THERMODYNAMICS

Introduction........................................................................................................................................................................................................................................ 2
Zeroth Law of thermodynamics ................................................................................................................................................................................................ 5
Energy Interactions ........................................................................................................................................................................................................................ 6
Entropy ...............................................................................................................................................................................................................................................21
Available energy, Availability and Irreversibility ...........................................................................................................................................................27
Properties of Pure Substances..................................................................................................................................................................................................29
Mixture of gases ..............................................................................................................................................................................................................................35
Thermodynamics Relations .......................................................................................................................................................................................................37
Introduction
It is the science of energy transfer and its effects on properties of system.
Energy transfer may be heat or work or both heat and work.
The main aim of thermodynamics study is to convert disorganized form of energy (heat) in organized form of energy (work)
in an efficient manner.
Applications of thermodynamics
Refrigeration, Air conditioning, steam power plant, IC engines etc.
Basic Concepts
System
It is the region in space upon which the study is focused or concentrated.
Surroundings
Anything external to system where effect of system is failed is known as surroundings.
𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑆𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠
Boundary
A separation between system and surroundings I known a boundary.

Types of system
Types of system Mass transfer Energy transfer Examples
Closed   Water in sealed container
Open   Turbine, pump
Isolated   Universe
Note
In a closed system as there is no mass transfer, the system mass remains constant and hence it is also known as controlled
mass system.
Control Volume
It is the volume enclosing (or) surrounding the device which we wish to analyze. Across the control volume both mass
transfer and energy transfer can take place.
Microscopic and macroscopic approach of thermodynamics
Microscopic
In microscopic approach, the behavior of individual molecules is taken into consideration. The approach is also known as
statistical thermodynamics. This approach is useful at low densities (High altitudes).
Macroscopic
In macroscopic approach, individual molecular behavior is not taken into consideration. That is average behavior of
molecules is taken into consideration. This approach is also known as classical thermodynamics.
We follow Classical Thermodynamics.
Thermodynamic Equilibrium
A system is said to be in thermodynamic equilibrium if it is in
1. Thermal equilibrium (equality of temperature)
2. Mechanical equilibrium (equality of temperature)
3. Chemical equilibrium (equality of chemical potential)
Pure Substance
A substance is said to be a pure substance if it is
• Homogenous in chemical composition
• Homogenous in chemical aggregation

A pure substance can exist in single or more than one phase.

Note
Dry air is a pure substance, but moist air (liquid air) is not a pure substance i.e., in moist air water vapor can be condensed
and separated. A pure substance can be a mixture of gases also.
Property of a system
Any measurable characteristic is a property.
Example – Pressure, temperature, volume, density etc...
Properties are of 2 types.
1. Intensive 2. Extensive
Intensive properties They are independent of size or mass.
Examples- Pressure, temperature, density, viscosity etc…
Extensive properties They are dependent of size or mass.
Examples- mass, volume, all forms of energy etc…
Ratio of 2 extensive properties is an intensive property.
All specific properties (extensive property/mass) are intensive properties.
Examples – Specific volume, specific enthalpy, specific internal energy, specific entropy.
Important points w.r.t properties
→ Properties are point functions or state functions
→ Properties are independent of past history, that is they are independent of path.
→ Properties are exact differentials.
→ Properties are macroscopic characteristic of a system.
State of a system
The condition of a system is known as state of system.
Process
Any change of state is a process.
Reversible process
A process is said to be reversible process if when reversed, follows same path without leaving any effect on system and
surroundings.
Irreversible process
A process which is not a reversible process is irreversible process.
Friction is one of the reasons which makes the process irreversible.
Most of the practical process are irreversible process. Reversible process is discussed to simply analysis and they are efficient
process.

Quasi-Static process
A process which is carried out very slowly with a small difference in properties is known as Quasi-static process.
Note
Though all reversible processes are quasi static processes, but all quasi static processes are not reversible.
Thermodynamic Cycle
A system is said to be have undergone a cycle with initial and final state of a system is same.
Minimum no. of process required for a cycle are two.
The cyclic integral of any property is zero i.e., the change of property in a cycle is zero.

Gibbs phase rule

According to Gibbs phase rule 𝑃 + 𝐹 = 𝐶 + 2
P  No. of phases
F  minimum no. of independent intensive variables required to find the state (or) degree of freedom
C  No. of components

At triple point the degree of freedom is zero.

Concept of Continuum
Continuum means continuous, in continuum process matter is assumed to be distributed uniformly and continuously.
For applying the concept of continuum,
1. There should be large number of molecules
2. Mean free path should be small
3. Continuum process is a macroscopic approach.
𝜕𝑀 𝜕𝑁
𝑇ℎ𝑒 𝑎𝑝𝑝𝑟𝑜𝑎𝑐ℎ 𝑑𝑍 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦 𝑖𝑠 𝑎𝑛 𝑒𝑥𝑎𝑐𝑡 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑙 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑜𝑛𝑙𝑦 𝑖𝑓 ( ) =( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦
Zeroth Law of thermodynamics
Zeroth law was developed by fowler in 1931. This law was developed after first and second law of thermodynamics.
When a body A is in thermal equilibrium with body B and body B is in thermal equilibrium with body C, then A and C are in
thermal equilibrium.
Significance of Zeroth law
Without bringing two bodies into direct contact with the help of zeroth law it can be established whether they can be in
thermal equilibrium.
Thermometric principle
In this principle the property which is changing with temperature is calculated first and with the help of this property,
temperature is calculated.
Types of thermometers
Resistance thermometer
They are based on wheat stone bridge principle. In resistance thermometers, resistance is
thermometric principle.
𝑃 𝑅
=
𝑄 𝑆
𝑅 = 𝑅𝑜 (1 + 𝛼𝑡 + 𝛽𝑡 2 )
Thermocouple
Thermocouples are based on see beck effect, when two dissimilar metals are joined to form 2 junctions and these two
junctions are maintained at different temperatures then EMF or voltage is generated.
In thermocouple voltage or EMF plays the role of thermometric property.
Constant Volume gas thermometer
These thermometers are based on ideal gas laws and in thermometers pressure is thermometric property.
𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅 ⋅ 𝑇 → 𝑇 = 𝑓(𝑃)
Volume is constant. So, temperature is a function of pressure.
Constant Pressure gas thermometer
These thermometers are based on ideal gas laws and in thermometers volume is thermometric property.
𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅 ⋅ 𝑇 → 𝑇 = 𝑓(𝑉)
Pressure is constant. So, temperature is a function of Volume.
Temperature Scale
Temperature scales are arbitrary, i.e., randomly taken. In Celsius or centigrade scale ice point is taken as 0ᵒC and steam
point as 100ᵒC.
𝐾 = °𝐶 + 273.15
Triple point of water is taken as 0.01ᵒC (273.16 K).
Ideal gas temperature and kelvin scale are same. So, in ideal gas equation “PV=mRT”, temperature should be in Kelvin (K).
S.I unit of temperature is Kelvin.
A single fixed-point reference temperature is used as triple point of water (Tt. p=273.16 K)
𝑃⋅𝑉 =𝑚⋅𝑅⋅𝑇
𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇 ∝𝑃 → 𝑇 =𝐶⋅𝑃
𝑇𝑡.𝑝
𝑇𝑡.𝑝 = 𝐶 ⋅ 𝑃𝑡.𝑝 → 𝐶 =
𝑃𝑡.𝑝
𝑇𝑡.𝑝
𝑇= ×𝑃
𝑃𝑡.𝑝
𝑃
𝑇 = 273.15 ×
𝑃𝑡.𝑝
Ideal gas thermometer is independent of material of construction.
Adiabatic index (γ) for mono-atomic gases is 1.67, for diatomic gases is 1.4, for polyatomic gases is 1.33.
For air, γ is 1.41.
Energy Interactions
Work is said to be done by the system if the sole effect on things external to system can be equated to raising of weights.
Work transfer occurs only when it crosses the boundary. Therefore, Work transfer is a boundary phenomenon.

Convention of Work transfer

→ Work done by system is taken as positive.
→ Work done on system is taken as negative.
General equation for closed system work
𝐹
𝑃=
→ 𝐹 =𝑃⋅𝐴
𝐴
𝑊 = 𝐹𝑜𝑟𝑐𝑒 × 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡 = 𝐹 × 𝑑𝑥 = 𝑃 ⋅ 𝐴 × 𝑑𝑥 = 𝑃 × 𝐴 ⋅ 𝑑𝑥 = 𝑃 × 𝑑𝑉
This work is a closed system work or non-flow work or displacement work.
Work in P-V diagram

𝐴𝑟𝑒𝑎 = 𝑃 ⋅ 𝑑𝑉
𝑊𝑜𝑟𝑘 = 𝑃 ⋅ 𝑑𝑉 = 𝐴𝑟𝑒𝑎
Area under the circle when projected in volume axis gives non-flow or closed system work.

Conditions for applying the equation W=P.dV

1. System must be a closed system.
2. Work should cross the boundary (boundary phenomenon)
3. Process must be reversible process.
Though the end points are same for paths a & b work transfer is not same, because areas are
different for paths a & b.
Therefore, work transfer is not a function, it is a property. It is inexact differential.
Closed System Work transfer in various situations
Constant Volume or Isochoric process
𝑊=0
Examples
Fluid in a rigid container when heated or cooled, Piston cylinder arrangements with stops.
Special Case of constant volume Process
Here weights are lowered and work is done on the system. Therefore, paddle wheel work is negative.
Though dV=0, (P⋅ dV=0), work is not zero. because W=P.dV is valid only for reversible process.
Constant Pressure or Isobaric Process
𝑉2 𝑉2
𝑊 = ∫ 𝑃 ⋅ 𝑑𝑉 = 𝑃 ⋅ ∫ 𝑑𝑉
𝑉1 𝑉1

𝑊 = 𝑃(𝑉2 − 𝑉1 )

Constant temperature or Isothermal process

Removing weight and simultaneously adding heat for an ideal gas is an example of isothermal process.
In isothermal process though the temperature is constant there is heat transfer.
𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 → 𝑇 = 𝐾
𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅 ⋅ 𝑇 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐶
𝑃⋅𝑉 =𝐶 → 𝑃 =
𝑉
𝑃1 ⋅ 𝑉1 = 𝑃2 ⋅ 𝑉2 = 𝐶
𝑉2 𝑉2
𝐶 𝑉2
𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = ∫ 𝑃 ⋅ 𝑑𝑉 = ∫ ⋅ 𝑑𝑉 = 𝐶 𝑙𝑛
𝑉1 𝑉1 𝑉 𝑉1
𝑉2 𝑉2 𝑉2 𝑉2
𝑊 = 𝑃1 ⋅ 𝑉1 ⋅ 𝑙𝑛 = 𝑚 ⋅ 𝑅 ⋅ 𝑇1 ⋅ 𝑙𝑛 𝑊 = 𝑃2 ⋅ 𝑉2 ⋅ 𝑙𝑛 = 𝑚 ⋅ 𝑅 ⋅ 𝑇2 ⋅ 𝑙𝑛
𝑉1 𝑉1 𝑉1 𝑉1
When a gas undergoes Isothermal process, it is represented by a rectangular hyperbola on P-V diagram.
Conditions- 1. Closed system, 2. Reversible process, 3. Isothermal process, 4. Ideal gas
Adiabatic process
A process in which there is no heat transfer from the system is called Adiabatic process.
𝐹𝑜𝑟 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑡 𝑐𝑎𝑛 𝑏𝑒 𝑑𝑒𝑟𝑖𝑣𝑒𝑑 𝑃𝑉 𝛾 = 𝐶 , 𝑤ℎ𝑒𝑟𝑒 𝛾 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛 𝑎𝑠 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑖𝑛𝑑𝑒𝑥 𝑎𝑛𝑑 𝛾 > 1.
𝑉2 𝑉2 1−𝛾 1−𝛾 1−𝛾 1−𝛾 𝛾 1−𝛾 𝛾 1−𝛾
𝐶 𝑉 − 𝑉1 𝐶 ⋅ 𝑉2 − 𝐶 ⋅ 𝑉1 𝑃2 𝑉2 ⋅ 𝑉2 − 𝑃1 𝑉1 ⋅ 𝑉1
𝑊 = ∫ 𝑃 ⋅ 𝑑𝑉 = ∫ 𝛾
⋅ 𝑑𝑉 = 𝐶 ( 2 )=( )=( )
𝑉1 𝑉1 𝑉 1−𝛾 1−𝛾 1−𝛾
𝑃2 𝑉2 − 𝑃1 𝑉1
𝑊=
1−𝛾
Conditions- 1. Closed system, 2. Reversible process, 3. Adiabatic process
Note
An adiabatic system need not be isolated system because in an isolated system there is no energy interaction,
there can be work interaction.
Poly-tropic process
𝐴 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑛 𝑤ℎ𝑖𝑐ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑎𝑛𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑜𝑙𝑙𝑜𝑤𝑠 𝑡ℎ𝑒 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠ℎ𝑖𝑝 𝑃𝑉 𝑛 = 𝐶 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛 𝑎𝑠 𝑃𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠,
𝑤ℎ𝑒𝑟𝑒𝑎𝑠 ‘𝑛’ 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛 𝑎𝑠 𝑃𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 𝑖𝑛𝑑𝑒𝑥 (𝑛). 𝐺𝑒𝑛𝑒𝑟𝑎𝑙𝑙𝑦, 1 < 𝑛 < 𝛾.
In Poly-tropic process there is both heat transfer and work transfer, where a in adiabatic there I only work transfer.
𝑃2 𝑉2 − 𝑃1 𝑉1
𝑊=
1−𝑛
Conditions- 1. Closed system, 2. Reversible process, 3. Poly-tropic process
Examples
Gas in a balloon when heated, Piston cylinder arrangement with spring when heated.
Representation of various process on P-V diagram

𝐼𝑛 𝑃𝑉 𝑚 = 𝐶
→ 𝑚 = 0 → 𝑃 = 𝐶 → 𝐼𝑠𝑜𝑏𝑎𝑟𝑖𝑐
→ 𝑚 = ∞ → 𝑃 = 0 → 𝑉 = 𝐶 → 𝐼𝑠𝑜𝑐ℎ𝑜𝑟𝑖𝑐
→ 𝑚 = 1 → 𝑃𝑉 = 𝐶 → 𝑇 = 𝐾 → 𝐼𝑠𝑜𝑐ℎ𝑜𝑟𝑖𝑐
→ 𝑚 = 𝛾 → 𝑃𝑉 𝛾 = 𝐶 → 𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐
→ 𝑚 = 𝑛 → 𝑃𝑉 𝑛 = 𝐶 → 𝑃𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐

Slope of Isothermal curves on P-V diagram

𝑇 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑖𝑛 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑢𝑟𝑣𝑒.
𝑃𝑉 = 𝑚𝑅𝑇 → 𝑃𝑉 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑇 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
Differentiating,
𝑑𝑃 𝑃
𝑃 ⋅ 𝑑𝑉 + 𝑉 ⋅ 𝑑𝑃 = 0 → =−
𝑑𝑉 𝑉
𝑷
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑢𝑟𝑣𝑒 𝑠𝑙𝑜𝑝𝑒 𝑜𝑛 𝑃 − 𝑉 𝑔𝑟𝑎𝑝ℎ 𝑖𝑠 − .
𝑽
Slope of Adiabatic curves on P-V graph
𝑃𝑉 𝛾 = 𝐶
Differentiating,
𝑑𝑃 𝑃⋅𝛾
𝑃(𝛾 ⋅ 𝑉 𝛾−1 ⋅ 𝑑𝑉) + 𝑉 𝛾 ⋅ 𝑑𝑃 = 0 → =−
𝑑𝑉 𝑉
𝑃
𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑐𝑢𝑟𝑣𝑒 𝑠𝑙𝑜𝑝𝑒 𝑜𝑛 𝑃 − 𝑉 𝑔𝑟𝑎𝑝ℎ 𝑖𝑠 − ⋅𝛾
𝑉
Comparison of Adiabatic slope and Isothermal slope
𝑃 𝑃
𝑚𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 = − ⋅ 𝛾 = 𝛾 ⋅ (− ) = 𝛾 ⋅ 𝑚𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙
𝑉 𝑉
𝑚𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 = 𝛾 ⋅ 𝑚𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙
𝑚𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐
𝛾= >1, 𝑎𝑠 𝛾 > 1
𝑚𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙
𝑚𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 > 𝑚𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙

𝑃2 𝑇2
→ 𝐼𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒, = (𝑇 𝑖𝑛 𝐾𝑒𝑙𝑣𝑖𝑛)
𝑃1 𝑇1
𝑉2 𝑇2
→ 𝐼𝑛 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒, = (𝑇 𝑖𝑛 𝐾𝑒𝑙𝑣𝑖𝑛)
𝑉1 𝑇1
→ 𝐼𝑛 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, 𝑃1 𝑉1 = 𝑃2 𝑉2
1 𝛾−1
𝑉1 𝑇2 𝛾−1 𝑇2 𝑃2 𝛾
→ 𝐼𝑛 𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, =( ) =( )
𝑉2 𝑇1 𝑇1 𝑃1
𝑛−1
𝑇2 𝑃2 𝑛
→ 𝐼𝑛 𝑃𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, =( )
𝑇1 𝑃1
Heat
Energy interactions due to temperature difference is called Heat interaction.
𝑄∝𝑚
𝑄 ∝ 𝛥𝑇
𝑄 = 𝑚 ⋅ 𝑐 ⋅ 𝛥𝑇
c is proportionality constant, it is known as specific heat.
𝑇ℎ𝑒 𝑢𝑛𝑖𝑡 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑖𝑠 𝐾𝐽⁄𝑘𝑔 °𝐶 𝑜𝑟 𝐾𝐽⁄𝑘𝑔 𝐾

Physical meaning of specific heat

It is amount of heat required to raise the temperature of unit mass of substance through unit degree temperature difference.
Physically specific heat represents heat absorbing capacity. Greater the specific heat greater the heat absorbing capacity.
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑓𝑜𝑟 𝑤𝑎𝑡𝑒𝑟 𝑖𝑠 4.187 𝐾𝐽⁄𝑘𝑔 𝐾 , 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑓𝑜𝑟 𝑎𝑖𝑟 𝑖𝑠 1.005 𝐾𝐽⁄𝑘𝑔 𝐾 .
Specific heat for water is more. So, it absorbs more heat compared to air per kg.
For a same temperature rise in constant pressure and constant volume process, Heat absorbed in constant pressure process
is more because heat supplied in cosntant volume is completely consumed in raising temperature where as in constant
pressure pressure heat supplied does some work also. So, heat absorbed per unit mass in constant pressure process is more.
𝑄𝑝 > 𝑄𝑣
(𝑚 ⋅ 𝑐 ⋅ 𝛥𝑇)𝑝 > (𝑚 ⋅ 𝑐 ⋅ 𝛥𝑇)𝑣
𝑐𝑝 > 𝑐𝑣
𝑐𝑝
𝛾= → 𝛾 > 1 (𝑐𝑝 > 𝑐𝑣 )
𝑐𝑣
Specific heat at constant pressure (cp) is greater than specific heat at constant
volume (cv), because cp includes internal energy and external work, whereas cv
includes internal energy only.
Specific heat of Solids and liquids
In case of solids and liquids, cp and cv are almost same because the expansion of solids and liquids are negligible and hence
work transfer is zero.
𝑐𝑝 ≅ 𝑐𝑣 (𝑊 = 0)
𝑐𝑝 = 𝑐𝑣 = 𝐶 → 𝑠𝑜𝑙𝑖𝑑𝑠 𝑎𝑛𝑑 𝑙𝑖𝑞𝑢𝑖𝑑𝑠
𝑐𝑝 > 𝑐𝑣 → 𝑔𝑎𝑠𝑒𝑠
Convention of Heat transfer
Heat supplied to the system is taken as positive and heat rejection from the system is taken as negative.
First Law of Thermodynamics
For a closed system undergoing a cycle, net heat transfer (ΣQ) is equal to net-work transfer (ΣW).
𝛴𝑄 = 𝛴𝑊 → 𝑉𝑎𝑙𝑖𝑑 𝑜𝑛𝑙𝑦 𝑓𝑜𝑟 𝑐𝑦𝑐𝑙𝑒
This equation is applicable for reversible and irreversible cycles.
Change in internal energy in a cycle is zero.
Consequences of first law of thermodynamics
First consequence
Heat transfer is path function.
𝛴𝑑𝑄 = 𝛴đ𝑊
𝑑𝑄1𝑎2 + 𝑑𝑄2𝑏1 = đ𝑊1𝑎2 + đ𝑊2𝑏1 ①
𝑑𝑄1𝑎2 + 𝑑𝑄2𝑐1 = đ𝑊1𝑎2 + đ𝑊2𝑐1 ②
⟹ ①−②
𝑑𝑄2𝑏1 − 𝑑𝑄2𝑐1 = đ𝑊2𝑏1 − đ𝑊2𝑐1 → đ𝑊2𝑏1 ≠ đ𝑊2𝑐1 → 𝑑𝑄2𝑏1 ≠ 𝑑𝑄2𝑐1
Though the end points are same for paths b & c. Heat transfer is not same. Therefore, heat transfer is not a property, it’s a
path function, it’s an inexact differential.
Important points w.r.t Heat & work
→ Both are not properties
→ Both are inexact differentials
→ Both are path functions
→ Both are boundary phenomena
→ Both are energies in transit (transient phenomena), i.e., they appear only during a process, once the process is over
they lose their meaning.
Second Consequence
Energy is a property.
𝑑𝑄2𝑏1 − 𝑑𝑄2𝑐1 = đ𝑊2𝑏1 − đ𝑊2𝑐1
(đ𝑄 − đ𝑊)2𝑏1 = (đ𝑄 − đ𝑊)2𝑐1
(đ𝑄 − đ𝑊) 𝑖𝑠 𝑠𝑎𝑚𝑒 𝑓𝑜𝑟 𝑏𝑜𝑡ℎ 𝑝𝑎𝑡ℎ𝑠 𝑖. 𝑒. , 𝒃 & 𝒄
Though paths b & c are different, (đQ-đW) is same for paths b & c.
So, (đQ-đW) must be property.
This Property is known as Energy.
(đ𝑄 − đ𝑊)2𝑏1 = (đ𝑄 − đ𝑊)2𝑐1 = 𝑑𝐸
đ𝑄 − đ𝑊 = 𝑑𝐸
đ𝑄 = đ𝑊 + 𝑑𝐸
This is the first law of thermodynamics equation for any (reversible or irreversible) process.
Note
The equation đQ=dE+P.dV is valid for closed system undergoing reversible process only because đW=P.dV is applicable for
only closed system undergoing reversible process.
Energy
𝐸 = 𝐾. 𝐸 + 𝑃. 𝐸 + 𝑈
(U  sum of all forms of molecular energy)
𝑑𝐸 = 𝑑(𝐾. 𝐸) + 𝑑(𝑃. 𝐸) + 𝑑𝑈
𝑊ℎ𝑒𝑛 𝑑(𝐾. 𝐸) & 𝑑(𝑃. 𝐸) 𝑎𝑟𝑒 𝑛𝑒𝑔𝑙𝑖𝑔𝑖𝑏𝑙𝑒.
𝑑𝐸 = 𝑑𝑈
đ𝑄 = 𝑑𝑈 + đ𝑊 → 𝐹𝑖𝑟𝑠𝑡 𝑙𝑎𝑤 𝑜𝑓 𝑇ℎ𝑒𝑟𝑚𝑜𝑑𝑦𝑛𝑎𝑚𝑖𝑐𝑠 𝑒𝑞𝑛
Above equation is the first law of thermodynamics equation for a closed system undergoing process when kinetic energy and
potential energy changes are neglected.
Internal energy
All forms of energy associated with molecules is known as Internal energy. It’s an extensive property.
Specific Internal energy (u)
𝑈
𝑢=
𝑚
Internal energy per unit mass is known as specific internal energy.
It’s an intensive property, it is generally expressed in KJ/kg.
Third consequence
The energy of an isolated system is always constant.
đ𝑄 = 𝑑𝐸 + đ𝑊
đ𝑄 = 0, đ𝑊 = 0 → 𝑑𝐸 = 0

𝐸2 − 𝐸1 = 0 → 𝐸2 = 𝐸1 → 𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Fourth Consequence
Motion machine of first kind (PMM-1) is impossible.
There can be no machine which produces work continuously without absorbing any heat.
If such a machine is developed, it violates first law of cycle.
Heat transfer for various processes
Constant Volume process
đ𝑄 = 𝑑𝑈 + đ𝑊
đ𝑄 = 𝑑𝑈 (đ𝑊 = 0)
In a constant volume process heat transfer is equal to change in internal energy.
Enthalpy
In thermodynamics the term (U + PV) appears frequently and for convenience this term is taken as enthalpy.
It’s an extensive property. Generally, it is expressed in KJ.
The equation H=U+PV is valid for any process, any system and for any working fluid.
Constant pressure process
đ𝑄 = 𝑑𝑈 + đ𝑊
đ𝑄 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 = 𝑑𝑈 + 𝑑(𝑃𝑉) = 𝑑(𝑈 + 𝑃𝑉) = 𝑑𝐻
đ𝑄 = 𝑑𝐻
Heat transfer in constant pressure process, closed system process is equal to change in enthalpy.
Ideal gas
𝑑𝑈 = 𝑚 ⋅ 𝑐𝑣 ⋅ 𝑑𝑇
𝑑𝐻 = 𝑚 ⋅ 𝑐𝑝 ⋅ 𝑑𝑇
𝑈 = 𝑓(𝑇)
The equation dU=mcvdT is valid for an ideal gas undergoing any process.
The equation dU=mcvdT is valid for real gas only under constant volume conditions
The equation dH=mcpdT is valid for an ideal gas undergoing any process.
The equation dH=mcpdT is valid for real gas only under constant volume conditions
Isothermal process
đ𝑄 = 𝑑𝑈 + đ𝑊
𝑈 = 𝑓(𝑇) → 𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑈 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑑𝑈 = 0
đ𝑄 = đ𝑊
When an ideal gas undergoes isothermal process, heat transfer is equal to work transfer.
Adiabatic process
đ𝑄 = 0
There is no heat transfer in adiabatic process.
To show that (cp-cv = R) for an ideal gas
𝐻 = 𝑈 + 𝑃𝑉 → 𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)
𝐹𝑜𝑟 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 → 𝑑𝐻 = 𝑚𝑐𝑝 𝑑𝑇, 𝑑𝑈 = 𝑚𝑐𝑣 𝑑𝑇, 𝑃𝑉 = 𝑚𝑅𝑇
𝑚𝑐𝑝 𝑑𝑇 = 𝑚𝑐𝑣 𝑑𝑇 + 𝑚𝑅𝑑𝑇 → 𝑐𝑝 = 𝑐𝑣 + 𝑅
𝑐𝑝 − 𝑐𝑣 = 𝑅
𝑐𝑝 𝑅 𝑅
= 𝛾 → 𝑐𝑣 = → 𝑐𝑝 = 𝛾 ⋅
𝑐𝑣 𝛾−1 𝛾−1
Polytropic Heat transfer
đ𝑄 = 𝑑𝑈 + đ𝑊
𝑃1 𝑉1 − 𝑃2 𝑉2
𝑑𝑈 = 𝑚𝑐𝑣 𝑑𝑇 đ𝑊𝑝𝑜𝑙𝑦 =
𝑛−1
𝑃1 𝑉1 − 𝑃2 𝑉2 𝑅 𝑃1 𝑉1 − 𝑃2 𝑉2
đ𝑄𝑝𝑜𝑙𝑦 = 𝑚𝑐𝑣 𝑑𝑇 + =𝑚⋅ ⋅ 𝑑𝑇 +
𝑛−1 𝛾−1 𝑛−1
𝑚 ⋅ 𝑅 ⋅ (𝑇2 − 𝑇1 ) 𝑃1 𝑉1 − 𝑃2 𝑉2 𝑃2 𝑉2 − 𝑃1 𝑉1 𝑃1 𝑉1 − 𝑃2 𝑉2 1 1
đ𝑄𝑝𝑜𝑙𝑦 = + = + = (𝑃1 𝑉1 − 𝑃2 𝑉2 ) ⋅ ( − )
𝛾−1 𝑛−1 𝛾−1 𝑛−1 𝑛−1 𝛾−1
𝛾−𝑛 𝑃1 𝑉1 − 𝑃2 𝑉2 𝛾−𝑛
đ𝑄𝑝𝑜𝑙𝑦 = 𝑃1 𝑉1 − 𝑃2 𝑉2 ( )=( )⋅( )
(𝛾 − 1) ⋅ (𝑛 − 1) 𝑛−1 𝛾−1
𝛾−𝑛
đ𝑄𝑝𝑜𝑙𝑦 = đ𝑊𝑝𝑜𝑙𝑦 ×
𝛾−1
Polytropic Specific heat
𝛾−𝑛
đ𝑄𝑝𝑜𝑙𝑦 = đ𝑊𝑝𝑜𝑙𝑦 ×
𝛾−1
𝑃1 𝑉1 − 𝑃2 𝑉2 𝛾−𝑛 𝑚𝑅𝑇1 − 𝑚𝑅𝑇2 𝛾 − 𝑛 𝑚𝑅(−𝑑𝑇) 𝛾 − 𝑛 𝛾−𝑛 𝑛−𝛾
đ𝑄𝑝𝑜𝑙𝑦 =( )× =( )× = × = −𝑚𝑐𝑣 𝑑𝑇 ⋅ = 𝑚𝑐𝑣 𝑑𝑇 ⋅
𝑛−1 𝛾−1 𝑛−1 𝛾−1 𝛾−1 𝑛−1 𝑛−1 𝑛−1
𝑛−𝛾
đ𝑄𝑝𝑜𝑙𝑦 = 𝑚 ⋅ (𝑐𝑣 ⋅ ) ⋅ 𝑑𝑇
𝑛−1
𝑛−𝛾
𝑐𝑣⋅𝑃𝑜𝑙𝑦𝑡𝑟𝑜𝑝𝑖𝑐 = 𝑐𝑣 ⋅
𝑛−1
1 < 𝑛 < 𝛾 (𝑐𝑣 > 0)
𝑐𝑝𝑜𝑙𝑦 < 0 (𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒)
For, 1<n<γ, cpolytropic is negative, i.e., during this process though heat is supplied, there is a reduction in temperature this is
because compared to heat supply the work transfer is more, this extra work transfer comes from internal energy of the
system, as there is a decrease in internal energy there is decrease in temperature.
Derivation of PVγ = constant for Adiabatic process
đ𝑄 = 𝑑𝑈 + đ𝑊
đ𝑄 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 → 𝑓𝑜𝑟 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑎𝑛𝑑 𝑐𝑙𝑜𝑠𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚
𝐹𝑜𝑟 𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, đ𝑄 = 0 & 𝑑𝑈 = 𝑚𝑐𝑣 𝑑𝑇 → 0 = 𝑚𝑐𝑣 𝑑𝑇 + 𝑃 ⋅ 𝑑𝑉
𝑚𝑐𝑣 𝑑𝑇 = −𝑃 ⋅ 𝑑𝑉 ①
𝐻 = 𝑈 + 𝑃𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = (𝑑𝐻 + 𝑃𝑑𝑉) + 𝑉𝑑𝑃 = đ𝑄 + 𝑉𝑑𝑃 = 𝑉𝑑𝑃(đ𝑄 = 0)
𝑑𝐻 = 𝑚𝑐𝑝 𝑑𝑇 = 𝑉 ⋅ 𝑑𝑃 ②

