?
The Zeroth Law The First Law The Second Law
 Who Discovered Thermodynamics?

Classical Thermodynamics

“ It is the only physical theory of universal content,

which I am convinced,
that within the framework of applicability of its basic concepts
will never be overthrown.”
 Why Study Thermodynamics?

Cooling Solutions

Practically every walk of

Refrigeration, cryogenics everyday modern life is Engines, turbines,
propulsion systems
built on applications of
thermodynamics!

Materials Processing –
Semiconductor doping,
Design of buildings – heat chip fabrication
transfer
Materials Manufacturing
 Course Outline

1 • Definitions, Conventions and Fundamental Concepts

2 • Kinetic Theory of Gases, Zeroth and the First Law, Heat and Work Interactions

• Internal Energy Changes in Different Processes

3 • Carnot Engine

4 • Review of Single-Variable Calculus – Differentiation

5 • Review of Single-Variable Calculus – Integration and Differential Equations

6 • Introduction to Partial Differentiation

 A Thermodynamic System

A Thermodynamic “System” “Boundary”

A Part of the universe separated Physical or Imaginary

from its surroundings by a boundary.
 Types of Systems

Classification based on the properties of the boundary – Whether it allows energy/mass transfer!

Open System
Evaporation Heat

Rain

System

Energy Mass

Surroundings
 Types of Systems

Closed System

System
Heat

Energy Mass

Surroundings
 Types of Systems

Isolated System

System

Energy Mass

Surroundings
 Characterization of a Thermodynamic System

• Mass (m – kg) or number of moles (n – mol)

• Volume (V – m3)

• Density (ρ – kg/m3)

• Pressure (P – N/m2 or Pa); Temperature (T – K)

• Kinetic Energy, Potential Energy (E – J)

• Heat Capacity (C – J/K):

Heat (Q) required to increase the system temperature by 1 K.

Specific Heat Capacities (C – J/kg.K) & Molar Heat Capacity (J/mol.K)

Constant pressure: CP

Constant volume: CV
 Characterization of a Thermodynamic System

Internal Energy of a System (U – J)

Energy of the system attributed only to the motion its constituent atoms/molecules i.e. the kinetic
energies and the potential energies arising from interactions between themselves, or due to electric,
magnetic, gravitational fields etc.

Potential Kinetic
Energies Energies

Free of any other energy due to external impulse – e.g. kinetic energy (translational or rotational )of the
system as a whole or potential energy due to external mechanical force/electric or magnetic field.

Thermodynamics deals predominantly the changes in the internal energy (ΔU)

of a system due to heat supplied to it and work done on it!
 Characterization of a Thermodynamic System

Whether a certain property of a material/system depends upon the quantity of matter in it?

Yes No

Extensive Property Intensive Property

(additive) (non-additive)

Mass/number of moles Density

Volume Pressure
Temperature

1kg water + 1 kg water = 2kg water

1liter water + 1 liter water = 2 liter water
1kg/m3 density + 1kg/m3 density = 1 kg/m3 density
1 atm pressure + 1 atm pressure = 1 atm pressure
300 K temperature + 300 K temperature = 300 K temperature
 Characterization of a Thermodynamic System

Extensive Property Intensive Property

Heat Capacity Specific Heat Capacity

Molar Heat Capacity

Specific Internal Energy

Internal Energy (U) U = U/m (J/kg)

Molar Internal Energy

U = U/n (J/mol)

Volume (V) Molar Volume

V = V/n

Molar properties are the properties of 1 mol of a substance/system.

All the molar properties are, by definition, intensive properties.
Dividing one extensive property by another gives an intensive property!
 State of a System

Thermodynamic State of a system

A thermodynamics state of a system provides ‘complete’ information about it. It is specified by the
values of a suitable set of minimum number of system properties – known as state variables.

For example, thermodynamic state of a pure gas enclosed in a container can be specified by P, V, T, n.

Are all four parameters needed to completely specify the state of the system?
No! – Knowledge of any two allows the third to be calculated easily.

How are these quantities measured? – By instruments, macroscopically!

Classical Thermodynamics only deals with macroscopic properties of the system and disregards the
internal atomistic/molecular level details! The state of the system is thus also called as ‘macrostate’.

T P

Macroscopically measured values of properties are

simply the average values!

EQUILIBRIUM
 Equilibrium State

EQUILIBRIUM – The State of Stability

A system left undisturbed by any external influence for sufficient enough time tends to reach
a stable state at which none of its properties change anymore and maintain it thereafter.

Thermal Equilibrium:
A cup of hot coffee is left out Reaches the same
The temperature of the system
in open. temperature as air.
is uniform throughout.

Mechanical Equilibrium:
A power-fan in a room is Still air without
The pressure is uniform throughout the
turned off any draft.
system and there is no flow of matter.

A spoonful of sugar is added
to a glass of water.
Chemical Equilibrium:
Uniformly
The chemical composition of the system
sweet water.
remains uniform throughout.

A system is in a state of thermodynamic equilibrium if it is in

thermal, mechanical and chemical equilibrium.
 Equilibrium State

T P

The macroscopic properties of the system can be measured only if the system is in
thermodynamic equilibrium!

