Unit 1 - Basic Concepts of Thermodynamics

Introduction & Terminologies

 Therme + Dunamis (Greek words)
 Heat energy + motion or power
 Thermodynamics – deals with
 Energy and its transformation including heat, work and physical
properties of substances
 Thermodynamic equilibrium and feasibility of processes
 System – anything under study usually a certain quantity of matter or a specific
region of space
 Surroundings – region outside the system
 Boundary – that which separates the system and surroundings
 Real or imaginary
 Fixed or movable
 Universe = system + surroundings
Types of systems
 Closed system
 Fixed amount of mass – no mass can enter or leave the system – no
mass transfer
 Volume may vary – boundary is movable
 Energy transfer takes place – both heat and work possible
 Example: Gas Trapped within a cylinder piston device

 Open System
 Mass transfer takes place
 Energy transfer also takes place
 Volume is fixed and therefore called CONTROL VOLUME
 Boundary is fixed – CONTROL SURFACE – can be real and imaginary
  Example: Flow through compressors, turbines, nozzles etc…

 Isolated System
 No energy and mass transfer
 A special case of closed system
 Example: Universe, Thermos-flask, Ice-box
 Adiabatic System
 A special case of open system
 No heat transfer only
 Example: Insulated turbines, pumps, compressors

Open Vs Closed system

S. No Closed System Open System

1. Non-flow system Flow system

2. Control Mass Control Volume

3. Boundary – is movable Boundary – is fixed, called Control Surface – combination of real and
imaginary boundaries

4. No mass transfer, only Both mass and energy transfer

energy transfer

5. Special case: Isolated Special case: Adiabatic system

system

6. Example: Gas trapped in a Example: Compressors, turbines, pumps, nozzles

cylinder piston device
 Isolated Vs Adiabatic System

S. No Isolated System Adiabatic System

1. Special case of Closed system Special case of Open System

2. No mass and energy transfer across Mass and energy transfer except heat transfer takes place
the boundary of the system across the boundary of system

3. Closed system which is insulated to Open system which is insulated to heat transfer so that no
energy transfer so that it becomes heat enters or leaves the boundary of the system
isolated from the surroundings

4. Example: Thermos flask, Icebox Example: Pump, Insulated steam turbine

 Homogenous system
 If it consists of a single physical phase either solid, liquid or gas only
 Treated as one constituent for analysis
 Analysis becomes simple
 Example: ice, water, steam, sugar dissolved in water
 Heterogenous system
 Mixture of two or more than two phases of matter
 Each constituent has its own properties independent of each other –
cannot be analysed as a single constituent
 Example: Mixture of ice and water, Dal, rice and water in a pressure
cooker
Approach
 Macroscopic Approach
 A certain or specific quantity of matter is considered without events
occurring at molecular level
 CLASSICAL THERMODYNAMICS
 Direct and easy way of solution
 Structure of the matter is considered
 Only few variables needed to describe the state of the system
 Values of these variables can be measured
  Microscopic Approach
 More elaborate
 Large number of molecules in a system, each have the same mass but
move with a velocity independent of others
 Each molecule has its own position, temperature, etc…
 Involve large number of equations, three location coordinates and three
components of velocity
 Very difficult to adopt in practice even with high speed computers
 Propertied of the system – based on average behaviour of large group
of molecules under consideration
 Knowledge of structure of matter is necessary
 Large number of variables needed to describe the state of the system
 Values of the variables cannot be measured easily
Working Fluid
 Matter contained within the system boundaries
 Used in thermodynamic device as a medium for energy transport between the
system and surroundings while undergoing a thermodynamic process or cycle
 May be gas, liquid or vapor or any non-reactive mixture

System Working Fluid

Petrol Engine Air-Petrol mixture

Steam Power Plant Steam

Gas Turbine Power plant Combustion gases

THERMODYNAMIC PROPERTIES
 Any characteristics of a system is called a PROPERTY.
 Every system has a certain characteristics by which its physical condition may
be described.
 Example: Temperature, Pressure and Volume
 A property is a measurable characteristic describing the state of the
system
 Has a definite value when the system is in a particular state
  Distinguish one system from another
 Magnitude of property depends on state of the system and is
independent of the path followed by a system during a process.
 A property is an EXACT or PERFECT DIFFERENTIAL
Exact or Perfect Differential
 Consider an equation of state relating three properties of a system such as x, y
and z
1
 𝑓(𝑥, 𝑦, 𝑧) = 0
 Suppose it is possible to solve eqn.1 explicitly for each of the variable as
 𝑥 = 𝑥(𝑦, 𝑧)
 𝑦 = 𝑦(𝑧, 𝑥) 2

 𝑧 = 𝑧(𝑥, 𝑦)
 In Eqn.2, considering last expression; z is dependent variable and x&y are
independent variables
 Differential of dependent property can be written in terms of its partial derivatives
and the differentials of independent variables
𝜕𝑧 𝜕𝑧
 𝑑𝑧 = (𝜕𝑥) 𝑑𝑥 + (𝜕𝑦) 𝑑y
𝑦 𝑥

𝜕𝑧 𝜕𝑧
 If 𝑀 = (𝜕𝑥) and 𝑁 = (𝜕𝑦)
𝑦 𝑥

 then 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦 3

 If Eqn.3 has a solution, then dz is an exact differential else it is inexact.

 If variable z is to be adequately defined by the thermodynamic co-ordinates x and
y, the value of z must be the same irrespective of the order taken in approaching
it.
 In evaluating dz, it should be possible to make the changes dx and dy in either
sequence, without changing the result.
 If the function, 𝑧 = 𝑧(𝑥, 𝑦) and its partial derivatives are continuous, then the
second derivative of z with respect to x and y is independent of the order of
differentiation.
𝜕 𝜕𝑧 𝜕 𝜕𝑧
4
 ( ) = 𝜕𝑥 (𝜕𝑦)
𝜕𝑦 𝜕𝑥
5
𝜕𝑀 𝜕𝑁
 ( 𝜕𝑦 ) = ( 𝜕𝑥 )
𝑥 𝑦

 Eqn.5 is a necessary condition for the existence of a function of x and y satisfying

Eqn.3
 A function which satisfies Eqn.5 is called Point Function or a Property of the
system.
Example 1
The heat interaction with a system is given in terms of two independent functions T
𝑅𝑇
and v by the equation 𝑑𝑞 = 𝑓(𝑇)𝑑𝑇 + 𝑑𝑣, Where R is a constant and T and v are
𝑣
the temperature and specific volume of the system. Is dq an exact differential?
𝜕𝑀 𝜕𝑁
Solution: For 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦, ( 𝜕𝑦 ) = ( 𝜕𝑥 )
𝑥 𝑦

𝑅𝑇
𝑀 ↔ 𝑓(𝑇), 𝑁 ↔ , 𝑦 ↔ 𝑣, 𝑥 ↔ 𝑇, 𝑧 ↔ 𝑞
𝑣
𝜕𝑀 𝜕𝑓(𝑇)
( ) =( ) =0
𝜕𝑦 𝑥 𝜕𝑣 𝑇
𝑅𝑇
𝜕𝑁 𝜕( 𝑣 ) 𝑅
( ) =( ) =
𝜕𝑥 𝑦 𝜕𝑇 𝑣
𝑣

𝜕𝑀 𝜕𝑁
( ) ≠( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦

Therefore, dq is an INEXACT Differential.

Example 2
Recognize whether the following quantities are properties or non-properties:
(a) 𝑝 𝑑𝑣 + 𝑣 𝑑𝑝 (b) 𝑝 𝑑𝑣 (c) 𝑣 𝑑𝑝
where P and v are pressure and specific volume respectively.
Solution: (a) 𝑝 𝑑𝑣 + 𝑣 𝑑𝑝
𝜕𝑀 𝜕𝑁
For 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦, ( 𝜕𝑦 ) = ( 𝜕𝑥 )
𝑥 𝑦

𝑀 ↔ 𝑃, 𝑁 ↔ 𝑣, 𝑦 ↔ 𝑃, 𝑥 ↔ 𝑣
𝜕𝑀 𝜕𝑝
( ) =( ) =1
𝜕𝑦 𝑥 𝜕𝑝 𝑣
𝜕𝑁 𝜕𝑣
( ) =( ) =1
𝜕𝑥 𝑦 𝜕𝑣 𝑝
𝜕𝑀 𝜕𝑁
( ) =( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦

Therefore, 𝑝 𝑑𝑣 + 𝑣 𝑑𝑝 is a PROPERTY
(b) 𝑝 𝑑𝑣
(c) 𝑣 𝑑𝑝
are NOT PROPERTIES as they are not of the form 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦 and cannot be
evaluated.
Example 3
If the pressure p, specific volume v and absolute temperature T are functionally related
𝑣 𝑝
as 𝑇 𝑑𝑝 + 𝑇 𝑑𝑣, Examine whether the quantity is a property.
𝜕𝑀 𝜕𝑁
Solution: For 𝑑𝑧 = 𝑀 𝑑𝑥 + 𝑁 𝑑𝑦, ( 𝜕𝑦 ) = ( 𝜕𝑥 )
𝑥 𝑦

𝑣 𝑝
𝑀↔ , 𝑁 ↔ , 𝑦 ↔ 𝑣, 𝑥 ↔ 𝑝
𝑇 𝑇
𝑣
𝜕𝑀 𝜕 (𝑇 ) 1
( ) =( ) =
𝜕𝑦 𝑥 𝜕𝑣 𝑇
𝑝

𝑝
𝜕𝑁 𝜕 (𝑇) 1
( ) =( ) =
𝜕𝑥 𝑦 𝜕𝑝 𝑇
𝑣

𝜕𝑀 𝜕𝑁
( ) =( )
𝜕𝑦 𝑥 𝜕𝑥 𝑦
𝑣 𝑝
The quantity 𝑑𝑝 + 𝑑𝑣 is an EXACT DIFFERENTIAL and is therefore a PROPERTY.
𝑇 𝑇

Intrinsic Vs Extrinsic Properties

 Intrinsic Properties
 Fundamental properties
 Cannot be defined in terms of other properties
 Example: Length, mass, time, pressure, temperature
 Extrinsic Properties
 Derived properties
 Values cannot be assigned independently
 Characteristics of motion or position of system and measured with
reference to datum
 Example: velocity, acceleration, potential energy, kinetic energy,
enthalpy etc.
Intensive Vs Extensive Properties
 Intensive Properties
  That do not depend on the extent of the system
 Which are independent of mass only
 Example: pressure, temperature, density, velocity

 Extensive Properties
 That which depends on the extent of the system
 Which depends on mass only
 Example: mass, area, volume, total energy, etc.

E (kJ) E/2 (kJ) E/2 (kJ)

m (kg) m/2 (kg) m/2 (kg)

3 3 3
V (m /s) V/2 (m /s) V/2 (m /s)
3 3 3
ρ (kg/m ) ρ (kg/m ) ρ (kg/m )

v (m/s) v (m/s) v (m/s)

T (⁰C) T (⁰C) T (⁰C)

P (Pa) P (Pa) P (Pa)

Example 3
If the pressure p, specific volume v and absolute temperature T are functionally related
𝑣 𝑝
as 𝑇 𝑑𝑝 + 𝑇 𝑑𝑣, Examine whether the quantity is a property.