② 𝑚𝑐𝑝 𝑑𝑇 𝑉 ⋅ 𝑑𝑃 𝑐𝑝 𝑉 ⋅ 𝑑𝑃
⇒ = → =𝛾=
① 𝑚𝑐𝑣 𝑑𝑇 −𝑃 ⋅ 𝑑𝑉 𝑐𝑣 −𝑃 ⋅ 𝑑𝑉
𝑑𝑉 𝑑𝑃 𝑑𝑃 𝑑𝑉
𝛾 =− → +𝛾 =0
𝑉 𝑃 𝑃 𝑉
𝑑𝑃 𝑑𝑉
∫ + ∫𝛾 = ∫ 0 → 𝑙𝑛 𝑃 + 𝛾 ⋅ 𝑙𝑛 𝑉 = 𝐶 → 𝑙𝑛(𝑃𝑉 𝛾 ) = 𝐶
𝑃 𝑉
𝑃𝑉 𝛾 = 𝐶
The above equation is valid for an ideal gas undergoing reversible adiabatic process only.
Note
1 𝛾−1
𝑉1 𝑇2 𝛾−1 𝑇2 𝑃2 𝛾
𝑊ℎ𝑖𝑙𝑒 𝑑𝑒𝑟𝑖𝑣𝑖𝑛𝑔 =( ) & =( ) , 𝑤𝑒 ℎ𝑎𝑣𝑒 𝑢𝑠𝑒𝑑 𝑃𝑉 𝛾 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
𝑉2 𝑇1 𝑇1 𝑃1
Therefore, all these equations must be used only when an ideal gas undergoes reversible adiabatic process.
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑃𝑉 𝛾 = 𝐶 𝑖𝑠 𝑣𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑏𝑜𝑡ℎ 𝑜𝑝𝑒𝑛 𝑎𝑛𝑑 𝑐𝑙𝑜𝑠𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚𝑠.
Free expansion
The expansion of gas against vacuum (zero resistance) is known as free expansion.
đ𝑄 = 𝑑𝑈 + đ𝑊
0 = 𝑑𝑈 + 0 → 𝑑𝑈 = 0 → 𝑈𝑖 = 𝑈𝑓
Free expansion work is equal to zero.
For work transfer, there should be external resistance, in free expansion, as there is no external resistance work transfer is
zero.
Free expansion of an ideal gas
𝑈𝑓 = 𝑈𝑖 → 𝑇𝑓 = 𝑇𝑖
𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑈 = 𝑓(𝑇)
Though in free expansion of an ideal gas, Ti =Tf doesn’t mean the process is isothermal.
For an isothermal process, all points should pass through the same temperature, during
free expansion, initially during expansion temperature decreases and finally molecules
come in contact with walls of container due to friction heat is generated and temperature
increases.
Though Ti =Tf as temperature is not constant throughout. It’s not an Isothermal process.
In free expansion, though work is equal to zero, P. dV≠0, this sis because W=P. dV is valid
only for closed system undergoing reversible process, but free expansion is irreversible
process.
𝐻 = 𝑈 + 𝑃𝑉 = 𝑈 + 𝑚𝑅𝑇
𝐴𝑠 𝑈 = 𝑓(𝑇) & 𝑚 𝑎𝑛𝑑 𝑅 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠.
𝐻 = 𝜙(𝑇)
𝑈𝑓 = 𝑈𝑖 𝑇𝑓 = 𝑇𝑖 𝐻𝑓 = 𝐻𝑖
Note
For an ideal gas, internal energy (U) and enthalpy (H) both are functions of temperature.
Universal Gas Constant (R̅ )
𝑚
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 (𝑛) = →𝑚 =𝑛⋅𝑀
𝑀
𝑃 ⋅ 𝑉 = 𝑛 ⋅ 𝑅̅ ⋅ 𝑇 = 𝑛 ⋅ (𝑀 ⋅ 𝑅) ⋅ 𝑇 = 𝑚 ⋅ 𝑅 ⋅ 𝑇
𝑅̅
(𝑅̅ = 𝑅 ⋅ 𝑀) → 𝑅 =
𝑀
𝑃 ⋅ 𝑉 = 𝑛 ⋅ 𝑅̅ ⋅ 𝑇
𝑃⋅𝑉 =𝑚⋅𝑅⋅𝑇

𝑅̅ = 8.314 𝑘𝐽⁄𝐾 ⋅ 𝑚𝑜𝑙 − 𝐾

Flow work
The work transfer in causing the fluid either to enter or leave the control volume is called as flow work.
𝐹𝑜𝑟𝑐𝑒 = 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 × 𝐴𝑟𝑒𝑎
𝑊𝑜𝑟𝑘 = 𝐹𝑜𝑟𝑐𝑒 × 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡
𝐹𝑙𝑜𝑤 𝑤𝑜𝑟𝑘 = 𝐹 × 𝑥 = 𝑃 ⋅ 𝑑𝐴 ⋅ 𝑥 = 𝑃 ⋅ 𝑑𝑉
𝐹𝑙𝑜𝑤 𝑤𝑜𝑟𝑘 𝑃 ⋅ 𝑑𝑉 𝑑𝑉
= =𝑃⋅ =𝑃⋅𝜈
𝑚𝑎𝑠𝑠 𝑑𝑚 𝑑𝑚
𝐼𝑓 𝑚𝑎𝑠𝑠 ‘𝑚’ 𝑒𝑛𝑡𝑒𝑟𝑠 𝐶𝑜𝑛𝑡𝑟𝑜𝑙 𝑣𝑜𝑙𝑢𝑚𝑒, 𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤 𝑤𝑜𝑟𝑘 = 𝑃 ⋅ 𝜈 ⋅ 𝑚 = 𝑃 ⋅ 𝑉
Note
If fluid enters at 1, the entry flow work is -P1V1, if fluid leaves at 2, then the exit flow work is +P2V2.
Steady flow energy equation
A flow is said to be steady flow if when fluid properties doesn’t change w.r.t time. For achieving steady flow conditions mass
entering Control volume must be equal to mass leaving Control volume. Similarly, energy entering control volume must be
equal to energy leaving Control Volume.

𝐸𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = 𝐸𝑙𝑒𝑎𝑣𝑖𝑛𝑔
1 1
𝑚𝐶12 + 𝑚𝑔𝑧1 + 𝑈1 + 𝑄 = 𝑚𝐶22 + 𝑚𝑔𝑧2 + 𝑈2 + 𝑊
2 2
1 1
𝑚𝐶12 + 𝑚𝑔𝑧1 + 𝑈1 + 𝑄 = 𝑚𝐶22 + 𝑚𝑔𝑧2 + 𝑈2 + (−𝑃1 𝑉1 + 𝑃2 𝑉2 + 𝑊𝐶.𝑉 )
2 2
1 1
𝑚𝐶12 + 𝑚𝑔𝑧1 + 𝑈1 + 𝑄 + 𝑃1 𝑉1 = 𝑚𝐶22 + 𝑚𝑔𝑧2 + 𝑈2 + 𝑃2 𝑉2 + 𝑊𝐶.𝑉
2 2
(𝑈1 + 𝑃1 𝑉1 = 𝐻1 𝑈2 + 𝑃2 𝑉2 = 𝐻2 )
1 1
𝑚𝐶12 + 𝑚𝑔𝑧1 + 𝐻1 + 𝑄 = 𝑚𝐶22 + 𝑚𝑔𝑧2 + 𝐻2 + 𝑊𝐶.𝑉
2 2
1 1
ℎ1 + 𝐶12 + 𝑔𝑧1 + 𝑞 = ℎ2 + 𝐶22 + 𝑔𝑧2 + 𝑤𝐶.𝑉 → 𝑆𝑡𝑒𝑎𝑑𝑦 𝑓𝑙𝑜𝑤 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
2 2
Applicable for reversible and irreversible process. this equation is first law of thermodynamics for open system under steady
flow conditions.
Examples of Steady flow devices
Nozzle, diffuser, turbine, compressor, boiler, condenser, throttling device etc…
Applications of steady flow equation
Nozzle
Nozzle is a device which is used for increasing velocity at the expense of pressure.
Nozzles are used in jet engines, impulse turbines etc…
Diffuser
Diffuser is a device which is used for increasing pressure at the expense of velocity.
In nozzles and diffusers, there is no work transfer i.e., WC. V = 0.
1 1
ℎ1 + 𝐶12 + 𝑔𝑧1 + 𝑞 = ℎ2 + 𝐶22 + 𝑔𝑧2 + 𝑤𝐶.𝑉
2 2
(𝑧1 = 𝑧2 ) (𝑞 = 0) (𝑤𝐶.𝑉 = 0)
1 1
ℎ1 + 𝐶12 = ℎ2 + 𝐶22
2 2
1
ℎ1 = ℎ2 + 𝐶22 (𝑖𝑓 𝐶1 ≪ 𝐶2 )
2
Turbine
1 1
ℎ1 + 𝐶12 + 𝑔𝑧1 + 𝑞 = ℎ2 + 𝐶22 + 𝑔𝑧2 + 𝑤𝐶.𝑉
2 2
ℎ1 = ℎ2 + 𝑤𝐶.𝑉
𝑤𝐶.𝑉 = ℎ1 − ℎ2
𝑤𝑡𝑢𝑟𝑏𝑖𝑛𝑒 = ℎ1 − ℎ2
Assumptions
1. Steady flow
2. Potential energy changes are neglected
3. Kinetic energy changes are neglected
4. Turbine is perfectly insulated
In turbine, work is developed at the expense of enthalpy i.e., as the fluid flows turbine enthalpy decreases and this decrease
in enthalpy is converted into work.
Compressor
𝑤𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟 = −𝑤𝑡𝑢𝑟𝑏𝑖𝑛𝑒 = −(ℎ1 − ℎ2 )
𝑤𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟 = ℎ2 − ℎ1
Assumptions
1. Steady flow
2. Potential energy changes are neglected
3. Kinetic energy changes are neglected
4. Turbine is perfectly insulated
In compressors, enthalpy increases because of work input.
Throttling device
Examples of throttling
Flow through a partially open valve, floe through a very small opening (orifice), flow through a porous plug.
Characteristics of Throttling
1. No heat transfer (Generally, the size of throttling device is so small and the time spent by the fluid in the device is
very small and hence there is no time available for heat transfer. Therefore, heat transfer is zero.)
2. There is no work transfer (Though there is a pressure drop in throttling due to friction work is lost)
3. It is an irreversible process.
4. It is isenthalpic process.
1 1
ℎ1 + 𝐶12 + 𝑔𝑧1 + 𝑞 = ℎ2 + 𝐶22 + 𝑔𝑧2 + 𝑤𝐶.𝑉
2 2
1 2 1
ℎ1 + 𝐶1 = ℎ2 + 𝐶22
2 2
ℎ1 ≈ ℎ2

Unsteady flow (Transient flow)

When fluid properties changes w.r.t time, then the floe is unsteady.
Examples are filling the tank, discharging the tank.
Let mi & me be the masses entering and leaving the control volume.
Let m1 & m2 be the masses in control volume under initial and final conditions.
Conservation of mass
𝑑𝑚 𝑑𝑚𝑖 𝑑𝑚𝑒
( ) = −
𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝑑𝑡
𝑑𝑚
( ) = 𝑚̇ 𝑖 − 𝑚̇ 𝑒
𝑑𝑡 𝐶.𝑉
Conservation of energy
1
𝐸𝑖 = 𝑚𝑖 𝐶𝑖2 + 𝑚𝑖 𝑔𝑧𝑖 + 𝑚𝑖 ℎ𝑖 + 𝑄
2
1
𝐸𝑒 = 𝑚𝑒 𝐶𝑒2 + 𝑚𝑒 𝑔𝑧𝑒 + 𝑚𝑒 ℎ𝑒 + 𝑊
2
𝑑𝐸 𝑑𝐸𝑖 𝑑𝐸𝑒
( ) = −
𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝑑𝑡
𝑑𝐸 𝑑 1 𝑑 1
( ) = ( 𝑚𝑖 𝐶𝑖2 + 𝑚𝑖 𝑔𝑧𝑖 + 𝑚𝑖 ℎ𝑖 + 𝑄) − ( 𝑚𝑒 𝐶𝑒2 + 𝑚𝑒 𝑔𝑧𝑒 + 𝑚𝑒 ℎ𝑒 + 𝑊)
𝑑𝑡 𝐶.𝑉 𝑑𝑡 2 𝑑𝑡 2
𝐸 =𝑃⋅𝐸+𝐾⋅𝐸+𝑈
𝑑𝐸 = 𝑑(𝐾. 𝐸) + 𝑑(𝑃. 𝐸) + 𝑑𝑈
𝑖𝑓 𝑐ℎ𝑎𝑛𝑔𝑒𝑠 𝑖𝑛 𝐾. 𝐸 𝑎𝑛𝑑 𝑃. 𝐸 𝑎𝑟𝑒 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑒𝑑 𝑖. 𝑒. , 𝑑(𝐾. 𝐸) ≈ 0 & 𝑑(𝑃. 𝐸) ≈ 0
𝑑𝐸 = 𝑑𝑈
Assumption 1
Neglect K.E and P.E
𝑑𝐸 𝑑𝑈 𝑑 𝑑
( ) = ( ) = (𝑚𝑖 ℎ𝑖 + 𝑄) − (𝑚𝑒 ℎ𝑒 + 𝑊)
𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝑑𝑡
Assumption 2
If hi & he doesn’t change w.r.t time
𝑑𝐸 𝑑𝑈 𝑑 𝑑 𝑑𝑚𝑖 𝑑𝑚𝑒
( ) = ( ) = (𝑚𝑖 ℎ𝑖 + 𝑄) − (𝑚𝑒 ℎ𝑒 + 𝑊) = ⋅ ℎ𝑖 + 𝑄̇ − ⋅ ℎ𝑒 − 𝑊̇
𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝑈 𝑑𝑚𝑖 𝑑𝑚𝑒
( ) = ⋅ ℎ𝑖 + 𝑄̇ − ⋅ ℎ𝑒 − 𝑊̇
𝑑𝑡 𝐶.𝑉 𝑑𝑡 𝑑𝑡

Second law of Thermodynamics

Need for second law
First law of thermodynamics simply says that energy is conserved. It doesn’t give any direction for a particular process. To
know whether the process is possible or not i.e., to know the direction, second law of thermodynamics must be applied. If the
direction is known then first law must be applied.
Hence second law is known as directional law.
It’s found from the experiments, complete conversion of low grade energy to high grade energy work is impossible to cycle.
Note
The complete conversion of heat into work is possible in a process i.e., when an ideal gas undergoes isothermal process, heat
transfer and work transfer are same. In such a process complete heat is converted into work.
Work is known as organized form of energy or high-grade energy.
Heat is disorganized form of energy or low-grade energy.
Thermal energy reservoirs
Source
It’s a reservoir which is capable of supplying heat without any temperature change.
Sink
It’s a reservoir which absorbs heat without undergoing any temperature change.
Note
Thermal Energy reservoirs, source and sink are closed systems with only heat transfer.
Statements of second law of thermodynamics
Kelvin planks Statement (Valid only for a cycle)
It’s impossible to develop a device operating on a cycle, which produces work continuously while exchanging heat with
single reservoir.
 𝑂𝑢𝑡𝑝𝑢𝑡 𝑊
𝜂= → 𝜂𝑡ℎ =
𝐼𝑛𝑝𝑢𝑡 𝑄
𝑊 𝑄
𝜂= = = 100%
𝑄 𝑄
The efficiency of PMM-2 is 100%. As PMM-2 is impossible. Therefore, 100% efficiency of any engine is
impossible according to second law of thermodynamics.
Heat engine
It’s a device operating on a cycle which converts part of heat into work and rejects remaining to a sink
or surrounding.
Heat engine is a work-producing device.
𝑊
𝜂=
𝑄1
→ 𝑊 = 𝑄1 − 𝑄2 = 𝑄𝑠 − 𝑄𝑟
𝑄1 − 𝑄2 𝑄2
𝜂𝑡ℎ = → 𝜂𝑡ℎ = 1 −
𝑄1 𝑄1

Clausius statement
It’s impossible to develop a device, operating on a cycle and which transfers heat from lower temperature
to higher temperature without any external work.