When a system is NOT in equilibrium, most of its properties are not even well defined!
 Changing the State of a System - Processes

A thermodynamic process changes the state of a system.

State 2
(x2=L;
KE2=0;
PE2=0)

State 1
(x1=0;
KE1=0;
PE1=0) W1 < W2 <W3

A property that depends solely on the state of the system is called a State Function.
(Hence also called – System properties – e.g. P, V, T, U, n)
A property that depends on the process or path taken is called a Path Function.
(Hence also called – Process properties – e.g. W, Q)
 Changing the State of a System - Processes

One of the simplest (and important) systems to study basics of thermodynamics is

a gas enclosed in a container.

Cylinder and Piston Assembly

System – Gas
Boundary – Cylinder walls and piston

Work

thermally conducting walls: Closed System

thermally insulating walls: Isolated System Pext

System-Environment
Interactions
State of the system can be specified by
(P, V, T, n)
V Pint
T
How to change it?

Heat
 Types of Processes

Type of Process What Happens? Initial State Final State

Isobaric Constant Pressure (P1, V1, T1) (P1, V2, T2)
Isochoric Constant Volume (P1, V1, T1) (P2, V1, T2)
Isothermal Constant Temperature (P1, V1, T1) (P2, V2, T1)
Adiabatic No heat supplied/ extracted (P1, V1, T1) (P2, V2, T2)

Pext

V Pint
T
 Pressure-Volume (PV) Diagrams

A (P1, V1) A point can be drawn on the PV diagram

P1 if and only if the system is in equilibrium!

Initial and final states are unquestionably

in equilibrium.
B (P2, V2)
P2

V
V1 V2

How is then possible to draw points along the path of process,

when the system is continually undergoing changes? ?
The processes must be Quasi-Static!
 Quasi-Static Processes

P1ext P1ext -δ P2ext

P1int P1int P2int

P P

A (P1, V1) A (P1, V1)

P1 P1
States in near-equilibrium

B (P2, V2)
P2

V V
V1 V1 V2
 Quasi-Static Processes

Involves infinite number of steps.

Each step must bring about infinitesimal change.

The ‘driving force’ is infinitesimally larger than the ‘opposing force’.

It takes forever to complete!

A Quasi-static process is an idealized concept!

A (P1, V1)
Extremely important because it allows one to P1
construct the path of a process and thus follow the
thermodynamic behavior of the system along it!

B (P2, V2)
P2

V
V1 V2
 Reversible and Irreversible Processes

A reversible process is a process in which the initial state of the state of the
system can be restored back from the final state without any change in the system
itself or its surroundings.

In order for a process to be reversible,

1. It must be a quasi-static process
2. There must not occur any loss of energy due to neither (a) friction nor (b) heat
transfer!

Energy is lost due to friction as heat!

P1ext P1ext -δ

P1int P1int
δQ
Energy is again lost due to friction as heat!
 Reversible and Quasi-Static Processes

A reversible process is necessarily a quasi-static process.

The opposite may not always be true! A quasi-static process may or may not be reversible.

In thermodynamics, (at least in the introductory texts), friction effects are neglected.
What is typically essential is to maintain the system close to equilibrium all the time.
A reversible process allows that to happen.

Hence, ‘reversible’ and ‘quasi-static’ can be used interchangeably.

It is still essential to keep in mind the distinction between the two.
 Irreversible Processes

P1ext P2ext

P1int P2int

An irreversible process is a process in which the initial state of the state of the system can’t be restored
back from the final state without changing thermodynamic properties of system or surroundings.

P P

A (P1, V1) A (P1, V1)

P1 P1
An irreversible process!

Cannot be drawn as a B (P2, V2)

P2
curve on PV diagram

V V
V1 V1 V2
 Pressure-Volume (PV) Diagrams

Isobaric Expansion/Compression Process

A (P, V1) Calculating the magnitude of work done (W)
P B (P, V2)

V
V1 V2

Pext =Pint =P
Pext =Pint =P

Δz

V2
V1
T
 Different Types of Processes

Isobaric Process P
Isochoric Process
P
A (P1, V1)
A (P1, V1)
P1=P2 B (P2, V2)
B (P2, V2)

V
V V1=V2

Isothermal Process Adiabatic Process

P P

A (P1, V1) A (P1, V1)

B (P2, V2) B (P2, V2)

V V
 Work and Heat as Path Functions

Path 1 Path 2
1. Isochoric A (P1, V1) D (P1, V2) 1. Isobaric
(AC) P1 (AD)
2. Isobaric 2. Isochoric
(CB) (DB)

B (P2, V2)
P2
C (P2, V1)

V
V1 V2

Even though the initial and final states are the same,
magnitude of work done in two different paths are different!

W is the property of the process!

W is path function

Q is also a path function

 Lecture 1: Summary

What is thermodynamics and its importance

Fundamental concepts: Systems, Properties of systems, state of System

Irreversible, quasi-static and reversible processes

System-environment interactions: Heat and Work

P-V diagrams for gaseous systems