State
 Condition of a thermodynamic system characterized by certain properties like
pressure, temperature, specific volume etc…
Path
 A locus of series of states through which a system passes between initial and
final states.

Process
 The transformation of a thermodynamic system from one state to another state
is called a PROCESS.
 Flow Process Vs Non-flow process
 Quasi static process
 Reversible vs Irreversible process
 Adiabatic Process
 Isothermal, Isobaric & Isochoric Processes
 Isentropic and Isenthalpic processes
Cycle
 If a system undergoes a series of processes in such a way that its initial and
final states are identical then the system is said to have undergone a cyclic
process or a cycle.
Point Function
 When a system undergoes a change from one state to another, the properties
of the system also change which depend only on end states and not on the path
followed between these two states.
 These properties are called state functions or point functions
 Represented by a point
 Example: pressure, volume, temperature and entropy
 Exact differentials denoted by ‘d’
 Change of pressure or volume is dp & dv

Path Function
 Quantity whose value depends on the path followed during the process.
 Requires a particular path and direction
 Inexact differentials
 Denoted by δ
 Differential amount of work or heat is written as δW and δQ

Quasi-Static Process
  When a process proceeds in such a manner that the system remains
infinitesimally close to equilibrium state at all times is QUASI STATIC
PROCESS.
 System adjusts itself internally so that properties in one part of the system does
not change any faster than in the other part.
 Ideal process
 Why quasi-static process?
 Easy for analysis
 Work producing devices deliver maximum work
 Work absorbing devices require minimum work
 A STANDARD for all the other processes
Thermodynamic Equilibrium
 Thermal equilibrium – NO temperature difference
 Mechanical equilibrium – NO unbalanced forces
 Phase equilibrium – Mass of each phase reaches equilibrium level and stays
there
 Chemical equilibrium – No chemical reaction / chemical composition remains
same
 Internal equilibrium – An isolated system where there is no interaction with
surroundings
Zeroth Law of Thermodynamics
 When a body A is in thermal equilibrium with a body B and also separately with
a body C, then B and C will be in thermal equilibrium with each other.

A - 50°C B - 50°C

B - 50°C C - 50°C

C - 50°C
Temperature
 Temperature – a measure of hotness or coldness ??
 A metal chair will feel colder than a wooden chair.
 Several properties of materials change with temperature in a repeatable and
predictable way – thermometric property – basis for accurate temperature
measurement

S. No Temperature Probe Thermometric Property

1 Constant Volume Gas Thermometer Pressure

2 Thermistor Electrical Resistance

3 Resistance Thermometer Electrical Resistance

4 Thermocouple Emf induced

5 Total Radiation Pyrometer Radiation

6 Optical Pyrometer Brightness

Temperature Scales
 Ice Point: the temperature at which a mixture of ice and water are in equilibrium
at a pressure of 1 atmosphere.
 Steam Point: the temperature at which water vapor condenses at a pressure of
1 atmosphere
 Two-point scales – when temperature values are assigned at two different
points (0⁰C and 100⁰C & 32⁰F and 212⁰F)
 Kelvin scale
 Lowest temperature is absolute zero (0 K)
 Only one non-zero reference point needs to be assigned to establish the
slope of linear scale.
Ideal Gas Temperature Scale
 Nearly identical to Kelvin scale
 Constant volume gas thermometer – at low pressure, temperature is directly
proportional to pressure at constant volume
 Temperature varies linearly with pressure at constant volume
 𝑇 = 𝑎 + 𝑏𝑝
  Ideal gas temperature scale developed by measuring pressure at two different
points (ice point and steam point)
 Values of a and b can be determined & then temperature for a corresponding
pressure can be measured.
 If ice point and steam point are taken as 0 and 100 – similar to Celsius scale

Absolute Gas Temperature scale

 T=a+bp
 At absolute pressure of zero, b = - 273.15⁰C regardless of the type and amount
of gas in the thermometer.
 All the straight lines passing through the data points in this case will intersect
the temperature axis at - 273.15⁰C
 - 273.15⁰C is the lowest temperature that can be obtained by a gas
thermometer
 Absolute Gas Temperature scale can be obtained by assigning a value of zero
to constant ‘a’ (0 K – Zero Kelvin)
 T=bp
 Thus, we need to specify the temperature at only one point to define an
ABSOLUTE GAS TEMPERATURE SCALE

Pressure
 Normal force exerted by a fluid per unit area.
 Atmospheric pressure
 Absolute pressure
  Gauge pressure
 𝑃𝑎𝑏𝑠 = 𝑃𝑎𝑡𝑚 + 𝑃𝑔𝑎𝑢𝑔𝑒

Barometer

Example 1
The pressure in a constant gas thermometer is measured as 32 mm of mercury above
atmospheric pressure at triple point. Determine the temperature in °C, when the
pressure is 76 mm of mercury above atmospheric pressure. The barometer reads 752
mm of mercury.
Given: 𝑃𝑎𝑡𝑚 = 752 𝑚𝑚 𝑜𝑓 𝐻𝑔, 𝑃𝑔𝑎𝑢𝑔𝑒, 𝑡𝑝 = 32 𝑚𝑚 𝑜𝑓 𝐻𝑔, 𝑃𝑔𝑎𝑢𝑔𝑒,1 =
76 𝑚𝑚 𝑜𝑓 𝐻𝑔, 𝑇𝑡𝑝 = 273.15 𝐾

Solution: 𝑃𝑡𝑝 = 𝑃𝑎𝑡𝑚 + 𝑃𝑔𝑎𝑢𝑔𝑒, 𝑡𝑝 = 752 + 32 = 784 𝑚𝑚 𝑜𝑓 𝐻𝑔

𝑃1 = 𝑃𝑎𝑡𝑚 + 𝑃𝑔𝑎𝑢𝑔𝑒, 1 = 752 + 76 = 828 𝑚𝑚 𝑜𝑓 𝐻𝑔

𝑃𝑡𝑝 ∝ 𝑇𝑡𝑝
𝑃𝑡𝑝 𝑃1
=
𝑇𝑡𝑝 𝑇1
𝑃1 ∗ 𝑇𝑡𝑝 828 ∗ 273.15
𝑇1 = = = 288.48 𝐾
𝑃𝑡𝑝 784
Example 2
The temperature scale of a certain thermometer is given by the relation, 𝑇 =
𝐴 ln 𝑝 + 𝐵, where A and B are constants, and ‘p’ is the thermometric property of the
fluid in thermometer. At ice point and steam point, if the thermometric property is found
to be 1.5 and 7.5 respectively, what will be the temperature corresponding to the
thermometric property of 3.5 on Celsius scale⁇
Given: 𝑃𝑖 = 1.5, 𝑇𝑖 = 0℃, 𝑃𝑠 = 7.5, 𝑇𝑠 = 100℃, 𝑃 = 3.5, 𝑇 = ⁇
Solution: 𝑇 = 𝐴 ln 𝑝 + 𝐵
𝑇𝑖 = 𝐴 𝑙𝑛 𝑝𝑖 + 𝐵
𝑇𝑠 = 𝐴 𝑙𝑛 𝑝𝑠 + 𝐵
𝐴 ln 1.5 + 𝐵 = 0
1
𝐴 ln 7.5 + 𝐵 = 100
Solving Equations 1 and 2 2

𝐴 = 62.13, 𝐵 = −25.2
𝑇 = 62.13 ln 3.5 − 25.2 = 52.64℃
Example 3
It is proposed to construct a new scale with the value 5°N assigned to ice point and
20°N to steam point. The pressure of an ideal gas at constant volume is considered
as a thermometric property.
a) Set up a linear relationship between pressure and temperature in °N on a new scale.
b) What is the Kelvin absolute zero on this scale?
c)Derive an expression between °N and K.
Solution: 𝑇 = 𝑎𝑃 + 𝑏
In Celsius Scale, 𝑇𝑖 = 0℃, 𝑇𝑠 = 100℃
𝑇𝑖 = 𝑎𝑃𝑖 + 𝑏
𝑇𝑠 = 𝑎𝑃𝑠 + 𝑏
By substituting the corresponding values,
𝑎𝑃𝑖 + 𝑏 = 0
𝑎𝑃𝑠 + 𝑏 = 100
On solving the above equations
100 −100𝑃
𝑎(𝑃𝑠 − 𝑃𝑖 ) = 100 𝑎 = (𝑃 −𝑃 ) 𝑏 = −𝑎𝑃𝑖 = (𝑃 −𝑃 )𝑖
𝑠 𝑖 𝑠 𝑖
 100 𝑃 100 𝑃𝑖 100(𝑃 − 𝑃𝑖 )
𝑇(℃) = 𝑎𝑃 + 𝑏 = − =
(𝑃𝑠 − 𝑃𝑖 ) (𝑃𝑠 − 𝑃𝑖 ) (𝑃𝑠 − 𝑃𝑖 )
𝑇(℃) (𝑃 − 𝑃𝑖 )
= 1
100 (𝑃𝑠 − 𝑃𝑖 )
In the New scale, 𝑇𝑖 = 50 𝑁, 𝑇𝑠 = 200 𝑁
𝑇𝑖 = 𝑐𝑃𝑖 + 𝑑
𝑇𝑠 = 𝑐𝑃𝑠 + 𝑑
By substituting the corresponding values,
𝑐𝑃𝑖 + 𝑑 = 5
𝑐𝑃𝑠 + 𝑑 = 20
On solving the above equations
15 15𝑃𝑖
𝑐(𝑃𝑠 − 𝑃𝑖 ) = 15 𝑐 = (𝑃 𝑑 = 5 − 𝑐𝑃𝑖 = 5 − (𝑃
𝑠 −𝑃𝑖 ) 𝑠 −𝑃𝑖 )

15 𝑃 15 𝑃𝑖 15(𝑃 − 𝑃𝑖 )
𝑇(0 𝑁) = 𝑐𝑃 + 𝑑 = +5− = 5+
(𝑃𝑠 − 𝑃𝑖 ) (𝑃𝑠 − 𝑃𝑖 ) (𝑃𝑠 − 𝑃𝑖 )
𝑇(⁰𝑁) − 5 (𝑃 − 𝑃𝑖 )
= 2
15 (𝑃𝑠 − 𝑃𝑖 )
From Equations 1 and 2
𝑇(℃) 𝑇(⁰𝑁) − 5
=
100 15
b) T = 0 K = -273⁰C
𝑇(℃) 𝑇(⁰𝑁) − 5
=
100 15
𝑇(℃) −273
𝑇(⁰𝑁) = 15 + 5 = 15 ( ) + 5 = −35.950 𝑁
100 100
0 𝐾 = −273℃ = −35.950 𝑁
𝑇(℃) 𝑇(⁰𝑁)−5
c) =
100 15

𝑇(𝐾) − 273 𝑇(⁰𝑁) − 5

=
100 15
100
𝑇(𝐾) = [ (𝑇(⁰𝑁) − 5)] + 273
15
Work transfer
• Work transfer is considered as occurring between system and surroundings
 • Work is a form of energy in transit which crosses the boundary of a system
• Work is said to be done by a system if the sole effect on things external
to the system can be reduced to the raising of weight.
• The weight may not be actually raised but the net effect external to the system
would be the raising of a weight.