Refrigerator
A refrigerator is a device which maintains lower temperature compared to surroundings.
As lower temperatures are maintained continuously refrigerator should operate in a cycle.
𝑊 + 𝑄2 = 𝑄1 → 𝑊 = 𝑄1 − 𝑄2
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑒𝑓𝑓𝑒𝑐𝑡
𝐶𝑂𝑃 =
𝐸𝑛𝑒𝑟𝑔𝑦 𝑒𝑓𝑓𝑒𝑐𝑡
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑒𝑓𝑓𝑒𝑐𝑡 = 𝑄2
𝑄2 𝑄2
𝐶𝑂𝑃𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 = =
𝑊 𝑄1 − 𝑄2

Heat pump
Heat pump is a device which maintains higher temperatures compared to surroundings. As
higher temperature is to be maintained continuously, heat pump operates on a cycle.
𝑊 + 𝑄2 = 𝑄1 → 𝑊 = 𝑄1 − 𝑄2
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑒𝑓𝑓𝑒𝑐𝑡
𝐶𝑂𝑃 =
𝐸𝑛𝑒𝑟𝑔𝑦 𝑒𝑓𝑓𝑒𝑐𝑡
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑒𝑓𝑓𝑒𝑐𝑡 = 𝑄1
𝑄1 𝑄1
𝐶𝑂𝑃ℎ𝑒𝑎𝑡 𝑝𝑢𝑚𝑝 = =
𝑊 𝑄1 − 𝑄2
Note
Heat engine, refrigerator, heat pump operates on a cycle.
Relationship between COP of a heat pump and COP of a refrigerator operating between same temperature limits.
𝑄1 𝑄1 𝑄2 𝑄2
𝐶𝑂𝑃ℎ𝑒𝑎𝑡 𝑝𝑢𝑚𝑝 = = 𝐶𝑂𝑃𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 = =
𝑊 𝑄1 − 𝑄2 𝑊 𝑄1 − 𝑄2
𝑄1 𝑄2
𝐶𝑂𝑃𝐻.𝑃 − 𝐶𝑂𝑃𝑅 = − =1
𝑄1 − 𝑄2 𝑄1 − 𝑄2
𝐶𝑂𝑃𝐻.𝑃 = 𝐶𝑂𝑃𝑅 + 1
Equibalance of kelvin Plank and Clausius statement

Violation of Kelvin Plank statement

Similarly, it can be proved that violation of Kelvin Plank statement leads to violation of Clausius statement.
Note
A process which satisfies first law of thermodynamics need not be practically possible.

Carnot cycle
A cycle is said it be reversible cycle, when all processes in a cycle are reversible.

1—2  Reversible Isothermal heat addition (Expansion)

2—3  Reversible adiabatic expansion
3—4  Reversible Isothermal heat rejection (Compression)
4—1  Reversible Adiabatic compression

Carnot cycle consists of two isothermal processes and two Adiabatic processes.
Isothermal process is a slow process and adiabatic process is a fast process and hence, these two combinations are difficult
to achieve in process, moreover as process is a reversible process and reversible process is a quasi-static process. It should
occur very slowly and the complete cycle runs very slowly, because of these reasons Carnot cycle is not a practical cycle. But
it’s used for comparing other cycle.
Carnot’s theorem
For different engines operating between same temperature limits, no engine can
have efficiency greater than Carnot cycle or reversible cycle.
Let us assume that efficiency of irreversible engine is greater than reversible engine
efficiency.
𝜂1 > 𝜂2
𝑊1 𝑊2
>
𝑄1 𝑄1
𝑊1 > 𝑊2
As E2 is a reversible engine, let us reverse the engine.

Violation of Kelvin-Planck’s Statement

Hence, our assumption is wrong.
Therefore, irreversible cycle efficiency can never be greater than reversible cycle efficiency operating between same
temperature limits.
Important points w.r.t Reversible cycle
1. All reversible engine operating between same temperature limits have same efficiency.
2. Efficiency of a reversible cycle is independent of working fluid.
3. Reversible cycle efficiency depends only on temperature limits.
Thermodynamics Temperature cycle
𝑄𝑅 𝑄2
𝜂1 = 1 − =1−
𝑄𝑆 𝑄1
E1 is reversible engine.
𝜂1 = 𝑓1 (𝑇1 , 𝑇2 )
𝑄2
1− = 𝑓(𝑇1 , 𝑇2 )
𝑄1
𝑄2 𝑄1 1
= 1 + 𝑓(𝑇1 , 𝑇2 ) → =
𝑄1 𝑄2 1 + 𝑓(𝑇1 , 𝑇2 )
𝑄1
= 𝜙(𝑇1 , 𝑇2 )
𝑄2
𝑄2
𝑆𝑖𝑚𝑖𝑙𝑎𝑟𝑙𝑦, = 𝜙(𝑇2 , 𝑇3 )
𝑄3
𝑄1
𝑆𝑖𝑚𝑖𝑙𝑎𝑟𝑙𝑦, = 𝜙(𝑇1 , 𝑇3 )
𝑄3
𝑄1
𝑄1 ⁄𝑄 𝜙(𝑇1 , 𝑇3 ) 𝜓(𝑇1 )
3
= = =
𝑄2 𝑄2⁄ 𝜙(𝑇2 , 𝑇3 ) 𝜓(𝑇2 )
𝑄3
𝑄1 𝑇1
=
𝑄2 𝑇2
This equation is valid only for a reversible cycle.
Efficiency of a reversible cycle
𝑄1 𝑇1
𝜂 =1− → 𝜂 =1−
𝑄2 𝑇2
𝑄1 𝑇1
= → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝑄2 𝑇2
COP of a reversible Refrigerator
𝑄2
𝐶𝑂𝑃 = (𝑓𝑜𝑟 𝑎𝑛𝑦 𝑟𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 𝑐𝑦𝑐𝑙𝑒)
𝑄1 − 𝑄2
𝑄1 𝑇1
= → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝑄2 𝑇2
𝑄2 1 1 𝑇2 𝑇2
𝐶𝑂𝑃 = = = = 𝐶𝑂𝑃 =
𝑄1 − 𝑄2 𝑄1 − 1 𝑇1 − 1 𝑇1 − 𝑇2 𝑇1 − 𝑇2
𝑄2 𝑇2
COP will be maximum for reversible cycles.

Irreversible (or)
Device Reversible
Reversible
𝑇ℎ 𝑄ℎ
Engine Efficiency 1− 1−
𝑇𝑙 𝑄𝑙
𝑇𝑙 𝑄2
Refrigerator COP
𝑇ℎ − 𝑇𝑙 𝑄1 − 𝑄2
𝑇ℎ 𝑄1
Heat pump COP
𝑇ℎ − 𝑇𝑙 𝑄1 − 𝑄2

Clausius Inequality
đ𝑄
𝑇ℎ𝑒 𝑐𝑦𝑐𝑙𝑒 𝑖𝑛𝑡𝑒𝑔𝑟𝑎𝑙 𝑜𝑓 𝑖𝑠 𝑙𝑒𝑠𝑠 𝑡ℎ𝑎𝑛 𝑜𝑟 𝑒𝑞𝑢𝑎𝑙 𝑡𝑜 𝑧𝑒𝑟𝑜.
𝑑𝑇
đ𝑄
∮ ≤0
𝑑𝑇
đ𝑄
∮ < 0 → 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
𝑑𝑇
đ𝑄
∮ = 0 → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
𝑑𝑇
Case 1 (Reversible Cycle)
𝑄1 𝑄2
𝐹𝑜𝑟 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒𝑠 →
=
𝑇1 𝑇2
đ𝑄 𝑄1 𝑄2 𝑄1 𝑄2 𝑄1 𝑄1
∮ = + (− ) = − = − =0
𝑇 𝑇1 𝑇2 𝑇1 𝑇2 𝑇1 𝑇1
đ𝑄
∮ =0
𝑇
Case 2 (Irreversible Case)
𝜂𝑟𝑒𝑣 > 𝜂𝑖𝑟𝑟𝑒𝑣
𝑊1 𝑊2
> → 𝑊1 > 𝑊2
𝑄1 𝑄1
→ (𝑄1 − 𝑄2⋅𝑟𝑒𝑣 ) > (𝑄1 − 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 ) → 𝑄2⋅𝑟𝑒𝑣 < 𝑄2⋅𝑖𝑟𝑟𝑒𝑣
đ𝑄 𝑄1 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 𝑄1 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 𝑄2⋅𝑟𝑒𝑣 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 𝑄2⋅𝑟𝑒𝑣 − 𝑄2⋅𝑖𝑟𝑟𝑒𝑣
∮ = + (− )= − = − =
𝑇 𝑇1 𝑇2 𝑇1 𝑇2 𝑇2 𝑇2 𝑇2
𝐴𝑠, 𝑄2⋅𝑟𝑒𝑣 < 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 → 𝑄2⋅𝑟𝑒𝑣 − 𝑄2⋅𝑖𝑟𝑟𝑒𝑣 < 0

đ𝑄
∮ <0
𝑇
𝑖𝑟𝑟𝑒𝑣
 Significance of Clausius equation
With the help of Clausius inequality, Nature of cycle can be established. Whether the cycle is irreversible or irreversible can
be established with Clausius inequality.
đ𝑄
∮ = 0 → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
𝑇
đ𝑄
∮ < 0 → 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
𝑇
đ𝑄
∮ > 0 → 𝐼𝑚𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
𝑇
To show that it’s impossible to reach absolute zero (0 K), according to second law of thermodynamics.

𝑄1 𝑄2 𝑄1
= → 𝑄2 = × 𝑇2
𝑇1 𝑇2 𝑇1
If T2 = 0 K,
𝑄1
𝑄2 = × 0 → 𝑄2 = 0
𝑇1

It’s a violation of Kelvin Plank’s Statement, so it is not possible.

Entropy
Case 1 (Reversible Cycle)
1 − 𝑎 − 2 − 𝑏 − 1 → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
1 − 𝑎 − 2 − 𝑐 − 1 → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
đ𝑄
∮ =0
𝑇
𝑟𝑒𝑣
đ𝑄 đ𝑄
( ) +( ) =0 ①
𝑇 1𝑎2 𝑇 2𝑏1
đ𝑄 đ𝑄
( ) +( ) =0 ②
𝑇 1𝑎2 𝑇 2𝑐1
①−② ⟹
đ𝑄 đ𝑄 đ𝑄 đ𝑄
→( ) −( ) =0→ ( ) =( )
𝑇 2𝑏1 𝑇 2𝑐1 𝑇 2𝑏1 𝑇 2𝑐1
đ𝑄 đ𝑄
( ) =( ) = 𝑑𝑆
𝑇 𝑟𝑒𝑣, 𝑏 𝑇 𝑟𝑒𝑣, 𝑐

đ𝑄
( ) = 𝑑𝑆
𝑇 𝑟𝑒𝑣
đ𝑄
𝑇ℎ𝑜𝑢𝑔ℎ 𝑝𝑎𝑡ℎ𝑠 𝐴 & 𝐵 & 𝐶 𝑎𝑟𝑒 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡 ( ) 𝑎𝑟𝑒 𝑠𝑎𝑚𝑒 𝑓𝑜𝑟 𝑝𝑎𝑡ℎ𝑠 𝐵 & 𝐶.
𝑇 𝑟𝑒𝑣
đ𝑄
𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒, ( ) 𝑚𝑢𝑠𝑡 𝑏𝑒 𝑎 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦 𝑎𝑛𝑑 𝑖𝑠 𝑘𝑛𝑜𝑤𝑛 𝑎𝑠 𝐸𝑛𝑡𝑟𝑜𝑝𝑦
𝑇 𝑟𝑒𝑣
Case 2 (Irreversible process)
1 − 𝑎 − 2 − 𝑏 − 1 → 𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
1 − 𝑎 − 2 − 𝑐 − 1 → 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑐𝑦𝑐𝑙𝑒
đ𝑄 đ𝑄 đ𝑄
∮ =0→( ) +( ) =0
𝑇 𝑇 1𝑎2 𝑇 2𝑏1
𝑟𝑒𝑣