Displacement work

Pdv Work in various processes

• Constant Volume Process (V = C)
❖ dV = 0, therefore, 𝑊 = ∫ 𝑝 𝑑𝑉 = 0
• Constant Pressure Process (P = C)
𝑉
❖ 𝑊 = ∫ 𝑝 𝑑𝑉 = ∫𝑉 2 𝑝 𝑑𝑉 = 𝑝(𝑉2 − 𝑉1 )
1

• Constant Temperature Process (pV = C)

❖ 𝑝𝑉 = 𝑝1 𝑉1
𝑉 𝑉 𝑝1 𝑉1 𝑉 𝑑𝑉 𝑉
❖ 𝑊 = ∫ 𝑝 𝑑𝑉 = ∫𝑉 2 𝑝 𝑑𝑉 = ∫𝑉 2 𝑑𝑉 = 𝑝1 𝑉1 ∫𝑉 2 = 𝑝1 𝑉1 ln (𝑉2 ) =
1 1 𝑉 1 𝑉 1
𝑝1
𝑝1 𝑉1 ln (𝑝 )
2

• Polytropic Process (pVn = C)

❖ 𝑝𝑉 𝑛 = 𝑝1 𝑉1 𝑛 = 𝑝2 𝑉2 𝑛
 𝑉 𝑉 𝑝1 𝑉1 𝑛 𝑉 𝑑𝑉 𝑉
❖ 𝑊 = ∫ 𝑝 𝑑𝑉 = ∫𝑉 2 𝑝 𝑑𝑉 = ∫𝑉 2 𝑑𝑉 = 𝑝1 𝑉1 𝑛 ∫𝑉 2 𝑉 𝑛 = 𝑝1 𝑉1 𝑛 ∫𝑉 2 𝑉 −𝑛 𝑑𝑉
1 1 𝑉𝑛 1 1

p1 V1 n 1−𝑛 1−n p2 V2 n V21−n − p1 V1 n V11−n p2 V2 − p1 V1

= [V − V1 ] = =
1−𝑛 2 1−𝑛 1−𝑛

Work & HEAT transfer

Flow work
• 𝑑𝑊𝑓𝑙𝑜𝑤 = 𝑝 𝑑𝑉 = 𝑝𝑣 𝑑𝑚

• Flow work at inlet, (𝑑𝑊𝑓𝑙𝑜𝑤 )𝑖𝑛 = 𝑝1 𝑣1 𝑑𝑚1

𝐴1 𝑉1 𝑑𝑚1
• Mass flow rate, 𝜔̇ 1 = =
𝑣1 𝑑𝑡

• Flow work at exit, (𝑑𝑊𝑓𝑙𝑜𝑤 )𝑜𝑢𝑡 = 𝑝2 𝑣2 𝑑𝑚2

• Flow work per unit mass, 𝑑𝑊𝑓𝑙𝑜𝑤 = 𝑝𝑣

Free expansion with zero work transfer

Heat transfer

Example 1
An object of 40 kg mass falls freely under the influence of gravity from an elevation of
100 m above the earth’s surface. The initial velocity is directed downwards with a
magnitude of 100 m/s. Ignoring the effect of air resistance, what is the magnitude of
the velocity in m/s of the object just before it strikes the earth?
𝑚
Given: 𝑚 = 40 𝑘𝑔, 𝑍1 = 100 𝑚, 𝑉1 = 100 , 𝑍2 = 0
𝑠

𝑉2 = ?
1 1
𝑚𝑔𝑍1 + 𝑚𝑉1 2 = 𝑚𝑔𝑍2 + 𝑚𝑉2 2
2 2
1 1
𝑉2 2 = 𝑔𝑍1 + 𝑉1 2 = 2[(9.81 ∗ 100) + 1002 ] = 11962
2 2
𝑉2 = 109.37 𝑚/𝑠
Example 2
Gas from a bottle of compressed helium is used to inflate an inelastic flexible balloon,
originally folded completely flat to a volume of 0.5 m3. If the barometer reads 760 mm
of mercury, what is the amount of work done upon the atmosphere by the balloon?
Sketch the system before and after the process.
Given: 𝑉𝑏𝑎𝑙𝑙𝑜𝑜𝑛 = 0.5 𝑚3 , 𝑃 = 1.01325 𝑏𝑎𝑟

𝑊 = ∫(𝑝 𝑑𝑉)𝑏𝑜𝑡𝑡𝑙𝑒 + (𝑝 𝑑𝑉)𝑏𝑎𝑙𝑙𝑜𝑜𝑛 = 0 + (1.01325 ∗ 0.5) = 50.66 𝑘𝐽

Work done by the balloon on the atmosphere = 50.66 kJ

Work done by the atmosphere on the balloon = -50.66 kJ
Example 3
When the valve of the evacuated bottle in the previous example is opened,
atmospheric air rushes into it. If the atmospheric pressure is 101.325 kPa and 0.6 m 3
of air (measured at atmospheric conditions) enters into the bottle, calculate the work
done by air.

𝑊 = ∫(𝑝 𝑑𝑉)𝑏𝑜𝑡𝑡𝑙𝑒 + (𝑝 𝑑𝑉)𝑏𝑎𝑙𝑙𝑜𝑜𝑛 = 0 + (1.01325 ∗ (−0.6)) = −60.8 𝑘𝐽

Example 4
A piston and cylinder machine containing a fluid system has a stirring device in the
cylinder. The piston is frictionless and it is held down against the fluid due to the
atmospheric pressure of 101.325 kPa. The stirring device is turned 10000 revolutions
with an average torque against the fluid of 1.275 Nm. Meanwhile the piston of 0.6 m
diameter moves out 0.8 m. Find the net work transfer for the system.
Work done by the stirring device, 𝑊1 = 2𝜋𝑁𝑇 = 2 ∗ 𝜋 ∗ 1.275 ∗ 10000 = 80 𝑘𝐽
Work done by the cylinder-piston device on surroundings,
𝜋
𝑊2 = 𝑝𝐴 𝐿 = 1.01325 ∗ 105 ∗ ∗ 0.62 ∗ 0.8 = 22.9 𝑘𝐽
4
Net Work Transfer, 𝑊𝑛𝑒𝑡 = 𝑊1+ 𝑊2 = −80 + 22.9 = −57.1 𝑘𝐽
Example 5
Consider a cylinder piston arrangement as shown in figure. The piston is loaded with
a mass mp the outside atmospheric pressure P0, a linear spring and a single point force
F1.The piston traps the gas inside with a pressure P.

∑ 𝐹 ↑ = 𝑃𝐴

∑ 𝐹 ↓ = 𝑚𝑝 𝑔 + 𝑃0 𝐴 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1

𝑃𝐴 = 𝑚𝑝 𝑔 + 𝑃0 𝐴 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1
𝑚𝑝 𝑔 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1
𝑃 = 𝑃0 +
𝐴
𝑚𝑝 𝑔 𝐹1 𝑘𝑠 𝐴(𝑥 − 𝑥0 ) 𝑚𝑝 𝑔 𝐹1 𝑘𝑠 (𝑉 − 𝑉0 )
𝑃 = 𝑃0 + + + 2
= 𝑃0 + + +
𝐴 𝐴 𝐴 𝐴 𝐴 𝐴2
𝑃 = 𝐶1 + 𝐶2 𝑉

∑ 𝐹 ↑ = 𝑃𝐴

∑ 𝐹 ↓ = 𝑚𝑝 𝑔 + 𝑃0 𝐴 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1

𝑃𝐴 = 𝑚𝑝 𝑔 + 𝑃0 𝐴 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1
𝑚𝑝 𝑔 + 𝑘𝑠 (𝑥 − 𝑥0 ) + 𝐹1
𝑃 = 𝑃0 +
𝐴
𝑚𝑝 𝑔 𝐹1 𝑘𝑠 𝐴(𝑥 − 𝑥0 ) 𝑚𝑝 𝑔 𝐹1 𝑘𝑠 (𝑉 − 𝑉0 )
𝑃 = 𝑃0 + + + 2
= 𝑃0 + + +
𝐴 𝐴 𝐴 𝐴 𝐴 𝐴2
𝑃 = 𝐶1 + 𝐶2 𝑉
Pure Substance
 One that has homogenous and invariable chemical composition
 May have one or more phases but the chemical composition remains unaltered
 Example: liquid water, mixture of water and vapor & mixture of ice and liquid
water
Vapor – Liquid – Solid Phase equilibrium

Temperature Volume diagram of water

Terminologies
 Saturation temperature – temperature at which vaporization of water takes
place
 Saturation pressure – pressure corresponding to saturation temperature
 Dryness fraction – fraction of vapor present in a mixture of water and vapor
𝑚𝑔
 𝑥=𝑚
𝑓 +𝑚𝑔

 Critical point – point of inflection with zero slope where saturated vapor and
saturated liquid states are identical
 Critical temperature of water,374.14℃ 𝑎𝑛𝑑 22.09 𝑀𝑃𝑎
Pressure Temperature curve
Sublimation line – where solid and vapor phases are in
equilibrium
Fusion line – where solid and liquid phases are in equilibrium
Vaporization line – where liquid and vapor phases are in
equilibrium
Triple point – where all the three phases are in equilibrium
Independent properties of a pure substance
 The state of a simple compressible pure substance is defined by two
independent properties.
 If the specific volume and temperature of steam are specified, state of steam is
determined.
 Consider saturated liquid and saturated vapor states, what is their pressure and
temperature?
 Require pressure & specific volume or pressure & dryness fraction to define the
state of steam
PV diagram of water

PV diagram of pure substance other than water

Example 1
Determine the state for each of the water states using steam tables,
a) 120˚C and 500 kPa
b) 120˚C and 0.5 m3/kg
a) Given: T = 120˚C & P = 500 kPa = 5 bar
Referring to Steam tables under Saturated pressure table (Table 2)
For Psat=5 bar, Tsat=151.8˚C
Here, T < Tsat
Therefore, the given condition represents liquid state.
It is in LIQUID phase.
b) T = 120˚C & v = 0.5 m3/kg
Referring to Steam tables under Saturated temperature table (Table 1)
For T = 120˚C
𝑣𝑓 = 0.001061 𝑚3 /𝑘𝑔

𝑣𝑔 = 0.89152 𝑚3 /𝑘𝑔

𝑣𝑓 < 𝑣 < 𝑣𝑔

Therefore, the given condition lies in the vapor+liquid region

𝑣 = 𝑣𝑓 + 𝑥𝑣𝑓𝑔

0.5 = 0.001061 + 𝑥(0.89152 − 0.001061)

𝑥 = 0.56
It is in LIQUID + VAPOR state.
Example 2
a) For P = 3 bar and v = 0.5 m3/kg
Referring to Steam tables under Saturated pressure table (Table 2)
For P = 3bar, 𝑇 = 133.5℃
𝑣𝑓 = 0.001074 𝑚3 /𝑘𝑔

𝑣𝑔 = 0.60553 𝑚3 /𝑘𝑔

𝑣𝑓 < 𝑣 < 𝑣𝑔

Therefore, the given condition lies in the vapor+liquid region

𝑣 = 𝑣𝑓 + 𝑥𝑣𝑓𝑔

0.5 = 0.001074 + 𝑥(0.60553 − 0.001074)

𝑥 = 0.83
b) For P = 3 bar and v = 1 m3/kg
Referring to Steam tables under Saturated pressure table (Table 2)
For P = 3bar,
𝑣𝑓 = 0.001074 𝑚3 /𝑘𝑔

𝑣𝑔 = 0.60553 𝑚3 /𝑘𝑔
 𝑣 > 𝑣𝑔

Therefore, the given condition should lie in the superheated region.

Referring to Superheated Steam tables for specific volume (Table 3)

For P = 3bar
T = 350 K and v = 0.9535 m3/kg
T = 400 K and v = 1.031 m3/kg
Use Interpolation formula
𝑥 − 𝑥1 𝑦 − 𝑦1
=
𝑥2 − 𝑥1 𝑦2 − 𝑦1
1 − 0.9535 𝑇 − 350
=
1.031 − 0.9535 400 − 350
𝑻 = 𝟑𝟖𝟎 𝑲
Example 3
Find the enthalpy and entropy of steam when the pressure is 2 MPa and the specific
volume is 0.09 m3/kg.
Referring to steam tables (saturated steam pressure table)
𝑚3
For P = 20 bar, 𝑣𝑓 = 0.001177 𝑘𝑔 , 𝑣𝑔 = 0.1 𝑚3 /𝑘𝑔

𝑣 = 𝑣𝑓 + x𝑣𝑓𝑔

0.09 = 0.001177 + 𝑥(0.1)

𝑥 = 0.89
𝑘𝐽
For P = 20 bar, ℎ𝑓 = 908.8 𝑘𝑔 , ℎ𝑔 = 2800 𝑘𝐽/𝑘𝑔

ℎ = ℎ𝑓 + xℎ𝑓𝑔 = 908.8 + (0.89 ∗ [2800 − 908.8]) = 2591.97 𝑘𝐽/𝑘𝑔

𝑘𝐽
For P = 20 bar, 𝑠𝑓 = 2.447 𝑘𝑔𝐾 , 𝑠𝑔 = 6.341 𝑘𝐽/𝑘𝑔K

𝑠 = 𝑠𝑓 + x𝑠𝑓𝑔 = 2.447 + (0.89 ∗ [6.341 − 2.447]) = 5.913 𝑘𝐽/𝑘𝑔𝐾

Example 4
Find the enthalpy, entropy and volume of steam at 1.4 MPa and 380⁰C.
Referring to steam tables (Saturated steam pressure tables)
For P = 14 bar, 𝑇𝑠𝑎𝑡 = 195℃
𝑇 > 𝑇𝑠𝑎𝑡 , Therefore the steam is superheated.
 T (⁰C) v (𝒎𝟑 /kg) h (kJ/kg) s (kJ/kgK)

350 0.2002 3150.7 7.139

380 ?? ?? ??

400 0.2177 3258.2 7.305

Use interpolation formula

𝑥 − 𝑥1 𝑦 − 𝑦1
=
𝑥2 − 𝑥1 𝑦2 − 𝑦1
𝑥 − 0.2002 380 − 350
=
0.2177 − 0.2002 400 − 350
𝒗 = 𝟎. 𝟐𝟏𝟎𝟕 𝒎𝟑 /𝒌𝒈
ℎ = 3215.2 𝑘𝐽/𝑘𝑔
𝑠 = 7.239 𝑘𝐽/𝑘𝑔𝐾
Equation of State
Ideal gas EOS / Characteristic gas equation
1
• Boyles law, 𝑣 ∝ at constant temperature
𝑝

• Charles law, 𝑣 ∝ 𝑇 at constant pressure

𝑇
• 𝑣 ∝ 𝑝

𝑅𝑇
• 𝑣= , 𝑅 → 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑜𝑟 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟𝑖𝑠𝑡𝑖𝑐 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑝

• 𝑝𝑣 = 𝑅𝑇 → 𝐼𝑑𝑒𝑎𝑙 𝐺𝑎𝑠 𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑆𝑡𝑎𝑡𝑒/𝐶ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟𝑖𝑠𝑡𝑖𝑐𝐺𝑎𝑠𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛

Other forms of Ideal Gas EOS
• 𝑚 = 𝑛𝑀
• 𝑝𝑉 =𝑚𝑅𝑇
𝑉
• 𝑣̅ = 𝑛

• 𝑝 𝑉 = 𝑛 𝑅𝑢 𝑇
• 𝑝 ̅𝑣 = 𝑅 𝑇
• 𝑅𝑢 = 𝑀𝑅 = 8314.47 𝐽/𝑘𝑚𝑜𝑙𝐾
𝑅𝑢
• 𝑅= 𝑀
Change of state of an ideal gas
• For an ideal gas undergoing change of state from 𝑝1 , 𝑣1 𝑎𝑛𝑑 𝑇1 to 𝑝2 , 𝑣2 𝑎𝑛𝑑 𝑇2
𝑝1 𝑣1
• =𝑅 1
𝑇1
𝑝2 𝑣2
• =𝑅 2
𝑇2

• From Equations 1 and 2

𝑝1 𝑣1 𝑝2 𝑣2
• = =𝐶
𝑇1 𝑇2

Ideal gas model

• A gas follows Ideal Gas Model when the following features are met
• It has no intermolecular forces of attraction or repulsion
• It does not change its phase during a thermodynamic process
• It obeys Charles law, Boyle’s law and Characteristic Gas Equation
• The internal energy of a gas decreases with decreasing pressure and
disappears when absolute pressure reaches zero.
• At zero pressure, all (real) gases behave in a similar manner and this state of
identical behaviour is referred as IDEAL STATE.
Example 1
The gauge pressure in an automobile tyre at a temperature of 25°C is 1.75 bar. Due to running
condition, the temperature of air in the tyre rises to 70°C. determine the gauge pressure after
running. Assume atmospheric pressure to be 1.0132 bar and volume of air in the tyre to be
constant.
Given: 𝑇1 = 25℃ + 273 = 298 𝐾, 𝑃𝑔1 = 1.75 𝑏𝑎𝑟,

𝑇2 = 70℃ + 273 = 343 𝐾, 𝑃𝑎𝑡𝑚 = 1.0132 𝑏𝑎𝑟

Solution: 𝑃1 = 𝑃𝑔1 + 𝑃𝑎𝑡𝑚 = 1.75 + 1.0132 = 2.7632 𝑏𝑎𝑟
𝑝1 𝑣1 𝑝2 𝑣2
=
𝑇1 𝑇2
𝑝1 𝑇2 2.7632 ∗ 105 ∗ 343
𝑝2 = = = 3.18 𝑏𝑎𝑟
𝑇1 298
𝑃2 = 𝑃𝑔2 + 𝑃𝑎𝑡𝑚

3.18 = 𝑃𝑔2 + 1.0132

𝑃𝑔2 = 2.1668 𝑏𝑎𝑟

Example 2
A cylinder of 50 liter capacity contains oxygen at 18°C and at a pressure of 10 MPa. Calculate
(a) mass of oxygen in the cylinder (b) the molar volume (c) density of oxygen. The molecular
mass of oxygen is 32 kg/kmol.
Given:
Solution:
𝑝𝑉 =𝑚𝑅𝑇
𝑅𝑢 8314.4
𝑅= = = 259.83 𝐽/𝑘𝑔𝐾
𝑀 32
𝑝 𝑉 100 ∗ 105 ∗ 50 ∗ 10−3
𝑚= = = 6.61 𝑘𝑔
𝑅𝑇 259.83 ∗ 291
𝑝𝑣̅ = 𝑅𝑢 𝑇
𝑅𝑢 𝑇 8314.4 ∗ 291
𝑣̅ = = = 0.24 𝑚3 /𝑘𝑚𝑜𝑙
𝑝 100 ∗ 105
𝑝 = 𝜌𝑅𝑇
𝑝 100 ∗ 105
𝜌= = = 132.26 𝑘𝑔/𝑚3
𝑅𝑇 259.83 ∗ 291
Example 3
10 kg of CO at 40°C occupies 3 m3. Determine the gas pressure in bar. An additional mass of
CO is then very slowly added to raise the tank pressure to 10 bar. Assuming that the gas
temperature remains constant, How much extra mass has been added?
Given: 𝑚1 = 10 𝑘𝑔, 𝑇1 = 40℃ = 313 𝐾 = 𝑇2 , 𝑉1 = 3 𝑚3 , 𝑝2 = 10 𝑏𝑎𝑟
𝑚1 𝑅𝑇1 10∗297∗313
Solution: 𝑝1 = = = 3.098 𝑏𝑎𝑟
𝑉1 3

𝑚 ∝𝑝
𝑚2 𝑝2
=
𝑚1 𝑝1
𝑝2 ∗ 𝑚1 10 ∗ 10
𝑚2 = = = 32.28 𝑘𝑔
𝑝1 3.098
𝐴𝑑𝑑𝑖𝑡𝑖𝑜𝑛𝑎𝑙 𝑚𝑎𝑠𝑠 𝑎𝑑𝑑𝑒𝑑, 𝑚 = 𝑚2 − 𝑚1 = 32.28 − 10 = 22.28 𝑘𝑔
Example 4
A spherical balloon of 8 m radius is floating in the atmosphere at 100 kPa pressure and 300 K
temperature. Determine the mass and the number of moles of air displaced by the balloon. If
hydrogen gas is filled in the balloon under the same conditions of temperature and pressure,
Calculate the mass and number of moles of hydrogen. Molecular masses of air and hydrogen
are taken as 28.97 and 2 respectively.
 𝑘𝑔 𝑘𝑔
Given: 𝑟𝑏 = 8 𝑚, 𝑃 = 100 𝑘𝑃𝑎 = 1 𝑏𝑎𝑟, 𝑇 = 300 𝐾, 𝑀𝑎𝑖𝑟 = 28.97 𝑘𝑚𝑜𝑙 , 𝑀𝐻2 = 2 𝑘𝑚𝑜𝑙

Solution:
𝑅𝑢 8314.4
𝑅𝑎𝑖𝑟 = = = 287 𝐽/𝑘𝑔𝐾
𝑀𝑎𝑖𝑟 28.97
𝑅𝑢 8314.4
𝑅𝐻2 = = = 4157.2 𝐽/𝑘𝑔𝐾
𝑀𝐻2 2
4 4
𝑉𝑏 = 𝜋𝑟𝑏 3 = 𝜋83 = 2144.66 𝑚3
3 3
When air is filled in the balloon,
𝑝𝑉 1 ∗ 105 ∗ 2144.6
𝑚= = = 2491 𝑘𝑔
𝑅𝑎𝑖𝑟 𝑇 287 ∗ 300
𝑚 2491
𝑛= = = 85.98 𝑘𝑚𝑜𝑙
𝑀 28.97
When Hydrogen is filled in the balloon,
𝑝𝑉 1 ∗ 105 ∗ 2144.6
𝑚= = = 172 𝑘𝑔
𝑅𝐻2 𝑇 4157.2 ∗ 300
𝑚 172
𝑛= = = 86 𝑘𝑚𝑜𝑙
𝑀 2
Example 5
An aerostat balloon is filled with hydrogen, it has a volume of 1000 m3 at a temperature of 300
K and pressure of 100 kPa. Determine the payload that can be lifted with the aid of aerostat.
Given: 𝑉 = 1000 𝑚3 , 𝑇 = 300 𝐾, 𝑃 = 100 𝑘𝑃𝑎 = 1 𝑏𝑎𝑟
Solution:
𝑝𝑉 1 ∗ 105 ∗ 1000
𝑚= = = 80.18 𝑘𝑔
𝑅𝐻2 𝑇 4157.2 ∗ 300