đ𝑄 đ𝑄
( ) = −( )
𝑇 1𝑎2 𝑇 2𝑏1

đ𝑄 đ𝑄 đ𝑄 đ𝑄 đ𝑄
∮ <0→ ( ) +( ) <0 → −( ) +( ) <0
𝑇 𝑇 1𝑎2 𝑇 2𝑐1 𝑇 2𝑏1 𝑇 2𝑐1
𝑖𝑟𝑟𝑒𝑣
đ𝑄 đ𝑄 đ𝑄 đ𝑄
−( ) + ( ) <0 →( ) >( )
𝑇 𝑟𝑒𝑣 𝑇 𝑖𝑟𝑟𝑒𝑣 𝑇 𝑟𝑒𝑣 𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄
𝑑𝑆 > ( )
𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄 đ𝑄
𝑑𝑆 = ( ) , 𝑑𝑆 > ( )
𝑇 𝑟𝑒𝑣 𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄
→ 𝑑𝑆 ≥ ( )
𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄 đ𝑄
𝑑𝑆𝑟𝑒𝑣 = 𝑑𝑆𝑖𝑟𝑟𝑒𝑣 , 𝑏𝑢𝑡 ( ) <( )
𝑇 𝑖𝑟𝑟𝑒𝑣 𝑇 𝑟𝑒𝑣
As long as end points are same, Entropy change will be same,
irrespective of the process, i.e., reversible or irreversible.
In order to calculate entropy change for irreversible process, it must be replaced by a reversible process within the same end
points.
Entropy change of a system in a reversible process
Case 1 (Reversible Heat supply)
đ𝑄
𝑑𝑆 =
𝑇
𝐻𝑒𝑎𝑡 𝑠𝑢𝑝𝑝𝑙𝑦 → đ𝑄 > 0, & 𝑇>0
𝐴𝑠 đ𝑄 & 𝑇 𝑎𝑟𝑒 𝑔𝑟𝑒𝑎𝑡𝑒𝑟 𝑡ℎ𝑎𝑛 𝑧𝑒𝑟𝑜, → 𝑑𝑆 > 0 → 𝑆2 − 𝑆1 > 0 → 𝑆2 > 𝑆1
In a reversible process when heat is supplied the system Entropy increases.
Case 2 (Reversible Heat rejection)
đ𝑄
𝑑𝑆 =
𝑇
𝐻𝑒𝑎𝑡 𝑟𝑒𝑗𝑒𝑐𝑡𝑖𝑜𝑛 → đ𝑄 < 0, & 𝑇>0
𝐴𝑠 đ𝑄 𝑖𝑠 𝑙𝑒𝑠𝑠 𝑡ℎ𝑎𝑛 𝑧𝑒𝑟𝑜 𝑎𝑛𝑑 𝑇 𝑔𝑟𝑒𝑎𝑡𝑒𝑟 𝑡ℎ𝑎𝑛 𝑧𝑒𝑟𝑜, → 𝑑𝑆 < 0 → 𝑆2 − 𝑆1 < 0 → 𝑆2 < 𝑆1
In a reversible process when heat is rejected the system Entropy decreases.
Case 3 (Reversible Adiabatic process)
đ𝑄
𝑑𝑆 =
𝑇
𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 → đ𝑄 = 0 → 𝑑𝑆 = 0 → 𝑆2 = 𝑆1
A reversible Adiabatic process is always Isentropic.
In a reversible process system entropy can increase, decrease depending on Heat transfer.
Entropy change in Irreversible process
đ𝑄
𝑑𝑆 > ( )
𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄
𝑑𝑆 = ( ) + 𝛿𝑆𝑔𝑒𝑛 (𝛿𝑆𝑔𝑒𝑛 > 0)
𝑇 𝑖𝑟𝑟𝑒𝑣
đ𝑄
𝐼𝑓 ( ) = −𝛿𝑆𝑔𝑒𝑛 , 𝑡ℎ𝑒𝑛 𝑑𝑆 = 0 (𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝐼𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐)
𝑇 𝑖𝑟𝑟𝑒𝑣
Though a reversible adiabatic process is isentropic, an isentropic process need not be reversible adiabatic.
Adiabatic
⏞
𝑅𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
đ𝑄 đ𝑄
𝑑𝑆 = 𝑑𝑆 = ( ) + 𝛿𝑆𝑔𝑒𝑛
𝑇 𝑇 𝑖𝑟𝑟𝑒𝑣
0 𝑑𝑆 = 0 + 𝛿𝑆𝑔𝑒𝑛
𝑑𝑆 = 𝑇 = 0
𝑆=0 𝑑𝑆 > 0 (𝛿𝑆𝑔𝑒𝑛 > 0)
𝐼𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐 𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑖𝑛𝑔
All adiabatic processes are not isentropic. If adiabatic process is isentropic, then it is reversible. If the adiabatic process is
irreversible then entropy increases. In an adiabatic process system entropy never decreases.
Physical meaning of Entropy
Entropy is a measure of randomness. Greater the disorderliness, greater the entropy and lesser the efficiency.
Entropy change of a Universe
𝑑𝑆𝑢𝑛𝑖 = 𝑑𝑆𝑠𝑢𝑟𝑟 + 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚
𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑒 𝑖𝑠 𝑎𝑛 𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚 → 𝑑𝑄 = 0
đ𝑄
𝑑𝑆 ≥ → 𝑑𝑆𝑢𝑛𝑖 ≥ 0
𝑇
According to second law of thermodynamics all those processes are possible, the change of entropy of universe is greater
than or equal to zero.
According to second law of thermodynamics, universe entropy never decreases. This is known as Principle of increases of
entropy.
System entropy can increase or decrease, surrounding entropy can increase or decrease but Universe entropy never
decreases.
𝑆𝑠𝑜𝑙𝑖𝑑𝑠 < 𝑆𝑙𝑖𝑞𝑢𝑖𝑑𝑠 < 𝑆𝑔𝑎𝑠𝑒𝑠
𝑑𝑆𝑢𝑛𝑖 > 0 → 𝑃𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑠 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
𝑑𝑆𝑢𝑛𝑖 = 0 → 𝑃𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑠 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒
𝑑𝑆𝑢𝑛𝑖 < 0 → 𝑃𝑟𝑜𝑐𝑒𝑠𝑠 𝑖𝑠 𝑖𝑚𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒
Entropy generation
đ𝑄
𝑑𝑆𝑎 = ( ) + 𝛿𝑆𝑔𝑒𝑛, 𝑎
𝑇 𝑖𝑟𝑟𝑒𝑣, 𝑎
đ𝑄
𝑑𝑆𝑏 = ( ) + 𝛿𝑆𝑔𝑒𝑛, 𝑏
𝑇 𝑖𝑟𝑟𝑒𝑣, 𝑏
𝑑𝑆𝑎 = 𝑑𝑆𝑏 → 𝑏𝑢𝑡 đ𝑄𝑎 < đ𝑄𝑏 → 𝛿𝑆𝑔𝑒𝑛, 𝑎 > 𝛿𝑆𝑔𝑒𝑛, 𝑏
Though entropy is a property, entropy generation is not a property, because entropy generation
depends on extent of irreversibility. greater the irreversibility’s, greater the entropic generation.
đ𝑄
𝑑𝑆 = + 𝛿𝑆𝑔𝑒𝑛 → 𝑑𝑆𝑢𝑛𝑖 = 0 + 𝛿𝑆𝑔𝑒𝑛 → 𝑑𝑆𝑢𝑛𝑖 = 𝛿𝑆𝑔𝑒𝑛
𝑇
𝛿𝑆𝑔𝑒𝑛 = 𝑑𝑆𝑠𝑢𝑟𝑟 + 𝑑𝑆𝑠𝑦𝑠
T-S diagram
𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑡ℎ𝑒 𝑐𝑢𝑟𝑣𝑒 = 𝑇 ⋅ 𝑑𝑆
đ𝑄
𝑑𝑆 = (𝑟𝑒𝑣) → đ𝑄 = 𝑇 ⋅ 𝑑𝑆
𝑇
đ𝑄 = 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑡ℎ𝑒 𝑐𝑢𝑟𝑣𝑒
The Area under the curve when projected on entropy axis gives reversible heat transfer.
Representation of Carnot cycle in T-S diagram
1 − 2 → 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐻𝑒𝑎𝑡 𝑎𝑑𝑑𝑖𝑡𝑖𝑜𝑛
2 − 3 → 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛
3 − 4 → 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐻𝑒𝑎𝑡 𝑟𝑒𝑗𝑒𝑐𝑡𝑖𝑜𝑛
4 − 1 → 𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝐴𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛
Carnot cycle can be represented by a rectangle in T-S diagram.
Note
A cycle which is clockwise in P-V diagram is also clockwise on T-S diagram.
Combined first and second law of thermodynamics
đ𝑄 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠) → 𝑓𝑖𝑟𝑠𝑡 𝑙𝑎𝑤
đ𝑄
𝑑𝑆 = → đ𝑄 = 𝑇 ⋅ 𝑑𝑆 (𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠) → 𝑠𝑒𝑐𝑜𝑛𝑑 𝑙𝑎𝑤
𝑇
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉
This equation is applicable for any process (reversible or irreversible) because this equation connects various properties and
this equation can be used for any working fluid.
𝐻 =𝑈+𝑃⋅𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 + 𝑉 ⋅ 𝑑𝑃 = (𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉) + 𝑉 ⋅ 𝑑𝑃 = đ𝑄 + 𝑉 ⋅ 𝑑𝑃 = 𝑇 ⋅ 𝑑𝑆 + 𝑉 ⋅ 𝑑𝑃
𝑑𝐻 = 𝑇 ⋅ 𝑑𝑆 + 𝑉 ⋅ 𝑑𝑃 → 𝑇 ⋅ 𝑑𝑆 = 𝑑𝐻 − 𝑉 ⋅ 𝑑𝑃
This equation is applicable for any process, i.e., reversible or irreversible and any working fluid.
Representation of constant volume and constant pressure processes on T-S diagram for an Ideal gas
Constant Volume
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉
𝐼𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 → 𝑑𝑉 = 0
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 → 𝑇 ⋅ 𝑑𝑠 = 𝑑𝑢 → 𝑇 ⋅ 𝑑𝑠 = 𝑐𝑣 ⋅ 𝑑𝑇 (𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇)
𝑑𝑇 𝑇
𝑇 ⋅ 𝑑𝑠 = 𝑐𝑣 ⋅ 𝑑𝑇 → =
𝑑𝑠 𝑐𝑣
𝑇
𝑆𝑙𝑜𝑝𝑒 = 𝑚𝑉=𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
𝑐𝑣
This equation is valid for both ideal and real gases because dU=cv dT is valid for both ideal and real gases under constant
volume conditions.
Constant Pressure
𝑑𝐻 = 𝑇 ⋅ 𝑑𝑆 + 𝑉 ⋅ 𝑑𝑃
𝐼𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 → 𝑑𝑃 = 0
𝑑𝐻 = 𝑇 ⋅ 𝑑𝑆 → 𝑑ℎ = 𝑇 ⋅ 𝑑𝑠 → 𝑐𝑝 ⋅ 𝑑𝑇 = 𝑇 ⋅ 𝑑𝑠 (𝑑ℎ = 𝑐𝑝 ⋅ 𝑑𝑇)
𝑑𝑇 𝑇
𝑐𝑝 ⋅ 𝑑𝑇 = 𝑇 ⋅ 𝑑𝑠 → =
𝑑𝑠 𝑐𝑣
𝑇
𝑆𝑙𝑜𝑝𝑒 = 𝑚𝑃=𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
𝑐𝑝
This is valid for any gas ideal or real. As cp > cv, slope of constant volume curves is greater than slope of constant pressure
curves in T-S diagram.
Entropy changes for an Ideal gas
𝑑𝑈 𝑃 ⋅ 𝑑𝑉 𝑚 ⋅ 𝑐𝑣 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑇 𝑑𝑉 𝑚 ⋅ 𝑐𝑣 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑑𝑉
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 → 𝑑𝑆 = + = + ⋅ = +
𝑇 𝑇 𝑇 𝑉 𝑇 𝑇 𝑉
𝑚⋅𝑅⋅𝑇
(𝑑𝑈 = 𝑚 ⋅ 𝑐𝑣 ⋅ 𝑑𝑇) (𝑃 = ) → 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝑉
𝑚 ⋅ 𝑐𝑣 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑑𝑉
𝑑𝑆 = +
𝑇 𝑉
𝑆2 𝑇2 𝑉2
𝑚 ⋅ 𝑐𝑣 𝑚⋅𝑅
∫ 𝑑𝑆 = ∫ ⋅ 𝑑𝑇 + ∫ ⋅ 𝑑𝑉
𝑆1 𝑇1 𝑇 𝑉1 𝑉
𝑇2 𝑉2
𝑆2 − 𝑆1 = 𝑚 ⋅ 𝑐𝑣 𝑙𝑛 + 𝑚 ⋅ 𝑅 𝑙𝑛 → 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝑇1 𝑉1
𝑑𝐻 𝑉 ⋅ 𝑑𝑃
𝑇 ⋅ 𝑑𝑆 = 𝑑𝐻 − 𝑉 ⋅ 𝑑𝑃 → 𝑑𝑆 =
−
𝑇 𝑇
𝑚 ⋅ 𝑐𝑝 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑇 𝑑𝑃 𝑚 ⋅ 𝑐𝑝 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑑𝑃
→ 𝑑𝑆 = ( )−( ⋅ )=( )−( )
𝑇 𝑃 𝑇 𝑇 𝑃
𝑚⋅𝑅⋅𝑇
(𝑑𝐻 = 𝑚 ⋅ 𝑐𝑝 ⋅ 𝑑𝑇) (𝑉 = ) → 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝑃
𝑚 ⋅ 𝑐𝑝 ⋅ 𝑑𝑇 𝑚 ⋅ 𝑅 ⋅ 𝑑𝑃
→ 𝑑𝑆 = −
𝑇 𝑃
𝑆2 𝑇2 𝑚 ⋅ 𝑐 𝑃2
𝑝 𝑚⋅𝑅
→ ∫ 𝑑𝑆 = ∫ ⋅ 𝑑𝑇 − ∫ ⋅ 𝑑𝑃
𝑆1 𝑇1 𝑇 𝑃1 𝑉
𝑇2 𝑃2
𝑆2 − 𝑆1 = 𝑚 ⋅ 𝑐𝑝 𝑙𝑛 − 𝑚 ⋅ 𝑅 𝑙𝑛 → 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝑇1 𝑃1
𝑉2 𝑃2
𝑺𝒉𝒐𝒘 𝒎𝒆 𝒕𝒉𝒂𝒕 𝒇𝒐𝒓 𝒂𝒏 𝑰𝒅𝒆𝒂𝒍 𝒈𝒂𝒔 𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 + 𝑐𝑣 ⋅ 𝑙𝑛
𝑉1 𝑃1
𝑇2 𝑃2 𝑇2 𝑃2
𝑊𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡, 𝑆2 − 𝑆1 = 𝑚 ⋅ 𝑐𝑝 𝑙𝑛 + 𝑚 ⋅ 𝑅 𝑙𝑛 → 𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 − 𝑅 ⋅ 𝑙𝑛
𝑇1 𝑃1 𝑇1 𝑃1
𝑐𝑝 = 𝑐𝑣 + 𝑅 → 𝑅 = 𝑐𝑝 − 𝑐𝑣
𝑇2 𝑃2 𝑇2 𝑃2 𝑃2
→ 𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 − (𝑐𝑝 − 𝑐𝑣 ) ⋅ 𝑙𝑛 → 𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ (𝑙𝑛 − 𝑙𝑛 ) + 𝑐𝑣 ⋅ 𝑙𝑛
𝑇1 𝑃1 𝑇1 𝑃1 𝑃1
𝑇2 𝑃1 𝑃2 𝑉2 𝑃2
𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 × + 𝑐𝑣 ⋅ 𝑙𝑛 → 𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 + 𝑐𝑣 ⋅ 𝑙𝑛
𝑇1 𝑃2 𝑃1 𝑉1 𝑃1
𝑃1 𝑉1 𝑃2 𝑉2 𝑇2 𝑃1 𝑉2
( = ) → 𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 ⟹ × =
𝑇1 𝑇2 𝑇1 𝑃2 𝑉1
𝑉2 𝑃2
𝑠2 − 𝑠1 = 𝑐𝑝 ⋅ 𝑙𝑛 + 𝑐𝑣 ⋅ 𝑙𝑛
𝑉1 𝑃1

Entropy change for Solids and Liquids

𝑆𝑜𝑙𝑖𝑑𝑠 𝑎𝑛𝑑 𝑙𝑖𝑞𝑢𝑖𝑑𝑠 𝑎𝑟𝑒 𝑖𝑛𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑙𝑒, 𝑠𝑜 𝑑𝑉 = 0
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉 = 𝑑𝑈 + 0 → 𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈
→ 𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 = 𝑚 ⋅ 𝑐 ⋅ 𝑑𝑇 → 𝑇 ⋅ 𝑑𝑆 = 𝑚 ⋅ 𝑐 ⋅ 𝑑𝑇
𝑆2 𝑇2
𝑚⋅𝑐
∫ 𝑑𝑆 = ∫ ⋅ 𝑑𝑇
𝑆1 𝑇1 𝑇
𝑇2
𝑆2 − 𝑆1 = 𝑚 ⋅ 𝑐 ⋅ 𝑙𝑛
𝑇1
Entropy change for a reservoir
đ𝑄
𝑑𝑆 =
𝑇
𝑄1
𝑑𝑆𝑠𝑜𝑢𝑟𝑐𝑒 = −
𝑇1
𝑄2
𝑑𝑆𝑠𝑖𝑛𝑘 =
𝑇2

Note
At equilibrium the entropy is maximum.
đ𝑸
𝒅𝑺 𝜹𝑺𝒈𝒆𝒏
= 𝑻 +
(𝐶ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝐸𝑛𝑡𝑟𝑜𝑝𝑦) (𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛)
(𝐸𝑛𝑡𝑟𝑜𝑝𝑦 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟)
In an adiabatic process as there is no heat transfer, entropy transfer is also zero. Therefore, in an adiabatic process the
entropy change is equal to entropy generation.
In a reversible process as there is no entropy generation, entropy change is equal to entropy transfer.
In a reversible adiabatic process, entropy transfer and entropy change both are zero, therefore, entropy change is zero.
Hence, reversible adiabatic process is always Isentropic.
đ𝑸
𝜹𝑺𝒈𝒆𝒏
𝒅𝑺 = 𝑻
+
(𝐸𝑥𝑡𝑒𝑟𝑛𝑎𝑙 𝐼𝑛𝑡𝑒𝑟𝑎𝑐𝑡𝑖𝑜𝑛) (𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦)
𝑑𝑆 = 𝐸 ⋅ 𝐼 + 𝐼 ⋅ 𝐼
𝑑𝑆𝑠𝑢𝑟𝑟 = 𝐸 ⋅ 𝐼
𝑑𝑆𝑠𝑦𝑠 = 𝐼 ⋅ 𝐼
đ𝑸
𝐼𝑛 𝑎𝑛 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, 𝐸𝑥𝑡𝑒𝑛𝑎𝑙 𝐼𝑛𝑡𝑒𝑟𝑎𝑐𝑡𝑖𝑜𝑛 ( ) = 0 → 𝑑𝑆𝑠𝑢𝑟𝑟 = 0
𝑻
In an Adiabatic process, there is no external interaction in the form of heat transfer. Therefore, entropy change of
surroundings is equal to zero in an adiabatic process.
Entropy change in Open system
đ𝑄̇
𝑑𝑆̇ = ̇
+ 𝛿𝑆𝑔𝑒𝑛
𝑇
𝑑𝑆 đ𝑄̇
( ) = + 𝛿𝑆𝑔𝑒𝑛̇ + 𝑚̇𝑖 𝑠𝑖 − 𝑚̇𝑒 𝑠𝑒
𝑑𝑡 𝐶⋅𝑉 𝑇
𝑑𝑆
𝑆𝑡𝑒𝑎𝑑𝑦 𝑓𝑙𝑜𝑤 → ( ) = 0
𝑑𝑡 𝐶⋅𝑉
đ𝑄 ̇
0= ̇
+ 𝛿𝑆𝑔𝑒𝑛 + 𝑚̇𝑖 𝑠𝑖 − 𝑚̇𝑒 𝑠𝑒
𝑇
đ𝑄̇
𝑚̇𝑖 𝑠𝑖 − 𝑚̇𝑒 𝑠𝑒 = ̇
+ 𝛿𝑆𝑔𝑒𝑛
𝑇
In case of steady flow, open and closed system equations are same.
Ideal gas
A gas is said to be an Ideal gas when there are no intermolecular forces. This occurs at Low densities. An Ideal gas follows all
gas laws. i.e., PV=mRT
𝑚 𝑃
𝑃𝑉 = 𝑚𝑅𝑇 → 𝑃 = 𝑅𝑇 = 𝜌𝑅𝑇 → 𝜌 =
𝑉 𝑅𝑇
Density will be low when pressures are low and temperatures are high. Therefore, a gas behaves as Ideal gas at Low
pressure and high temperature Conditions.
Available energy, Availability and Irreversibility
Available energy
The maximum possible work that can be obtained in a cycle is known as available energy.
𝑊
𝜂=
𝑄1
𝑊𝑚𝑎𝑥
𝜂𝑚𝑎𝑥 =
𝑄1
𝑇2
𝜂𝑚𝑎𝑥 = 𝜂𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 = 1 −
𝑇1
𝑊𝑚𝑎𝑥 𝑇2 𝑇2
= 1 − → 𝑊𝑚𝑎𝑥 = 𝑄1 (1 − )
𝑄1 𝑇1 𝑇1
This work can be further increased, if temperature of heat rejection (T2) is minimum.
The lowest possible temperature of heat rejection is that of surroundings (To).
𝑊 𝑤𝑖𝑙𝑙 𝑏𝑒 𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑤ℎ𝑒𝑛 𝑇2 = 𝑇𝑜