𝑣𝑜𝑙𝑢𝑚𝑒 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑏𝑎𝑙𝑙𝑜𝑜𝑛 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑖𝑟 𝑒𝑞𝑢𝑖𝑎𝑣𝑎𝑙𝑒𝑛𝑡 𝑡𝑜 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑎𝑙𝑙𝑜𝑜𝑛

𝑝𝑉 1 ∗ 105 ∗ 1000
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑖𝑟 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑑, 𝑚 = = = 1161.44 𝑘𝑔
𝑅𝑎𝑖𝑟 𝑇 287 ∗ 300
𝑃𝑎𝑦𝑙𝑜𝑎𝑑 𝑡ℎ𝑎𝑡 𝑐𝑎𝑛 𝑏𝑒 𝑙𝑖𝑓𝑡𝑒𝑑 = 1161.44 − 80.18 = 1081.26 𝑘𝑔
Example 6
A room of 1000 m3 volume, contains air at 1 bar and 300 K. In the room, there is a balloon
which contains air at 300 K. Suddenly, the balloon bursts. Before any air can escape through
the doors or windows, the pressure in the room becomes 1.3 bar, while its temperature is still
300 K. If the volume of the balloon was 50 m3, Find (a) mass of air originally in the room
(outside the balloon) (b) initial pressure in bar of air in the balloon (c) final mass of air in the
room.
Given: 𝑉𝑟 = 1000 𝑚3 , 𝑃1 = 1 𝑏𝑎𝑟, 𝑇 = 300 𝐾, 𝑃2 = 1.3 𝑏𝑎𝑟, 𝑉𝑏 = 50 𝑚3
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑖𝑟 𝑖𝑛 𝑡ℎ𝑒 𝑟𝑜𝑜𝑚 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑦 (𝑒𝑥𝑐𝑙𝑢𝑑𝑖𝑛𝑔 𝑏𝑎𝑙𝑙𝑜𝑜𝑛′ 𝑠 𝑣𝑜𝑙𝑢𝑚𝑒),
𝑉1 = 𝑉𝑟 − 𝑉𝑏 = 1000 − 50 = 950 𝑚3
a) Mass of air originally inside the room,
𝑃1 𝑉1 1 ∗ 105 ∗ 950
𝑚1 = = = 1103.37 𝑘𝑔
𝑅𝑎𝑖𝑟 𝑇 287 ∗ 300
b) Final mass of air inside the room
𝑃2 𝑉𝑟 1.3 ∗ 105 ∗ 1000
𝑚𝑓 = = = 1509.9 𝑘𝑔
𝑅𝑎𝑖𝑟 𝑇 287 ∗ 300
c) Initial pressure of air inside the balloon
𝑚𝑏 = 𝑚𝑓 − 𝑚1 = 1509.9 − 1103.37 = 406.5 𝑘𝑔
𝑚𝑏 𝑅𝑇 406.5 ∗ 287 ∗ 300
𝑃𝑏 = = = 7 𝑏𝑎𝑟
𝑉𝑏 50
Deviation from Ideal gas behavior
• At very low density of gases, the average distance between molecules is so large, such
that the particles would be independent of one another.
𝑎
• Van der walls Equation of state - (𝑝 + 𝑣̅2 ) (𝑣̅ − 𝑏) = 𝑅𝑢 𝑇

• a – to account for the existence of mutual attraction between the molecules

𝑎
• - force of cohesion
𝑣̅ 2

• b – to account for the volumes of molecules – known as co-volume

• Van der Waals EoS – applicable at higher pressures
• Not valid in all ranges of pressure and temperature
Compressibility factor
𝑝𝑣
• 𝑍 = 𝑅𝑇

• 𝑝𝑣 = 𝑍𝑅𝑇
• For an ideal gas, 𝑍 = 1.
• Deviation of Z from unity is a measure of deviation from Ideal Gas EoS
• At all temperatures, 𝑍 → 1 𝑤ℎ𝑒𝑛 𝑃 → 0
• As pressure approaches zero, Ideal Gas EoS is applicable
 • As temperature approaches above 300 K and above, Z approaches unity for a pressure
of 10 Mpa
• At low temperatures and high pressures, Z deviates from Ideal gas value

Compressibility chart
• When compressibility charts are considered for pure substances, all charts appear alike.
• Quantitatively they are different but in appearance they are alike.
• To put all these substances on a common basis, the properties are reduced with respect
to their values at critical point.
𝑃
• 𝑃𝑟 = 𝑃
𝑐

𝑇
• 𝑇𝑟 = 𝑇
𝑐
Example 7
The gas neon has a molecular weight of 20.183 and its critical temperature, pressure and
volume are 44.5 K, 2.73 MPa and 0.0416 m3/kg mol. Reading from a compressibility chart for
a reduced pressure of 2 and a reduced temperature of 1.3, the compressibility factor Z is 0.7.
What are the corresponding specific volume, pressure, temperature and reduced volume?
𝑚3
Given: 𝑇𝑐 = 44.5 𝐾, 𝑃𝑐 = 2.73 𝑀𝑃𝑎, 𝑣𝑐 = 0.416 𝑘𝑔 , 𝑇𝑟 = 1.3, 𝑃𝑟 = 2, 𝑍 = 0.7

Solution:
𝑃 = 𝑃𝑟 𝑃𝑐 = 2 ∗ 2.73 = 5.46 𝑀𝑃𝑎
𝑇 = 𝑇𝑟 𝑇 = 1.3 ∗ 44.5 = 57.85 𝐾
8314.4
𝑍𝑅𝑇 0.7 ∗ 20.183 ∗ 57.85
𝑣= = = 3.05 ∗ 10−3 𝑚3 /𝑘𝑔
𝑝 5.46 ∗ 106
𝑣 3.05 ∗ 10−3
𝑣𝑟 = = = 1.48
𝑣𝑐 0.416
Example 8
1 mole of carbon-dioxide at 88.7 bar and 61°C is compressed in reversible isothermal manner
till the volume halves. Calculate the work transfer during the process.
Given: 𝑛 = 1 𝑘𝑚𝑜𝑙, 𝑃 = 88.7 𝑏𝑎𝑟, 𝑇 = 61℃ = 334 𝐾
𝑝𝑣 = 𝑛𝑅𝑢 𝑇
For a real gas, 𝑝𝑣 = 𝑍𝑛𝑅𝑢 𝑇
𝑍𝑛𝑅𝑢 𝑇 𝑑𝑣 𝑣2
𝑊 = ∫ 𝑝 𝑑𝑣 = ∫ 𝑑𝑣 = 𝑍𝑛𝑅𝑢 𝑇 ∫ = 𝑍𝑛𝑅𝑢 𝑇 ln ( )
𝑣 𝑣 𝑣1
𝑃𝑐 = 73.9 𝑏𝑎𝑟, 𝑇𝑐 = 304 𝐾
𝑃 88.7
𝑃𝑟 = = = 1.2
𝑃𝑐 73.9
𝑇 334
𝑇𝑟 = = = 1.1
𝑇𝑐 304
From Compressibility chart for CO2, 𝑍 = 0.62
𝑣2 1
𝑊 = 𝑍𝑛𝑅𝑢 𝑇 ln ( ) = 0.62 ∗ 1 ∗ 8314.4 ∗ 334 ∗ ln ( ) = −1229 𝑘𝐽
𝑣1 2
Example 9
Determine the pressure exerted by carbon-dioxide in a container of 1.5 m3 capacity when it
contains 5 kg at 27°C, (a) Using ideal gas equation (b) Using Van der Waals equation. Use a =
3.6285 X 105 J4/kg mol2 and b = 0.0422 m3/kg mol, constants of Van der Waals equation.
Given: 𝑚 = 5 𝑘𝑔, 𝑉 = 1.5 𝑚3 , 𝑇 = 27℃
Solution:
8314.4
𝑚𝑅𝑇 5∗ ∗300
44
a) Ideal Gas EoS: 𝑝 = = = 1.8895 𝑏𝑎𝑟
𝑉 1.5
𝑉 𝑉𝑀 1.5∗44
b) Van der waals EoS: 𝑣̅ = 𝑛 = = = 13.2 𝑚3 /𝑘𝑚𝑜𝑙
𝑚 5
𝑎
(𝑝 + ) (𝑣̅ − 𝑏) = 𝑅𝑢 𝑇
𝑣̅ 2
𝑅𝑢 𝑇 𝑎 8314.4 ∗ 300 3.6285 ∗ 105
𝑝= − = − = 1.875 𝑏𝑎𝑟
(𝑣̅ − 𝑏) 𝑣̅ 2 (13.2 − 0.0422) 13.22
Example 10
Determine the density of the steam at 100 bar and 600°C by using (a) steam tables (b) perfect
gas equation (c) Van der Walls equation with a = 5.5113 X 105 J4/kg mol2 and b = 0.030
m3/kgmol and (d) Compressibility chart.
𝐽4
Given: 𝑃 = 100 𝑏𝑎𝑟, 𝑇 = 600℃ = 873𝐾, 𝑎 = 5.5113 ∗ 105 𝑘𝑚𝑜𝑙2 , 𝑏 = 0.030 𝑚3 /𝑘𝑚𝑜𝑙

Solution:
a) Steam tables: For P = 100 bar, 𝑇𝑠𝑎𝑡 = 311 ℃,
𝑇 > 𝑇𝑠𝑎𝑡 . 𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑠𝑡𝑒𝑎𝑚 𝑖𝑠 𝒔𝒖𝒑𝒆𝒓𝒉𝒆𝒂𝒕𝒆𝒅.
𝑚3 1 1
Referring to superheated steam tables, 𝑣 = 0.03837 𝑘𝑔 , 𝜌 = 𝑣 = 0.03837 = 26.06 𝑘𝑔/𝑚3
 𝑃 100∗105
b) Ideal gas EoS: 𝜌 = 𝑅𝑇 = 8314.4 = 24.8 𝑘𝑔/𝑚3
∗873
18

𝑎
c) Van der Waals EoS: (𝑝 + 𝑣̅2 ) (𝑣̅ − 𝑏) = 𝑅𝑢 𝑇

5.5113 ∗ 105
7
(10 + ) (𝑣̅ − 0.03) = 8314.4 ∗ 873
𝑣̅ 2

100𝑣̅ 3 − 75.58𝑣̅ 2 + 5.5113𝑣̅ − 0.16534 = 0

𝑣̅ = 0.68 𝑚3 /𝑘𝑔
𝑛𝑣̅ 0.68
𝑣= = = 0.0378 𝑚3 /𝑘𝑔
𝑚 18
1 1
𝜌= = = 26.46 𝑘𝑔/𝑚3
𝑣 0.0378
d) Compressibility chart
𝑃𝑐 = 221.2 𝑏𝑎𝑟, 𝑇𝑐 = 374.15℃ = 647.15 𝐾
𝑃 100
𝑃𝑟 = = = 0.45
𝑃𝑐 221.2
𝑇 873
𝑇𝑟 = = = 1.35
𝑇𝑐 647.15
Using compressibility chart, 𝑍 = 0.95
𝑍𝑅𝑢 𝑇 0.95 ∗ 8314.4 ∗ 873
𝑣= = = 0.0383 𝑚3 /𝑘𝑔
𝑝 𝑀𝐻2 𝑂 100 ∗ 105 ∗ 18
1 1
𝜌= = = 26.1 𝑘𝑔/𝑚3
𝑣 0.0383

UNIT 2 - FIRST LAW OF THERMODYNAMICS

First Law for a closed system undergoing a cycle

∑ 𝑄=∑ 𝑊
𝑐𝑦𝑐𝑙𝑒 𝑐𝑦𝑐𝑙𝑒

∮ 𝑑𝑄 = ∮ 𝑑𝑊

𝐸̇𝑖𝑛 = 𝐸̇𝑜𝑢𝑡
First Law applied to a system undergoing a change of state
𝑸 = ∆𝑬 + 𝑾
 𝑬̇𝒊𝒏 = 𝑬̇𝒐𝒖𝒕 + 𝑬̇𝒔𝒕𝒐𝒓𝒆𝒅

Energy – Property of a system

A-B is a cycle
𝑄𝐴 = ∆𝐸𝐴 + 𝑊𝐴

𝑄𝐵 = ∆𝐸𝐵 + 𝑊𝐵

∑ 𝑄=∑ 𝑊
𝑐𝑦𝑐𝑙𝑒 𝑐𝑦𝑐𝑙𝑒

𝑄𝐴 + 𝑄𝐵 = 𝑊𝐴 + 𝑊𝐵

𝑄𝐴 − 𝑊𝐴 = 𝑄𝐵 − 𝑊𝐵

∆𝐸𝐴 = ∆𝐸𝐵
A-C is another cycle
𝑄𝐴 = ∆𝐸𝐴 + 𝑊𝐴

𝑄𝐶 = ∆𝐸𝐶 + 𝑊𝐶

∑ 𝑄=∑ 𝑊 ∮ 𝑑𝐸 = 0
𝑐𝑦𝑐𝑙𝑒 𝑐𝑦𝑐𝑙𝑒

𝑄𝐴 + 𝑄𝐶 = 𝑊𝐴 + 𝑊𝐶

𝑄𝐴 − 𝑊𝐴 = 𝑄𝐶 − 𝑊𝐶

∆𝐸𝐴 = ∆𝐸𝐶

Different forms of stored energy

❖ Energy in storage – Internal energy
❖ E – refers to total energy stored in a system
❖ Macroscopic energy model
❖ Comprises macroscopic kinetic energy and macroscopic potential energy
❖ Microscopic energy model
❖ Refers to energy stored in the molecular level or atomic structure of the
system
❖ Referred to as INTERNAL ENERGY
❖ Denoted by U
❖ Energy of one molecule, 𝜀 = 𝜀𝑡𝑟𝑎𝑛𝑠 + 𝜀𝑟𝑜𝑡 + 𝜀𝑣𝑖𝑏 + 𝜀𝑐ℎ𝑒𝑚 + 𝜀𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑖𝑐 +
𝜀𝑛𝑢𝑐𝑙𝑒𝑎𝑟
 ❖ Total internal energy, 𝑈 = 𝑁𝜀, where N is the number of molecules in a
system
❖ For an ideal gas, there is no intermolecular forces of attraction or repulsion
❖ Internal energy depends only on temperature, 𝑈 = 𝑓(𝑇) 𝑜𝑛𝑙𝑦
Internal energy
❖ For an ideal gas, 𝐸 = 𝐸𝐾 + 𝐸𝑃 + 𝑈
❖ In the absence of motion and gravity, 𝐸 = 𝑈
❖ 𝑄 = ∆𝑈 + 𝑊
❖ In the differential form, 𝑑𝑄 = 𝑑𝐸 + 𝑑𝑊
❖ 𝑑𝑊 = 𝑑𝑊𝑝𝑑𝑣 + 𝑑𝑊𝑠ℎ𝑎𝑓𝑡 + 𝑑𝑊𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 + ⋯

❖ Only when p dV work is present, 𝑑𝑄 = 𝑑𝐸 + 𝑝𝑑𝑉

Specific heat at constant volume
𝜕𝑢
❖ 𝑐𝑣 = (𝜕𝑇)
𝑣
𝑇
❖ (∆𝑢)𝑣 = ∫𝑇 2 𝑐𝑣 𝑑𝑇
1

❖ 𝑑𝑄 = 𝑑𝑈 + 𝑝𝑑𝑉
❖ At constant volume, 𝑑𝑄 = 𝑑𝑈
❖ (𝑞)𝑣 = (∆𝑢)𝑣
𝑇
❖ (𝑞)𝑣 = ∫𝑇 2 𝑐𝑣 𝑑𝑇
1

𝜕𝑄
❖ 𝑐𝑣 = (𝜕𝑇 )
𝑣

❖ u, T and v are properties, therefore cv is a property

Enthalpy
❖ ℎ = 𝑢 + 𝑝𝑣
❖ Intensive property
❖ 𝑑𝑞 = 𝑑𝑢 + 𝑝𝑑𝑣
❖ 𝑑(𝑝𝑣) = 𝑝𝑑𝑣 + 𝑣𝑑𝑝
❖ At constant pressure, 𝑑(𝑝𝑣) = 𝑝𝑑𝑣
❖ 𝑑𝑞 = 𝑑𝑢 + 𝑑(𝑝𝑣) = 𝑑(𝑢 + 𝑝𝑣) = 𝑑ℎ
❖ Heat transferred at constant pressure increases the enthalpy of a system
❖ ℎ = 𝑢 + 𝑝𝑣 = 𝑢 + 𝑅𝑇 and ℎ = 𝑓(𝑇)𝑜𝑛𝑙𝑦
Specific heat at constant pressure
𝜕ℎ
❖ 𝑐𝑝 = (𝜕𝑇)
𝑝

𝑇
❖ (∆ℎ)𝑣 = ∫𝑇 2 𝑐𝑝 𝑑𝑇
1

❖ 𝑑𝑄 = 𝑑𝑈 + 𝑝𝑑𝑉
❖ ℎ = 𝑢 + 𝑝𝑣
❖ 𝑑ℎ = 𝑑𝑢 + 𝑑(𝑝𝑣) = 𝑑𝑢 + 𝑝𝑑𝑣 + 𝑣𝑑𝑝 = 𝑑𝑞 + 𝑣𝑑𝑝
❖ 𝑑𝑞 = 𝑑ℎ − 𝑣𝑑𝑝
❖ (𝑑𝑞)𝑝 = 𝑑ℎ − 𝑣𝑑𝑝

❖ (𝑞)𝑝 = (∆ℎ)𝑝
𝜕𝑄
❖ 𝑐𝑝 = ( 𝜕𝑇 )
𝑝

Energy of an Isolated system

❖ For an isolated system, 𝑑𝑄 = 0, 𝑑𝑊 = 0
❖ 𝑑𝑄 = 𝑑𝐸 + 𝑑𝑊
❖ 𝑑𝐸 = 0
❖ 𝐸 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
❖ ENERGY OF AN ISOLATED SYSTEM IS ALWAYS CONSTANT.

Perpetual Motion Machine of First Kind (PMMI)

❖ PMMI – There can be no machine which would continuously supply mechanical work
without some form of energy disappearing simultaneously.
❖ PMMI – a fictitious machine

Converse of PMMI
❖ Converse of PMMI – There can be no machine which would continuously consume
work without some form of energy appearing simultaneously.
Example 1
A stationary mass of gas is compressed without friction from an initial state of 0.3 m3 and
0.105 MPa to a final state of 0.15 m3 and 0.105 MPa, the pressure remaining constant
throughout the process. There is a transfer of 37.6 kJ of heat from the gas during the process.
How much does the internal energy of the gas change?
Given: 𝑉1 = 0.3 𝑚3 , 𝑃1 = 0.105 𝑀𝑃𝑎 = 𝑃2 , 𝑉2 = 0.15 𝑚3 , 𝑄 = −37.6 𝑘𝐽
Solution:
𝑄 = ∆𝑈 + 𝑊
𝑉
𝑊 = ∫𝑉 2 𝑝𝑑𝑉 = 𝑝(𝑉2 − 𝑉1 ) = 0.105 ∗ 106 ∗ (0.15 − 0.3) = −15.75 𝑘𝐽
1

∆𝑈 = 𝑄 − 𝑊 = −37.6 + 15.75 = −21.85 𝑘𝐽

Example 2
When a system is taken from state ‘a’ to state ‘b’ in figure along path acb, 84 kJ of heat flow
into the system, and the system does 32 kJ of work. (a) How much heat flows along path adb,
if the work done is 10.5 kJ? (b) when the system is returned from ‘b’ to ‘a’ along the curved
path, the work done on the system is 21 kJ. Does the system absorb or liberate heat? How
much amount of heat is absorbed or liberated? (c) If Ua = 0 and Ud = 42 kJ, find the heat
absorbed in the processes ‘ad’ and ‘db’.

Given: 𝑄𝑎𝑐𝑏 = 84 𝑘𝐽, 𝑊𝑎𝑐𝑏 = 32 𝑘𝐽

Solution:
A) 𝑊𝑎𝑑𝑏 = 10.5 𝑘𝐽, 𝑄𝑎𝑑𝑏 =?
𝑄𝑎𝑐𝑏 = ∆𝑈𝑎𝑐𝑏 + 𝑊𝑎𝑐𝑏 ∆𝑈𝑎𝑐𝑏 = 𝑄𝑎𝑐𝑏 − 𝑊𝑎𝑐𝑏 = 84 − 32 = 52 𝑘𝐽
𝑄𝑎𝑑𝑏 = ∆𝑈𝑎𝑑𝑏 + 𝑊𝑎𝑑𝑏 = 52 + 10.5 = 62.5 𝑘𝐽
 B) 𝑊𝑏𝑎 = −21 𝑘𝐽, 𝑄𝑏𝑎 =?
𝑄𝑏𝑎 = ∆𝑈𝑏𝑎 + 𝑊𝑏𝑎 = (𝑈𝑎 − 𝑈𝑏 ) + 𝑊𝑏𝑎 = −52 − 21 = −73 𝑘𝐽
-73 kJ denotes that heat is liberated.
C) 𝑈𝑎 = 0, 𝑈𝑑 = 42 𝑘𝐽, 𝑄𝑎𝑑 =? , 𝑄𝑑𝑏 =?
𝑄𝑎𝑑 = ∆𝑈𝑎𝑑 + 𝑊𝑎𝑑 = (𝑈𝑑 − 𝑈𝑎 ) + 𝑊𝑎𝑑 = (42 − 0) + 10.5 = 52.5 𝑘𝐽
𝑄𝑑𝑏 = ∆𝑈𝑑𝑏 + 𝑊𝑑𝑏 = (𝑈𝑏 − 𝑈𝑑 ) + 𝑊𝑑𝑏 = (52 − 42) + 0 = 10 𝑘𝐽
Example 3
A piston and cylinder machine contains a fluid system which passes through a complete cycle
of four processes. During a cycle, the sum of all heat transfers is -170 kJ. The system
completes 100 cycles per minute. Complete the following table showing the method for each
item, and compute the net rate of work output in kW.