𝑇𝑜
𝑊𝑚𝑎𝑥 (𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒) = 𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝐸𝑛𝑒𝑟𝑔𝑦 = 𝑄1 (1 − )
𝑇1
𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝐸𝑛𝑒𝑟𝑔𝑦 𝑄2
𝑄1 = (𝑚𝑎𝑥𝑖𝑚𝑢𝑚)
+
(𝑚𝑖𝑛𝑖𝑚𝑢𝑚)
𝑀𝑖𝑛𝑖𝑚𝑢𝑚 ℎ𝑒𝑎𝑡 𝑟𝑒𝑗𝑒𝑐𝑡𝑒𝑑 = 𝑈𝑛𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
𝑄1 = 𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 + 𝑈𝑛𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
𝑇𝑜 ⋅ 𝛥𝑆 = 𝑀𝑖𝑛𝑖𝑚𝑢𝑚 𝐻𝑒𝑎𝑡 𝑅𝑒𝑗𝑒𝑐𝑡𝑖𝑜𝑛 = 𝑈𝑛𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦
Unavailable energy (UAE)
The minimum heat rejection is known as Unavailable energy. i.e., area below atmospheric temperature. To represent
unavailable energy on T-S diagram.
Loss of Available energy (Increase in Unavailable energy) due to heat transfer-
𝑄1 = 𝑇1 ⋅ 𝛥𝑆
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑈𝑛𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 (𝑈𝐴𝐸) = 𝑇𝑜 ⋅ 𝛥𝑆
𝐹𝑖𝑛𝑎𝑙 𝑈𝐴𝐸 = 𝑇𝑜 ⋅ 𝛥𝑆 ′
𝑄1 = 𝑇2 ⋅ 𝛥𝑆 ′
𝑄1 𝑄1
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑈𝐴𝐸 = 𝑇𝑜 ⋅ 𝛥𝑆 ′ − 𝑇𝑜 ⋅ 𝛥𝑆 = 𝑇𝑜 (𝛥𝑆 ′ − 𝛥𝑆) = 𝑇𝑜 ( − )
𝑇2 𝑇1
𝑇1 − 𝑇2
𝐼𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 𝑈𝐴𝐸 = 𝑄1 ⋅ 𝑇𝑜 ( )
𝑇1 ⋅ 𝑇2

According to first law of thermodynamics, thermal energy at higher temperature and same amount of thermal energy at
lower temperature has same meaning. Therefore, first law is known as Quantitative law, According, to second law of
thermodynamics, thermal energy at higher temperature has greater significance when compared to equal amount of
thermal energy, because thermal energy at higher temperature can produce more work, hence second law is known as
Qualitative law.
⇒Thermal energy at higher temperature must be preserved and hence the steam turbines are insulated.

Availability
The maximum useful work that can be obtained in a process, when the system comes into equilibrium with atmospheric
conditions.

Note
For calculating availability, the reference point is atmospheric conditions.
Maximum work in a closed system
𝑑𝑆𝑢𝑛𝑖 ≥ 0
𝑑𝑆𝑢𝑛𝑖 = 0 (𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒)
𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟 = 0 → 𝑑𝑆𝑠𝑦𝑠 = −𝑑𝑆𝑠𝑢𝑟𝑟
𝑑𝑄𝑠𝑦𝑠 = −𝑑𝑄𝑠𝑢𝑟𝑟 ②
𝑑𝑄𝑠𝑢𝑟𝑟
𝑑𝑆𝑠𝑢𝑟𝑟 = → 𝑑𝑄𝑠𝑢𝑟𝑟 = 𝑇𝑜 ⋅ 𝑑𝑆𝑠𝑢𝑟𝑟
𝑇𝑜
đ𝑄𝑠𝑦𝑠 = 𝑑𝑈𝑠𝑦𝑠 + đ𝑊𝑠𝑦𝑠 → đ𝑊𝑠𝑦𝑠 = đ𝑄𝑠𝑦𝑠 − 𝑑𝑈𝑠𝑦𝑠
𝑑𝑊𝑠𝑦𝑠 = −đ𝑄𝑠𝑢𝑟𝑟 − 𝑑𝑈𝑠𝑦𝑠 (𝑑𝑄𝑠𝑦𝑠 = −𝑑𝑄𝑠𝑢𝑟𝑟 )
𝑑𝑊𝑠𝑦𝑠 = −(𝑇𝑜 𝑑𝑆𝑠𝑢𝑟𝑟 ) − 𝑑𝑈𝑠𝑦𝑠
𝑑𝑊𝑠𝑦𝑠 = 𝑇𝑜 (𝑑𝑆𝑠𝑦𝑠 ) − 𝑑𝑈𝑠𝑦𝑠 (𝑑𝑆𝑠𝑦𝑠 = −𝑑𝑆𝑠𝑢𝑟𝑟 )
𝑊𝑚𝑎𝑥 = 𝑇𝑜 (𝑆2 − 𝑆1 ) − (𝑈2 − 𝑈1 )
𝑊𝑚𝑎𝑥 = (𝑈1 − 𝑈2 ) − 𝑇𝑜 (𝑆1 − 𝑆2 )
In closed system as the system expands against atmospheric conditions, some amount of work out of the maximum work
done is used for displacing air. This work cannot be utilized.
 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑢𝑠𝑒𝑓𝑢𝑙 𝑤𝑜𝑟𝑘 = 𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑤𝑜𝑟𝑘 – 𝐴𝑡𝑚𝑜𝑠𝑝ℎ𝑒𝑟𝑖𝑐 𝑤𝑜𝑟𝑘.
𝑊𝑚𝑎𝑥 𝑢𝑠𝑒𝑓𝑢𝑙 = 𝑊𝑚𝑎𝑥 − 𝑊𝑎𝑡𝑚 = ((𝑈1 − 𝑈2 ) − 𝑇𝑜 (𝑆1 − 𝑆2 )) − (𝑃𝑜 (𝑉2 − 𝑉1 ))
𝑊𝑚𝑎𝑥 𝑢𝑠𝑒𝑓𝑢𝑙 (𝑈
⏟ 1 − 𝑇𝑜 𝑆1 + 𝑃𝑜 𝑉1 ) (𝑈
⏟ 2 − 𝑇𝑜 𝑆2 + 𝑃𝑜 𝑉2 )
= −
𝜙1 𝜙2
𝜙 = 𝑈 − 𝑇𝑜 𝑆 + 𝑃𝑜 𝑉 → 𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑐𝑙𝑜𝑠𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚

Maximum work in Open system

𝐶12 𝐶22
ℎ1 + + 𝑧1 𝑔 + 𝑞 = ℎ2 + + 𝑧2 𝑔 + 𝑤
2 2
(neglecting Potential and Kinetic Changes)
ℎ1 + 𝑞 = ℎ2 + 𝑤
𝑞 = (ℎ2 − ℎ1 ) + 𝑤 → 𝑞 = 𝑑ℎ + 𝑤
𝑊𝑚𝑎𝑥 = (𝑈1 + 𝑃𝑜 𝑉1 ) − (𝑈2 + 𝑃𝑜 𝑉2 ) − 𝑇𝑜 (𝑆1 − 𝑆2 ) → 𝑊𝑚𝑎𝑥 = 𝐻1 − 𝐻2 − 𝑇𝑜 (𝑆1 − 𝑆2 )
𝑤𝑚𝑎𝑥 = ℎ1 − ℎ2 − 𝑇𝑜 (𝑠1 − 𝑠2 ) → 𝑤𝑚𝑎𝑥 = (ℎ1 − 𝑇𝑜 𝑆1 ) − (ℎ2 − 𝑇𝑜 𝑆2 )
(ℎ − 𝑇 𝑆 ) (ℎ − 𝑇 𝑆 )
𝑊𝑚𝑎𝑥 𝑢𝑠𝑒𝑓𝑢𝑙
= ⏟1 𝑜 1 − ⏟2 𝑜 2
𝜙1 𝜙2
𝑊𝑚𝑎𝑥 𝑢𝑠𝑒𝑓𝑢𝑙 = 𝜙1 − 𝜙2
𝜙 = ℎ − 𝑇𝑜 𝑆 → 𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛 𝑓𝑜𝑟 𝑂𝑝𝑒𝑛 𝑠𝑦𝑠𝑡𝑒𝑚

Irreversibility
𝐼𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦 (𝐼) = 𝑊𝑚𝑎𝑥 − 𝑊𝑎𝑐𝑡𝑢𝑎𝑙
𝐼 = 𝑇𝑜 [(𝑑𝑆)𝑠𝑦𝑠 + (𝑑𝑆)𝑠𝑢𝑟𝑟 ]
𝐼 = 𝑇𝑜 (𝑑𝑆)𝑢𝑛𝑖 → 𝑉𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑏𝑜𝑡ℎ 𝑜𝑝𝑒𝑛 𝑎𝑛𝑑 𝑐𝑙𝑜𝑠𝑒𝑑 𝑠𝑦𝑠𝑡𝑒𝑚
𝛿𝑆𝑔𝑒𝑛 = 𝑑𝑆𝑢𝑛𝑖
𝐼 = 𝑇𝑜 ⋅ 𝛿𝑆𝑔𝑒𝑛
𝐼 ∝ 𝛿𝑆𝑔𝑒𝑛 → 𝐺𝑢𝑜𝑦 − 𝑆𝑡𝑜𝑑𝑜𝑙𝑎 𝑇ℎ𝑒𝑜𝑟𝑒𝑚
According to Guoy-Stodola’s theorem, irreversibility is directly proportionally to entropy generation.
→ 𝐺𝑖𝑏𝑏𝑠 𝐹𝑢𝑛𝑐𝑡𝑖𝑜𝑛 (𝐺) ⟹ 𝐺 = 𝐻 − 𝑇 ⋅ 𝑆
→ 𝐻𝑒𝑙𝑚ℎ𝑜𝑙𝑡𝑧 𝐹𝑢𝑛𝑐𝑡𝑖𝑜𝑛(𝐹) ⟹ 𝐹 = 𝑈 − 𝑇 ⋅ 𝑆
The difference between Gibbs function gives work in Open system.
The difference between Helmholtz function gives maximum work in closed system.

Properties of Pure Substances

A substance that has a fixed chemical composition throughout is called a pure substance.
A pure substance does not have to be of a single chemical element or compound, however a mixture of various chemical
elements or compounds also qualifies as a pure substance as long as the mixture is homogeneous.
Mixture of liquid and water vapor is a pure substance, but a mixture of liquid and gaseous air is not.
Examples: Water (solid, liquid, and vapor phases); Mixture of liquid water and water vapor; Carbon dioxide, CO2; Nitrogen,
N2; Mixtures of gases, such as air, as long as there is no change of phase.
The substances exist in different phases, e.g. at room temperature and pressure, copper is solid and mercury is a liquid.
It can exist in different phases under variations of condition. There are 3 Principal phases. Solid, Liquid and Gas each with
different molecular structures.
Phase-change Processes of Pure Substances
There are many practical situations where two phases of a pure substances coexist in equilibrium.
Solid: strong intermolecular bond; Liquid: intermediate intermolecular bonds; Gas: weak intermolecular bond
E.g. water exists as a mixture of liquid and vapor in the boiler and etc.
Phase change process

The constant pressure heating process can be illustrated as

The point where Saturated liquid line and saturated vapor line meets is called Critical point. It is difficult to distinguish
between liquid and vapor at this point.
Sub-Cooled or Under-cooled region
It is the region in which actual temperature is less than saturation temperature corresponding to that pressure.
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑏 − 𝑐𝑜𝑜𝑙𝑖𝑛𝑔 = 𝑇𝑠𝑎𝑡 − 𝑇𝑎𝑐𝑡
This region is also known as compressed liquid region, because the Pact is greater than Psat corresponding to that
temperature.
Super-Heated Region
It is the region in which actual temperature is greater than saturation temperature, corresponding to that pressure.
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑆𝑢𝑝𝑒𝑟 − ℎ𝑒𝑎𝑡 = 𝑇𝑎𝑐𝑡 − 𝑇𝑠𝑎𝑡

Wet region
It is the region in which both liquid and vapor exist in equilibrium, when the point is in wet region it will exist at saturation
temperature.
Sensible Heat (SH)
The heat transfer associated with temperature change is known as sensible heat.
Latent Heat
The heat transfer associated with phase change is known as latent heat.

𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 (𝐿𝐻) = 𝑄𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑎𝑛𝑔𝑒

→ 𝐿𝐻 = 𝑑ℎ = ℎ2 − ℎ1 → 𝐿𝐻 = ℎ𝑔 − ℎ𝑓 = ℎ𝑓𝑔
𝑄𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 = 𝑇𝑠𝑎𝑡 (𝑆2 − 𝑆1 )
→ 𝐿𝐻 = 𝑄𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 = 𝑇𝑠𝑎𝑡 (𝑆2 − 𝑆1 ) = 𝑇𝑠𝑎𝑡 (𝑆𝑓 − 𝑆𝑔 ) = 𝑇𝑠𝑎𝑡 ⋅ 𝑆𝑓𝑔
𝐿𝐻 = 𝑇𝑠𝑎𝑡 ⋅ 𝑆𝑓𝑔
With the increase in pressure, latent heat of vaporization increases.
At critical point, Latent heat of vaporization is zero.
Dryness fraction (Quality of mixture) (x)
It’s the ratio of mass of vapor to the total mass of mixture.
𝑚𝑣
𝑥=
𝑚𝑣 + 𝑚𝑙

All constant dryness fractions lines converge at critical point.

Specific volume of the mixture
𝑉 = 𝑉𝑣 + 𝑉𝑙
𝑉 = 𝑚𝜈 𝑚 = 𝑚𝑣 + 𝑚𝑙
𝑚 ⋅ 𝜈 = 𝑚𝑣 ⋅ 𝜈𝑣 + 𝑚𝑙 ⋅ 𝜈𝑙
𝑚𝑣 𝑚𝑙
𝜈= ⋅ 𝜈𝑣 + ⋅𝜈
𝑚 𝑚 𝑙
𝑚𝑣 𝑚𝑙
𝜈= ⋅ 𝜈𝑣 + ⋅𝜈
𝑚𝑣 + 𝑚𝑙 𝑚𝑣 + 𝑚𝑙 𝑙
𝜈 = 𝑥 ⋅ 𝜈𝑣 + (1 − 𝑥) ⋅ 𝜈𝑙
𝜈 = 𝜈𝑙 + 𝑥(𝑣𝑣 − 𝑣𝑙 ) 𝜈 = 𝜈𝑓 + 𝑥(𝑣𝑓 − 𝑣𝑔 )

Similarly,
𝐻 = 𝐻𝑓 + 𝐻𝑔 ⟹ ℎ = ℎ𝑓 + 𝑥(ℎ𝑔 − ℎ𝑓 )

𝑈 = 𝑈𝑓 + 𝑈𝑔 ⟹ 𝑢 = 𝑢𝑓 + 𝑥(𝑢𝑔 − 𝑢𝑓 )

𝑆 = 𝑆𝑓 + 𝑆𝑔 ⟹ 𝑠 = 𝑠𝑓 + 𝑥(𝑠𝑔 − 𝑠𝑓 )

Super-heated vapor can be treated as Ideal gas at low pressure. In vapor compression refrigeration system pressures are
low and hence super-heated vapor can be treated as an Ideal gas.
Enthalpy at various points

Case 1
When the point is on saturated vapor curve
ℎ1 = ℎ𝑓 + 𝐿 ⋅ 𝐻
ℎ𝑔 = ℎ𝑓 + 𝐿 ⋅ 𝐻
𝐿 ⋅ 𝐻 = ℎ𝑔 − ℎ𝑓
Case 2
When the point is on wet region
ℎ1 = ℎ𝑓 + 𝑥(−ℎ𝑓 + ℎ𝑔 )
ℎ1 = ℎ𝑓 + 𝑥(𝐿 ⋅ 𝐻)
Case 3
When the point is in super-heated region
ℎ1 = ℎ𝑔 + 𝛥ℎ
ℎ1 = ℎ𝑔 + 𝑐𝑝 ⋅ (𝛥𝑇)
ℎ1 = ℎ𝑔 + 𝑐𝑝 𝑠𝑎𝑡 ⋅ (𝑇1 − 𝑇𝑠𝑎𝑡 )
Entropy at various Points

Case 1
When the point is on saturated vapor curve,
𝑠1 = 𝑠𝑓 + 𝛥𝑠
𝐿𝐻
𝑠𝑔 = 𝑠𝑓 + 𝛥𝑠 → 𝑠𝑔 = 𝑠𝑓 +
𝑇𝑠𝑎𝑡
đ𝑞
𝑑𝑠 =
𝑇
𝐿𝐻 ℎ𝑔 − ℎ𝑓
𝛥𝑠 = =
𝑇𝑠𝑎𝑡 𝑇𝑠𝑎𝑡
Phase change is a reversible process because during phase change the complete system is at same temperature and same
pressure.
Case 2
When the point is in wet region
𝑠1 = 𝑠𝑓 + 𝑥(𝑠𝑔 − 𝑠𝑓 )
𝐿𝐻
𝑠1 = 𝑠𝑓 + 𝑥 ( )
𝑇𝑠𝑎𝑡
Case 3
When the point is in super-heated region
𝑠1 = 𝑠𝑔 + 𝛥𝑠
𝑇𝑓 𝑃𝑓 𝑇1
𝛥𝑠 = 𝑐𝑝 ⋅ 𝑙𝑛 − 𝑅 ⋅ 𝑙𝑛 = 𝑐𝑝 𝑣𝑎𝑝𝑜𝑟 ⋅ 𝑙𝑛
𝑇𝑖 𝑃𝑖 𝑇𝑠𝑎𝑡
𝑇1
𝑠1 = 𝑠𝑔 + 𝑐𝑝 𝑣𝑎𝑝𝑜𝑟 ⋅ 𝑙𝑛
𝑇𝑠𝑎𝑡

Mollier diagram
𝑇 ⋅ 𝑑𝑠 = 𝑑ℎ − 𝑣 ⋅ 𝑑𝑃
𝑇 ⋅ 𝑑𝑠 = 𝑑ℎ (𝑑𝑃 = 0)

𝑑ℎ
𝑇=
𝑑𝑠
Slope of constant pressure lines on h-s diagram
In super-heated region, constant pressure lines diverge because slope of constant pressure lines increases as temperature
increases.
During phase change as temperature is constant, slope is constant. Therefore, on Mollier diagram constant pressure lines
are straight lines in wet region.

P-V diagram

General Substances
𝑆𝑜𝑙𝑖𝑑 → 𝐿𝑖𝑞𝑢𝑖𝑑 ⟹ 𝑀𝑒𝑙𝑡𝑖𝑛𝑔 𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑆𝑜𝑙𝑖𝑑 ⟹ 𝐹𝑟𝑒𝑒𝑧𝑖𝑛𝑔
𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑔𝑎𝑠 ⟹ 𝑉𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
𝐺𝑎𝑠 → 𝐿𝑖𝑞𝑢𝑖𝑑 ⟹ 𝐶𝑜𝑛𝑑𝑒𝑛𝑠𝑎𝑡𝑖𝑜𝑛
𝑆𝑜𝑙𝑖𝑑 → 𝑔𝑎𝑠 ⟹ 𝑆𝑢𝑏𝑙𝑖𝑚𝑎𝑡𝑖𝑜𝑛
𝐺𝑒𝑛𝑒𝑟𝑎𝑙𝑙𝑦, 𝑆𝑜𝑙𝑖𝑑 → 𝐿𝑖𝑞𝑢𝑖𝑑 ⟹ 𝐸𝑥𝑝𝑎𝑛𝑑𝑠, 𝐿𝑖𝑞𝑢𝑖𝑑 → 𝑆𝑜𝑙𝑖𝑑 ⟹ 𝐶𝑜𝑛𝑡𝑟𝑎𝑐𝑡𝑠
𝑀𝑒𝑙𝑡𝑖𝑛𝑔
𝐵𝑢𝑡, 𝐼𝑐𝑒 → 𝑊𝑎𝑡𝑒𝑟 ⟹ 𝐶𝑜𝑛𝑡𝑟𝑎𝑐𝑡𝑠
𝐹𝑟𝑒𝑒𝑧𝑖𝑛𝑔
𝑊𝑎𝑡𝑒𝑟 → 𝐼𝑐𝑒 → 𝐸𝑥𝑝𝑎𝑛𝑑𝑠
When ice melts it contracts, when water freezes it expands.
For water slope of fusion curve on P-T diagram is negative.
 Representation of all 3 phases on P-V diagram

𝑃+𝐹 =𝐶+2
𝐴𝑡 𝑡𝑟𝑖𝑝𝑙𝑒 𝑝𝑜𝑖𝑛𝑡 → 3 + 𝐹 = 1 + 2 → 𝐹 = 0
Minimum no. of independent intensive variables required is zero.
On P-V diagram triple point is a line.
In P-T diagram triple point is a point.
According to Gibbs phase rule, degree of freedom at triple point is zero i.e., minimum no. of independent intensive variables
required to fix this state at triple point is zero. i.e., at triple point no intensive property can be changed. Intensive properties
are fixed at triple point. Therefore, triple point is a unique state.
𝑇𝑟𝑖𝑝𝑙𝑒 𝑝𝑜𝑖𝑛𝑡 𝑑𝑎𝑡𝑎 𝑓𝑜𝑟 𝑤𝑎𝑡𝑒𝑟 → 𝑇𝑡𝑟𝑖𝑝𝑙𝑒 𝑝𝑜𝑖𝑛𝑡 = 0.01°𝐶 𝑃𝑡𝑟𝑖𝑝𝑙𝑒 𝑝𝑜𝑖𝑛𝑡 = 0.00613 𝑏𝑎𝑟
Reference state in standard steam tables
The internal energy and entropy of saturated liquid at triple point temperature (0.01ᵒC) is arbitrarily taken as zero.

Mixture of gases
𝑚𝑎𝑠𝑠
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 =
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡
𝑚
𝑛=
𝑀
𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
𝑀𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝑥) =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
𝑛1 𝑛1 𝑛𝑖
𝑥1 = = 𝑥𝑖 =
𝛴𝑛 𝑛1 + 𝑛2 + 𝑛3 𝛴𝑛
 𝑃 ⋅ 𝑉 = 𝛴𝑛 ⋅ 𝑅̅ ⋅ 𝑇 ①
𝑃1 ⋅ 𝑉 = 𝑛1 ⋅ 𝑅̅ ⋅ 𝑇
𝑃2 ⋅ 𝑉 = 𝑛2 ⋅ 𝑅̅ ⋅ 𝑇 & 𝑠𝑜 𝑜𝑛
Adding all equation,
(𝑃1 + 𝑃2 + ⋯ ) ⋅ 𝑉 = (𝑛1 + 𝑛2 + ⋯ ) ⋅ 𝑅̅ ⋅ 𝑇 ②
𝐹𝑟𝑜𝑚 ① & ②
𝑃 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯ → 𝐷𝑎𝑙𝑡𝑜𝑛𝑠 𝑙𝑎𝑤 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑃1 ⋅ 𝑉 = 𝑛1 ⋅ 𝑅̅ ⋅ 𝑇 ③
③ 𝑃1 𝑛1
⟹ = = 𝑥1 → 𝑃1 = 𝑃 ⋅ 𝑥1
① 𝑃 𝛴𝑛
𝑃𝑖 = 𝑃 ⋅ 𝑥𝑖
Equivalent molecular weight of a mixture (Me)
𝑚
𝑛=
→𝑚 =𝑛⋅𝑀
𝑀
𝛴𝑚
𝛴𝑚 = 𝛴𝑛 ⋅ 𝑀 𝑀𝑒 =
𝛴𝑛
𝑚1 + 𝑚2 + ⋯ 𝑛1 ⋅ 𝑀1 + 𝑛2 ⋅ 𝑀2 + ⋯ 𝑛1 ⋅ 𝑀1 + 𝑛2 ⋅ 𝑀2 + ⋯
𝑀𝑒 = = =
𝑛1 + 𝑛2 + ⋯ 𝑛1 + 𝑛2 + ⋯ 𝛴𝑛
𝑛1 𝑛2
𝑀𝑒 = ⋅ 𝑀1 + ⋅ 𝑀2 + ⋯
𝛴𝑛 𝛴𝑛
𝑀𝑒 = 𝑥1 ⋅ 𝑀1 + 𝑥2 ⋅ 𝑀2 + ⋯
Equivalent gas constant (Re)
𝑃 ⋅ 𝑉 = 𝛴𝑚 ⋅ 𝑅𝑒 ⋅ 𝑇 ①
𝑃1 𝑉 = 𝑚1 ⋅ 𝑅1 ⋅ 𝑇 , 𝑃2 𝑉 = 𝑚2 ⋅ 𝑅2 ⋅ 𝑇 & 𝑠𝑜 𝑜𝑛
Adding all those, we get
(𝑃1 + 𝑃2 + ⋯ )𝑉 = (𝑚1 ⋅ 𝑅1 + 𝑚2 ⋅ 𝑅2 + ⋯ ) ⋅ 𝑇 ⟹ 𝑃. 𝑉 = (𝑚1 ⋅ 𝑅1 + 𝑚2 ⋅ 𝑅2 + ⋯ ) ⋅ 𝑇 ②
(𝑃 = 𝑃1 + 𝑃2 + 𝑃3 + ⋯ → 𝐷𝑎𝑙𝑡𝑜𝑛𝑠 𝑙𝑎𝑤 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒)
𝐹𝑟𝑜𝑚 ① &②
𝑚1 ⋅ 𝑅1 + 𝑚2 ⋅ 𝑅2 + ⋯ = 𝛴𝑚 ⋅ 𝑅𝑒
𝑚1 ⋅ 𝑅1 + 𝑚2 ⋅ 𝑅2 + ⋯ 𝑅̅
𝑅𝑒 = 𝑅𝑒 =
𝛴𝑚 𝑀𝑒
Equivalent cp, cv
𝛴𝑈 = 𝑈1 + 𝑈2 + ⋯
𝛴𝑚 ⋅ 𝑐𝑣𝑒 ⋅ 𝑇 = 𝑚1 ⋅ 𝑐𝑣1 ⋅ 𝑇 + 𝑚2 ⋅ 𝑐𝑣2 ⋅ 𝑇 + ⋯
𝑚1 ⋅ 𝑐𝑣1 + 𝑚2 ⋅ 𝑐𝑣2 + ⋯
𝑐𝑣𝑒 =
𝛴𝑚
𝛴𝐻 = 𝐻1 + 𝐻2 + ⋯ → 𝛴𝑚 ⋅ 𝑐𝑝𝑒 ⋅ 𝑇 = 𝑚1 ⋅ 𝑐𝑝1 ⋅ 𝑇 + 𝑚2 ⋅ 𝑐𝑣2 ⋅ 𝑇 + ⋯
𝑚1 ⋅ 𝑐𝑝1 + 𝑚2 ⋅ 𝑐𝑝2 + ⋯
𝑐𝑝𝑒 =
𝛴𝑚
𝑐𝑝𝑒 − 𝑐𝑣𝑒 = 𝑅𝑒
𝑐𝑝𝑒
𝛾𝑒 =
𝑐𝑣𝑒
• Each Individual gas can be treated as Ideal gas
• Mixture can be treated as Ideal gas
• Mixture is homogenous.
• Mixture is non-reactive.
Thermodynamics Relations
Theorem 1
𝜕𝑀 𝜕𝑁
𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑑𝑧 = 𝑀 ⋅ 𝑑𝑥 + 𝑁𝑑𝑦 𝑖𝑠 𝑎𝑛 𝑒𝑥𝑎𝑐𝑡 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑡𝑖𝑎𝑙 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑖𝑓 ( ) = ( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦
Theorem 2
𝑓 = 𝜙(𝑥, 𝑦, 𝑧)
𝜕𝑥 𝜕𝑦 𝜕𝑧
( ) ⋅( ) ⋅( ) =1
𝜕𝑦 𝑓 𝜕𝑧 𝑓 𝜕𝑥 𝑓
Theorem 3
𝑧 = 𝜙(𝑥, 𝑦)
𝜕𝑥 𝜕𝑦 𝜕𝑧
( ) ⋅ ( ) ⋅ ( ) = −1
𝜕𝑦 𝑧 𝜕𝑧 𝑧 𝜕𝑥 𝑧

Maxwell’s equation
I
𝑇 ⋅ 𝑑𝑆 = 𝑑𝑈 + 𝑃 ⋅ 𝑑𝑉
𝑑𝑈 = 𝑇 ⋅ 𝑑𝑆 − 𝑃 ⋅ 𝑑𝑉
𝑑𝑧 = 𝑀 ⋅ 𝑑𝑥 + 𝑁 ⋅ 𝑑𝑦
𝑧 = 𝑈, 𝑀 = 𝑇, 𝑥 = 𝑆, 𝑁 = −𝑃, 𝑦 = 𝑉
𝜕𝑀 𝜕𝑁 𝜕𝑇 𝜕𝑃
𝑡ℎ𝑒𝑛, ( ) = ( ) ⟹ ( ) = ( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑉 𝑆 𝜕𝑆 𝑉
II
𝑇 ⋅ 𝑑𝑆 = 𝑑𝐻 − 𝑉 ⋅ 𝑑𝑃
𝑑𝐻 = 𝑇 ⋅ 𝑑𝑆 + 𝑉 ⋅ 𝑑𝑃
𝑑𝑧 = 𝑀 ⋅ 𝑑𝑥 + 𝑁 ⋅ 𝑑𝑦
𝑧 = 𝐻, 𝑀 = 𝑇, 𝑥 = 𝑆, 𝑁 = 𝑉, 𝑦 = 𝑃
𝜕𝑀 𝜕𝑁 𝜕𝑇 𝜕𝑉
𝑡ℎ𝑒𝑛, ( ) =( ) ⟹ ( ) =( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑃 𝑆 𝜕𝑆 𝑃

III
𝐺 =𝐻−𝑇⋅𝑆
𝑑𝐺 = 𝑑𝐻 − 𝑑(𝑇𝑆) = 𝑑𝐻 − 𝑇 ⋅ 𝑑𝑆 − 𝑆 ⋅ 𝑑𝑇 = (𝑑𝐻 − 𝑇 ⋅ 𝑑𝑆) − 𝑆 ⋅ 𝑑𝑇 = 𝑉 ⋅ 𝑑𝑃 − 𝑆 ⋅ 𝑑𝑇
𝑑𝐺 = 𝑉 ⋅ 𝑑𝑃 − 𝑆 ⋅ 𝑑𝑇
𝑑𝑧 = 𝑀 ⋅ 𝑑𝑥 + 𝑁 ⋅ 𝑑𝑦
𝑧 = 𝐺, 𝑀 = 𝑉, 𝑥 = 𝑃, 𝑁 = −𝑆, 𝑦 = 𝑇
𝜕𝑀 𝜕𝑁 𝜕𝑉 −𝜕𝑆
𝑡ℎ𝑒𝑛, ( ) =( ) ⟹ ( ) =( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑇 𝑃 𝜕𝑃 𝑇