Q ΔE
Process W(kJ/min)
(kJ/min) (kJ/min)

a–b 0 2170 ?

b–c 21000 0 ?

c–d -2100 ? -36600

d–a ? ? ?

Given: ∑ 𝑄 = −170 𝑘𝐽, ∑ 𝑄𝑛𝑒𝑡 = −17000 𝑘𝐽/𝑚𝑖𝑛

Process a-b: 𝑄𝑎𝑏 = ∆𝐸𝑎𝑏 + 𝑊𝑎𝑏 , ∆𝐸𝑎𝑏 = 𝑄𝑎𝑏 − 𝑊𝑎𝑏 = 0 − 2170 =
−2170 𝑘𝐽/𝑚𝑖𝑛
Process b-c: 𝑄𝑏𝑐 = ∆𝐸𝑏𝑐 + 𝑊𝑏𝑐 , ∆𝐸𝑏𝑐 = 𝑄𝑏𝑐 − 𝑊𝑏𝑐 = 21000 − 0 =
21000 𝑘𝐽/𝑚𝑖𝑛
Process c-d: 𝑄𝑐𝑑 = ∆𝐸𝑐𝑑 + 𝑊𝑐𝑑 , 𝑊𝑐𝑑 = 𝑄𝑐𝑑 − ∆𝐸𝑐𝑑 = −2100 + 36600 =
34500 𝑘𝐽/𝑚𝑖𝑛
Process d-a: 𝑄𝑛𝑒𝑡 = 𝑄𝑎𝑏 + 𝑄𝑏𝑐 + 𝑄𝑐𝑑 + 𝑄𝑑𝑎
−17000 = 0 + 21000 − 2100 + 𝑄𝑑𝑎
𝑄𝑑𝑎 = −35900 𝑘𝐽/𝑚𝑖𝑛
𝑘𝐽
𝑊𝑛𝑒𝑡 = −17000 𝑚𝑖𝑛 = 𝑊𝑎𝑏 + 𝑊𝑏𝑐 + 𝑊𝑐𝑑 + 𝑊𝑑𝑎 = 2170 + 0 + 34500 + 𝑊𝑑𝑎
 𝑊𝑑𝑎 = −53670 𝑘𝐽/𝑚𝑖𝑛
∆𝐸𝑑𝑎 = 𝑄𝑑𝑎 − 𝑊𝑑𝑎 = −35900 + 53670 = 17770 𝑘𝐽/𝑚𝑖𝑛
𝑘𝐽
𝑊𝑛𝑒𝑡 = −17000 = −283.3 𝑘𝑊
𝑚𝑖𝑛
Example 4
The internal energy of a certain substance is given by 𝑢 = 3.56 𝑝𝑣 + 84 where u is in kJ/kg,
p is in Pa and v is in m3/kg. A system composed of 3 kg of this substance expands from an
initial pressure of 500 kPa and a volume of 0.22 m3 to a final pressure of 100 kPa in a process
in which pressure and volume are related by 𝑝 𝑣 1.2 = 𝑐. (a) If the expansion is quasi-static,
find Q, ΔU and W for the process. (b) In another process the same system expands according
to the same pressure volume relationship as in part (a) and from the same initial state to the
same final state as in part (a), but the heat transfer in this case is 30 kJ. Find the work transfer
in this process. (c)Explain the difference in work transfer in parts (a) and (b).
Given: 𝑚 = 3 𝑘𝑔, 𝑝1 = 500 𝑘𝑃𝑎, 𝑉1 = 0.22 𝑚3 , 𝑃2 = 100 𝑘𝑃𝑎, 𝑝 𝑣 1.2 = 𝑐, 𝑢 =
3.56 𝑝𝑣 + 84

Solution:𝑝1 𝑉11.2 = 𝑝2 𝑉21.2

1 1
𝑝1 𝑉1 1.2 1.2 5(0.22)1.2 1.2
𝑉2 = ( ) =( ) = 0.84 𝑚3
𝑝2 1

0.22
𝑢1 = 3.56𝑝1 𝑣1 + 84 = [3.56 ∗ 500 ∗ ( )] + 84 = 214.53 𝑘𝐽/𝑘𝑔
3

0.84
𝑢2 = 3.56𝑝2 𝑣2 + 84 = [3.56 ∗ 100 ∗ ( )] + 84 = 183.68 𝑘𝐽/𝑘𝑔
3

∆𝑢 = 𝑢2 − 𝑢1 = 183.68 − 214.53 = −30.85 𝑘𝐽/𝑘𝑔

𝑃2 𝑉2 −𝑃1 𝑉1 500∗103 ∗0.22−100∗103 ∗0.84
𝑊= 1−𝑛
= 1−1.2
= 127.5 𝑘𝐽

𝑄 = ∆𝑈 + 𝑊 = (−30.85 ∗ 3) + 127.5 = 34.95 𝑘𝐽

B) When 𝑄 = 30 𝑘𝐽
𝑊 = 𝑄 − ∆𝑈 = 30 + (30.85 ∗ 3) = 122.5 𝑘𝐽
C) W in (a) is for a quasi-static process using ∫ 𝑝𝑑𝑉 whereas (b)is not quasi −
static
Example 5
A fluid is confined in a cylinder by a spring loaded frictionless piston so that the pressure in
the fluid is a linear function of the volume (𝑝 = 𝑎𝑉 + 𝑏). The internal energy of the fluid is
given by 𝑈 = 34 + 3.15 𝑝𝑉 where U is in kJ, p is in Pa and V is in m3. If the fluid changes
from an initial state of 170 kPa, 0.03 m3 to a final state of 400 kPa, 0.06 m3, with no work
other than that done on the piston, find the direction and magnitude of the work and heat
transfer.
Given: 𝑉1 = 0.03 𝑚3 , 𝑃1 = 1.7 𝑏𝑎𝑟, 𝑉2 = 0.06 𝑚3 , 𝑃2 = 4 𝑏𝑎𝑟
𝑝 = 𝑎𝑉 + 𝑏 𝑈 = 34 + 3.15 𝑝𝑉
𝑉2 𝑎
Solution: 𝑊 = ∫ 𝑝𝑑𝑉 = ∫(𝑎𝑉 + 𝑏)𝑑𝑉 = 𝑎 + 𝑏𝑉 = 2 (𝑉2 2 − 𝑉1 2 ) + 𝑏(𝑉2- 𝑉1 )
2

𝑝 = 𝑎𝑉 + 𝑏
𝑝1 = 𝑎𝑉1 + b 𝑝2 = 𝑎𝑉2 + b
170000 = 0.03𝑎 + 𝑏
400000 = 0.06𝑎 + 𝑏
𝑘𝑁 𝑘𝑁
On solving the above equations, 𝑎 = −60 𝑚2 , 𝑏 = 7667 𝑚5

𝑎 −60
𝑊= (𝑉2 2 − 𝑉1 2 ) + 𝑏(𝑉2 - 𝑉1 ) = (0.062 − 0.032 ) + 7667(0.06 − 0.03) = 8.55 𝑘𝐽
2 2
𝑈1 = 34 + 3.15𝑝1 𝑉1 = 34 + 3.15(1.7 ∗ 105 ∗ 0.03) = 16.099 𝑘𝐽
𝑈2 = 34 + 3.15𝑝2 𝑉2 = 34 + 3.15(4 ∗ 105 ∗ 0.06) = 75.634 𝑘𝐽
∆𝑈 = 𝑈2 − 𝑈1 = 75.634 − 16.099 = 59.54 𝑘𝐽
𝑄 = ∆𝑈 + 𝑊 = 59.54 + 8.55 = 68.09 𝑘𝐽
Example 6
A stationary fluid system goes through a cycle as shown in figure comprising the following
processes:
(a) Process 1-2 isochoric heat addition of 235 kJ/kg
(b) Process 2-3 adiabatic expansion to its original pressure with loss of 70 kJ/kg in
internal energy.
(c) Process 3-1 isobaric compression to its original volume with heat rejection of 200
kJ/kg.
Prepare a balance sheet of energy quantities and find the overall change during the
cycle.

Process Process Q ∆u W
Definition (kJ/kg) (kJ/kg) (kJ/kg)

1-2 Isochoric Heat 235 0

addition

2-3 Adiabatic 0 -70

Expansion
 3-1 Isobaric -200
Compression

𝑘𝐽
Process 1-2: For Isochoric heat addition 𝑊1−2 = 0, 𝑄1−2 = 235 𝑘𝑔 ,

∆𝑈1−2 = 𝑄1−2 − 𝑊1−2 = 235 − 0 = 235 𝑘𝐽/𝑘𝑔

Process 2-3: For Adiabatic Expansion, 𝑄2−3 = 0, ∆𝑈2−3 = −70 𝑘𝐽/𝑘𝑔
𝑊2−3 = 𝑄2−3 − ∆𝑈2−3 = 0 − (−70) = 70 𝑘𝐽/𝑘𝑔
Process 3-1: For Isobaric compression, 𝑃 = 𝑐
1-2-3-1 is a cycle, ∑ 𝑄 = ∑ 𝑊

∑ 𝑄 = 𝑄1−2 + 𝑄2−3 + 𝑄3−1 = 235 + 0 − 200 = 35 𝑘𝐽/𝑘𝑔

𝑘𝐽
∑ 𝑊 = 35 = 𝑊1−2 + 𝑊2−3 + 𝑊3−1 = 0 + 70 + 𝑊3−1
𝑘𝑔

𝑊3−1 = 35 − 70 = −35 𝑘𝐽/𝑘𝑔

∆𝑈3−1 = 𝑄3−1 − 𝑊3−1 = −200 − (−35) = −165 𝑘𝐽/𝑘𝑔

∑ ∆𝑈 = ∆𝑈1−2 + ∆𝑈2−3 + ∆𝑈3−1 = 235 − 70 − 165 = 0

S.No Process Work done Change Heat Change Change in

of transferred of entropy
internal enthalpy
energy

1 𝑉=𝐶 0 𝑚𝑐𝑣 (𝑇2 𝑚𝑐𝑣 (𝑇2 𝑚𝑐𝑝 (𝑇2 𝑇2

𝑚𝑐𝑣 ln ( )
− 𝑇1 ) − 𝑇1 ) − 𝑇1 ) 𝑇1

2 𝑝=𝐶 𝑝(𝑉2 − 𝑉1 ) 𝑚𝑐𝑣 (𝑇2 𝑚𝑐𝑝 (𝑇2 𝑚𝑐𝑝 (𝑇2 𝑇2

𝑚𝑐𝑝 ln ( )
− 𝑇1 ) − 𝑇1 ) − 𝑇1 ) 𝑇1

3 𝑝𝑉 = 𝐶 𝑉2 0 𝑉2 0 𝑃1
𝑝1 𝑉1 ln ( ) 𝑝1 𝑉1 ln ( ) 𝑚𝑅 ln ( )
𝑉1 𝑉1 𝑃2
 4 𝑝𝑉 𝑛 𝑝2 𝑉2 − 𝑝1 𝑉1 𝑚𝑐𝑣 (𝑇2 𝑄 𝑚𝑐𝑝 (𝑇2 𝑇2
𝑚𝑐𝑛 ln ( )
1−𝑛 − 𝑇1 ) = ∆𝑈 + 𝑤 − 𝑇1 ) 𝑇1