IV
𝐹 =𝑈−𝑇⋅𝑆
𝑑𝐹 = 𝑑𝑈 − 𝑇 ⋅ 𝑑𝑆 − 𝑆 ⋅ 𝑑𝑇
𝑑𝐹 = −𝑃 ⋅ 𝑑𝑉 − 𝑆 ⋅ 𝑑𝑇
𝑑𝑧 = 𝑀 ⋅ 𝑑𝑥 + 𝑁 ⋅ 𝑑𝑦
𝑧 = 𝐹, 𝑀 = −𝑃, 𝑥 = 𝑉, 𝑁 = −𝑆, 𝑦=𝑇
𝜕𝑀 𝜕𝑁 𝜕𝑃 𝜕𝑆
𝑡ℎ𝑒𝑛, ( ) = ( ) ⟹ ( ) = ( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦 𝜕𝑇 𝑉 𝜕𝑉 𝑇
Physical meaning of Enthalpy
It’s the microscopic form of energy of flowing fluid.
Note
• Internal energy is also microscopic form of energy, but it’s for a stationary fluid.
• The microscopic form of energy of a flowing fluid is greater than microscopic form of energy of stationary fluid.
• The difference between microscopic energy of flowing fluid and stationary fluid is flow work (PV).
T- dS equations
𝑠 = 𝑓(𝑇, 𝜈)
𝜕𝑠 𝜕𝑠
𝑑𝑠 = ( ) ⋅ 𝑑𝑇 + ( ) ⋅ 𝑑𝜈
𝜕𝑇 𝜈 𝜕𝜈 𝑇
𝜕𝑠 𝜕𝑠
𝑇 ⋅ 𝑑𝑠 = 𝑇 ⋅ ( ) ⋅ 𝑑𝑇 + 𝑇 ⋅ ( ) ⋅ 𝑑𝜈
𝜕𝑇 𝜈 𝜕𝜈 𝑇
𝜕𝑠 𝑇 𝜕𝑠 𝜕𝑃
(( ) = ( ) =( ) )
𝜕𝑇 𝜈 𝑐𝑣 𝜕𝜈 𝑇 𝜕𝑇 𝜈
𝜕𝑃
𝑇 ⋅ 𝑑𝑠 = 𝑐𝑣 ⋅ 𝑑𝑇 + 𝑇 ⋅ ( ) ⋅ 𝑑𝜈 ①
𝜕𝑇 𝜈
𝑠 = 𝑓(𝑇, 𝑃)
𝜕𝑠 𝜕𝑠
𝑑𝑠 = ( ) ⋅ 𝑑𝑇 + ( ) ⋅ 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑠 𝜕𝑠
𝑇 ⋅ 𝑑𝑠 = 𝑇 ⋅ ( ) ⋅ 𝑑𝑇 + 𝑇 ⋅ ( ) ⋅ 𝑑𝑃
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝜕𝑠 𝑇 𝜕𝑠 −𝜕𝜈
(( ) = ( ) =( ) )
𝜕𝑇 𝑃 𝑐𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑃
𝜕𝜈
𝑇 ⋅ 𝑑𝑠 = 𝑐𝑃 ⋅ 𝑑𝑇 − 𝑇 ⋅ ( ) ⋅ 𝑑𝑃 ②
𝜕𝑇 𝑃

Energy equations
𝜕𝑃
𝑇 ⋅ 𝑑𝑠 = 𝑑𝑢 + 𝑃 ⋅ 𝑑𝜈 → 𝑑𝑢 = 𝑇 ⋅ 𝑑𝑠 − 𝑃 ⋅ 𝑑𝜈 = (𝑐𝑣 ⋅ 𝑑𝑇 + 𝑇 ( ) ⋅ 𝑑𝜈) − 𝑃 ⋅ 𝑑𝜈
𝜕𝑇 𝜈
𝜕𝑃
𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇 + (𝑇 ( ) − 𝑃) ⋅ 𝑑𝜈 → 𝑓𝑜𝑟 𝑎𝑛𝑦 𝑔𝑎𝑠
𝜕𝑇 𝜈
Case 1
Constant volume process (any gas)
𝜈 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 → 𝑑𝜈 = 0
𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇 → 𝑓𝑜𝑟 𝑎𝑛𝑦 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠
Case 2
𝑚⋅𝑅⋅𝑇
𝑃⋅𝑉 =𝑚⋅𝑅⋅𝑇 → 𝑃 =
𝑉
𝜕𝑃 𝑚 ⋅ 𝑅 𝑃 𝜕𝑃
= = → 𝑇⋅ =𝑃
𝜕𝑇 𝑉 𝑇 𝜕𝑇
𝜕𝑃
𝑑𝑢 = 𝑐𝑣 𝑑𝑇 + (𝑇 ( ) − 𝑃) ⋅ 𝑑𝜈 = 𝑐𝑣 ⋅ 𝑑𝑇 + (𝑃 − 𝑃) ⋅ 𝑑𝜈 = 𝑐𝑣 ⋅ 𝑑𝑇
𝜕𝑇 𝜈
𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇 → 𝑓𝑜𝑟 𝑎𝑛 𝑖𝑑𝑒𝑎𝑙 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇 𝑖𝑠 𝑣𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑟𝑒𝑎𝑙 𝑔𝑎𝑠 𝑜𝑛𝑙𝑦 𝑢𝑛𝑑𝑒𝑟 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠.
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑑𝑢 = 𝑐𝑣 ⋅ 𝑑𝑇 𝑖𝑠 𝑣𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠.
 𝐸𝑞𝑢𝑎𝑡𝑖𝑛𝑔 ① & ②
𝜕𝑃 𝜕𝜈
→ 𝑐𝑣 ⋅ 𝑑𝑇 + 𝑇 ⋅ ( ) ⋅ 𝑑𝜈 = 𝑐𝑃 ⋅ 𝑑𝑇 − 𝑇 ⋅ ( ) ⋅ 𝑑𝑃
𝜕𝑇 𝜈 𝜕𝑇 𝑃
𝜕𝑃 𝜕𝜈
→ 𝑇 ⋅ ( ) ⋅ 𝑑𝜈 + 𝑇 ⋅ ( ) ⋅ 𝑑𝑃 = (𝑐𝑝 − 𝑐𝑣 ) ⋅ 𝑑𝑇
𝜕𝑇 𝜈 𝜕𝑇 𝑃
𝑇 𝜕𝜈 𝑇 𝜕𝑃
𝑑𝑇 = ⋅ ( ) ⋅ 𝑑𝑃 + ⋅ ( ) ⋅ 𝑑𝜈 ①
𝑐𝑝 − 𝑐𝑣 𝜕𝑇 𝑃 𝑐𝑝 − 𝑐𝑣 𝜕𝑇 𝜈
𝜕𝑇 𝜕𝑇
𝑇 = 𝑓(𝑃, 𝑉) → 𝑑𝑇 = ( ) ⋅ 𝑑𝑃 + ( ) ⋅ 𝑑𝜈 ②
𝜕𝑃 𝜈 𝜕𝜈 𝑃
𝐹𝑟𝑜𝑚 ① & ②
𝑇 𝜕𝜈 𝜕𝑇 𝜕𝜈 𝜕𝑃
⋅ ( ) = ( ) → 𝑐𝑝 − 𝑐𝑣 = 𝑇 ⋅ ( ) ⋅ ( ) ③
𝑐𝑝 − 𝑐𝑣 𝜕𝑇 𝑃 𝜕𝑃 𝜈 𝜕𝑇 𝑃 𝜕𝑇 𝜈
𝜕𝑥 𝜕𝑦 𝜕𝑧
𝑊𝑒 𝑘𝑛𝑜𝑤 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒𝑟𝑜𝑟𝑒𝑚 3, → ( ) ⋅ ( ) ⋅ ( ) = −1
𝜕𝑦 𝑧 𝜕𝑧 𝑧 𝜕𝑥 𝑧
𝜕𝑃 𝜕𝜈 𝜕𝑇 𝜕𝑃 𝜕𝑃 𝜕𝜈
𝑇 = 𝑓(𝑃, 𝜈) ⟹ ( ) ⋅ ( ) ⋅ ( ) = −1 → ( ) = − ( ) ⋅ ( ) ④
𝜕𝜈 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝜈 𝜕𝑇 𝜈 𝜕𝜈 𝑇 𝜕𝑇 𝑃
𝑓𝑟𝑜𝑚 ③ & ④,
𝜕𝜈 𝜕𝑃 𝜕𝜈 𝜕𝑃 𝜕𝜈 2
𝑐𝑝 − 𝑐𝑣 = 𝑇 ⋅ ( ) ⋅ (− ( ) ⋅ ( ) ) ⟹ 𝑐𝑝 − 𝑐𝑣 = −𝑇 ⋅ ( ) ⋅ ( )
𝜕𝑇 𝑃 𝜕𝜈 𝑇 𝜕𝑇 𝑃 𝜕𝜈 𝑇 𝜕𝑇 𝑃
If T=0 K, cp = cv i.e., at absolute temperature.
Coefficient of Volume expansion (β)
1 𝜕𝜈
𝛽= ⋅( )
𝜈 𝜕𝑇 𝑃
This shows variation of volume w.r.t temperature, under constant pressure conditions.
Isothermal compressibility (KT)
1 𝜕𝜈
𝐾𝑇 = − ⋅ ( )
𝜈 𝜕𝑃 𝑇
𝜕𝑃 𝜕𝜈 2 1
𝑐𝑝 − 𝑐𝑣 = −𝑇 ⋅ ( ) ⋅ ( ) → 𝑐𝑝 − 𝑐𝑣 = −𝑇 ⋅ (− ) ⋅ (𝛽 ⋅ 𝜈)2
𝜕𝜈 𝑇 𝜕𝑇 𝑃 𝐾𝑇 ⋅ 𝜈
𝑇 ⋅ 𝜈 ⋅ 𝛽2
𝑐𝑝 − 𝑐𝑣 =
𝐾𝑇

Joule Thompson coefficient

It shows variation of temperature w.r.t pressure under isenthalpic or throttling conditions.
𝜕𝑇
𝜇=( )
𝜕𝑃 ℎ
𝑇 ⋅ 𝑑𝑠 = 𝑑ℎ − 𝜈 ⋅ 𝑑𝑃 → 𝑑ℎ = 𝑇 ⋅ 𝑑𝑠 + 𝜈 ⋅ 𝑑𝑃
𝜕𝜈
𝑊𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡 → 𝑇 ⋅ 𝑑𝑠 = 𝑐𝑃 ⋅ 𝑑𝑇 − 𝑇 ⋅ ( ) ⋅ 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝜈
𝑑ℎ = 𝑐𝑃 ⋅ 𝑑𝑇 − 𝑇 ⋅ ( ) ⋅ 𝑑𝑃 + 𝜈 ⋅ 𝑑𝑃
𝜕𝑇 𝑃
𝜕𝜈
𝑑ℎ = 𝑐𝑃 ⋅ 𝑑𝑇 − (𝑇 ⋅ ( ) − 𝜈) ⋅ 𝑑𝑃 → 𝑓𝑜𝑟 𝑎𝑛𝑦 𝑔𝑎𝑠
𝜕𝑇 𝑃
Case 1
𝐴𝑛𝑦 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, → 𝑑ℎ = 𝑐𝑝 ⋅ 𝑑𝑇
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛, 𝑑ℎ = 𝑐𝑝 ⋅ 𝑑𝑇 𝑖𝑠 𝑣𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑎𝑛𝑦 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑝𝑟𝑜𝑐𝑒𝑠𝑠.
Case 2
𝐼𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑓𝑜𝑙𝑙𝑜𝑤𝑠, → 𝑃 ⋅ 𝑉 = 𝑚 ⋅ 𝑅 ⋅ 𝑇 → 𝑃 ⋅ 𝜈 = 𝑅 ⋅ 𝑇
𝑅⋅𝑇 𝜕𝜈 𝑅 𝑉 𝜕𝜈
→𝜈= →( ) = = → 𝑇⋅( ) −𝜈 =0
𝑃 𝜕𝑇 𝑃 𝑃 𝑇 𝜕𝑇 𝑃
𝜕𝜈
𝑆𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔, 𝑇 ⋅ ( ) − 𝜈 = 0 𝑖𝑛 𝑑ℎ 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛, 𝑤𝑒 𝑔𝑒𝑡 𝑑ℎ = 𝑐𝑝 ⋅ 𝑑𝑇
𝜕𝑇 𝑃
𝑇ℎ𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑑ℎ = 𝑐𝑝 ⋅ 𝑑𝑇 𝑖𝑠 𝑣𝑎𝑙𝑖𝑑 𝑓𝑜𝑟 𝑎𝑛 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑢𝑛𝑑𝑒𝑟𝑔𝑜𝑖𝑛𝑔 𝑎𝑛𝑦 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
𝜕𝜈
𝑑ℎ = 𝑐𝑃 ⋅ 𝑑𝑇 − (𝑇 ⋅ ( ) − 𝜈) ⋅ 𝑑𝑃
𝜕𝑇 𝑃
We know for throttling dh=0
𝜕𝜈 𝑑𝑇 1 𝜕𝜈
𝑐𝑃 ⋅ 𝑑𝑇 = (𝑇 ⋅ ( ) − 𝜈) ⋅ 𝑑𝑃 → = ⋅ (𝑇 ⋅ ( ) − 𝜈)
𝜕𝑇 𝑃 𝑑𝑃 𝑐𝑝 𝜕𝑇 𝑃
𝑑𝑇 1 𝜕𝜈
( ) = ⋅ (𝑇 ⋅ ( ) − 𝜈)
𝑑𝑃 ℎ 𝑐𝑝 𝜕𝑇 𝑃
𝑑𝑇 1 𝜕𝜈
𝜇 = ( ) = ⋅ (𝑇 ⋅ ( ) − 𝜈)
𝑑𝑃 ℎ 𝑐𝑝 𝜕𝑇 𝑃
𝜕𝜈
𝐹𝑜𝑟 𝑎𝑛 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠, 𝑇 ⋅ ( ) − 𝜈 = 0 ⟹ 𝜇 = 0 → 𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝜕𝑇 𝑃
Note
For an ideal gas, joule Thompson coefficient is zero i.e., when an ideal gas undergoes throttling temperature remains
constant.

𝜕𝑇
𝑆𝑙𝑜𝑝𝑒 𝑜𝑓 𝐼𝑠𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑖𝑐 𝑐𝑢𝑟𝑣𝑒𝑠 𝑜𝑛 𝑇 − 𝑃 𝑐𝑢𝑟𝑣𝑒 ( ) = 𝜇
𝜕𝑃 ℎ

Clasius Clapeyron equation

𝜕𝑃 𝜕𝑠
( ) =( )
𝜕𝑇 𝜈 𝜕𝜈 𝑇
During phase change, pressure and temperature are independent of volume.
𝑑𝑃 𝑠𝑔 − 𝑠𝑓 𝐿𝐻
= , 𝑠𝑔 − 𝑠𝑓 =
𝑑𝑇 𝜈𝑔 − 𝜈𝑓 𝑇
𝑑𝑃 𝐿𝐻
= → 𝑐𝑙𝑎𝑠𝑖𝑢𝑠 𝑐𝑙𝑎𝑝𝑒𝑦𝑟𝑜𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
𝑑𝑇 𝑇 ⋅ (𝜈𝑔 − 𝜈𝑓 )
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑖𝑠 𝑣𝑒𝑟𝑦 𝑠𝑚𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑎𝑟𝑒𝑑 𝑡𝑜 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟, 𝑠𝑜 → 𝜈𝑔 − 𝜈𝑓 ≈ 𝜈𝑔
𝑑𝑃 𝐿𝐻 𝑑𝑃 𝐿𝐻 𝑃 ⋅ 𝐿𝐻
= → = =
𝑑𝑇 𝑇 ⋅ 𝜈𝑔 𝑑𝑇 𝑇 ⋅ 𝑅 ⋅ 𝑇 𝑅 ⋅ 𝑇2
𝑃
𝑑𝑃 𝑃 ⋅ 𝐿𝐻
=
𝑑𝑇 𝑅 ⋅ 𝑇 2