Example 7
A certain gas occupies a volume of 0.3 m3 at a pressure of 2 bar. The temperature of gas at
this state is 350 K. The gas undergoes a thermodynamic constant volume process until the
pressure rises to 7 bar. Determine the temperature at the end of the process, change in internal
energy, change in enthalpy and change in entropy during this process. Take Cv = 0.712 kJ/kg
K and R = 0.287 kJ/kg K.
Given: 𝑉1 = 0.3 𝑚3 , 𝑃1 = 2 𝑏𝑎𝑟, 𝑃2 = 7 𝑏𝑎𝑟, 𝑇1 = 350 𝐾
Solution:
𝑃1 𝑉1 𝑃2 𝑉2 𝑇 350∗7
𝑇1
= 𝑇2
𝑇2 = 𝑃 1𝑉 ∗ 𝑃2 𝑉2 = 2
= 1225 𝐾
1 1

𝑃1 𝑉1 2∗105 ∗0.3
𝑚= = = 0.5973 𝑘𝑔
𝑅𝑇1 287∗350

∆𝑈 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) = 0.5973 ∗ 712 ∗ (1225 − 350) = 371.12 𝑘𝐽

∆𝐻 = 𝑚𝑐𝑝 (𝑇2 − 𝑇1 ) = 0.5973 ∗ 999 ∗ (1225 − 350) = 522.63 𝑘𝐽
𝑇 1225
∆𝑆 = 𝑚𝑐𝑣 ln ( 2) = 0.5973 ∗ 712 ∗ ln ( ) = 0.5328 𝑘𝐽/𝐾
𝑇1 350

Example 8
1 kg of nitrogen at a temperature of 150°C occupies a volume of 0.2 m3. The gas
undergoes a fully restricted constant-pressure expansion without friction to a final
volume of 0.36 m3. Calculate the final temperature, heat transferred and change in
entropy. Take Cv = 743 J/kg K and R = 297 J/kg K.
Given: 𝑚 = 1𝑘𝑔, 𝑇1 = 150℃ = 423 𝐾, 𝑉1 = 0.2 𝑚3 , 𝑉2 = 0.36 𝑚3
𝑉 0.36
𝑇2 = 𝑉2 𝑇1 = 0.20 ∗ 423 = 761.4 𝐾
1

𝑄 = 𝑚𝑐𝑝 (𝑇2 − 𝑇1 ) = 1 ∗ (743 + 297) ∗ (761.4 − 423) = 352 𝑘𝐽

𝑇2 761.4
∆𝑆 = 𝑚𝑐𝑝 ln ( ) = 1 ∗ (743 + 297) ∗ ln ( ) = 0.611 𝑘𝐽/𝐾
𝑇1 423
Example 9
A mass of 0.8 kg of air at 1 bar and 25°C is contained in a gas-tight frictionless piston-
cylinder device. The air is now compressed to a final pressure of 5 bar. During the process,
the heat is transferred from the air such that the temperature inside the cylinder remains
constant. Calculate the heat transferred and work done during the process and direction of
each in the process.
Given: 𝑚 = 0.8 𝑘𝑔, 𝑃1 = 1 𝑏𝑎𝑟, 𝑇1 = 25℃ = 298 𝐾, 𝑃2 = 5 𝑏𝑎𝑟, 𝑇1 = 𝑇2
Solution:
𝑃1 1
𝑄 = 𝑊 = 𝑚𝑅𝑇1 ln ( ) = 0.8 ∗ 287 ∗ 298 ∗ ln ( ) = −110.12 𝑘𝐽
𝑃2 5
First law applied to open systems
Open System

■ Control Volume & Control surface

■ 𝑄 = ∆𝐸 + 𝑊
■ 𝐸 = 𝐸𝐾 + 𝐸𝑃 + 𝑈
■ 𝑄 = ∆𝐸𝐾 + ∆𝐸𝑃 + ∆𝑈 + 𝑊

Steady flow process

■ Rates of flow of mass and energy across the control surface are constant – steady flow
process
■ Invariant with respect to time.

Mass Balance
■ 𝑚̇𝑖𝑛 = 𝑚̇𝑜𝑢𝑡 + 𝑚̇𝑠𝑡𝑜𝑟𝑒𝑑
■ If 𝑚̇𝑠𝑡𝑜𝑟𝑒𝑑 = 0, 𝑚̇𝑖𝑛 = 𝑚̇𝑜𝑢𝑡
𝐴1 𝑉1 𝐴2 𝑉2
■ =
𝑣1 𝑣2

■ 𝜌1 𝐴1 𝑉1 = 𝜌2 𝐴2 𝑉2
■ Continuity Equation
Flow work
■ Analogous to displacement work, ∫ 𝑝 𝑑𝑉 work
■ 𝑑𝑊𝑓𝑙𝑜𝑤 = 𝑝 𝑑𝑉
 ■ Where dV is the volume of the fluid element about to enter the system
■ 𝑑𝑊𝑓𝑙𝑜𝑤 = 𝑝 𝑣 𝑑𝑚

■ Flow work at inlet, (𝑑𝑊𝑓𝑙𝑜𝑤 )𝑖𝑛 = 𝑝1 𝑣1 𝑑𝑚1

■ Flow work at exit, (𝑑𝑊𝑓𝑙𝑜𝑤 )𝑜𝑢𝑡 = 𝑝2 𝑣2 𝑑𝑚2

■ Flow work per unit mass, 𝑑𝑊𝑓𝑙𝑜𝑤 = 𝑝𝑣

Energy Balance
■ Total work transfer, 𝑊 = 𝑊𝑥 − 𝑝1 𝑣1 𝑑𝑚1 + 𝑝2 𝑣2 𝑑𝑚2
𝑑𝑊 𝑑𝑊𝑥 𝑑𝑚1 𝑑𝑚2
■ In the rate form, = − 𝑝1 𝑣1 + 𝑝2 𝑣2
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
𝑑𝑊 𝑑𝑊𝑥
■ = − 𝑝1 𝑣1 𝑚̇1 + 𝑝2 𝑣2 𝑚̇2
𝑑𝑡 𝑑𝑡
𝑑𝑄 𝑑𝑊
■ 𝑚̇1 𝑒1 + = 𝑚̇2 𝑒2 +
𝑑𝑡 𝑑𝑡
𝑑𝑄 𝑑𝑊𝑥
■ 𝑚̇1 𝑒1 + = 𝑚̇2 𝑒2 + − 𝑝1 𝑣1 𝑚̇1 + 𝑝2 𝑣2 𝑚̇2
𝑑𝑡 𝑑𝑡

■ 𝑒 = 𝑒𝐾 + 𝑒𝑃 + 𝑢
𝑉2
■ 𝑒= + 𝑧𝑔 + 𝑢
2

𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
■ 𝑚̇1 ( + 𝑧1 𝑔 + 𝑢1 ) + 𝑝1 𝑣1 𝑚̇1 + = 𝑚̇2 ( + 𝑧2 𝑔 + 𝑢2 ) + 𝑝2 𝑣2 𝑚̇2 +
2 𝑑𝑡 2 𝑑𝑡

𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
■ 𝑚̇1 (𝑢1 + 𝑝1 𝑣1 + + 𝑧1 𝑔) + = 𝑚̇2 (𝑢2 + 𝑝2 𝑣2 + + 𝑧2 𝑔) +
2 𝑑𝑡 2 𝑑𝑡

𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
■ 𝑚̇1 (ℎ1 + + 𝑧1 𝑔) + = 𝑚̇2 (ℎ2 + + 𝑧2 𝑔) +
2 𝑑𝑡 2 𝑑𝑡
𝑑𝑚
■ Dividing by 𝑑𝑡

𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
■ ℎ1 + + 𝑧1 𝑔 + 𝑑𝑚 = ℎ2 + + 𝑧2 𝑔 +
2 2 𝑑𝑚

■ STEADY FLOW ENERGY EQUATION

𝑉2 2 −𝑉1 2
■ 𝑄 − 𝑊𝑥 = (ℎ2 − ℎ1 ) + + 𝑔(𝑍2 − 𝑍1 )
2

■ 𝑑𝑄 − 𝑑𝑊𝑥 = 𝑑ℎ + 𝑉 𝑑𝑉 + 𝑔𝑑𝑧
SFEE applied to Thermodynamic devices
❖ Nozzle
𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
❖ ℎ1 + + 𝑧1 𝑔 + 𝑑𝑚 = ℎ2 + + 𝑧2 𝑔 +
2 2 𝑑𝑚
𝑑𝑄 𝑑𝑊𝑥
❖ 𝑑𝑚
= 0, 𝑑𝑚
= 0, 𝑧2 − 𝑧1 = 0
 𝑉1 2 𝑉2 2
❖ ℎ1 + = ℎ2 +
2 2

❖ 𝑉1 < 𝑉2

❖ 𝑉1 2 ≪ 𝑉2 2
𝑉2 2
❖ ℎ1 = ℎ2 + 2

❖ 𝑉2 = √2(ℎ1 − ℎ2 )

❖ Diffuser
❖ 𝑉2 < 𝑉1

❖ 𝑉2 2 ≪ 𝑉1 2
𝑉1 2
❖ ℎ1 + = ℎ2
2

❖ 𝑉1 = √2(ℎ2 − ℎ1 )

Throttling Device
𝑑𝑄 𝑑𝑊𝑥
■ = 0, =0
𝑑𝑚 𝑑𝑚

𝑉1 2 𝑉2 2
■ ℎ1 + = h2 +
2 2

■ ℎ1 = h2
Turbine & Compressor
❖ Turbine
𝑑𝑄
❖ =0
𝑑𝑚

❖ 𝑧2 − 𝑧1 = 0
𝑉2 2 −𝑉1 2
❖ =0
2
𝑑𝑊𝑥
❖ ℎ1 = ℎ2 + 𝑑𝑚
𝑊𝑥
❖ = ℎ1 − ℎ2
𝑚

❖ Compressor
𝑊𝑥
❖ ℎ1 = ℎ2 − 𝑚
𝑊𝑥
❖ = ℎ2 − ℎ1
𝑚

Heat Exchanger
■ 𝑚̇ℎ ℎ1 + 𝑚̇𝑐 ℎ3 = 𝑚̇ℎ ℎ2 + 𝑚̇𝑐 ℎ4
 ■ 𝑚̇ℎ (ℎ1 − ℎ2 ) = 𝑚̇𝑐 (ℎ4 − ℎ3 )
Example 1
Air flows steadily at the rate of 0.5 kg/s through an air compressor, entering at 7 m/s velocity,
100 kPa pressure and 0.95 m3/kg volume and leaving at 5 m/s, 700 kPa and 0.19 m3/kg. The
internal energy of air leaving is 90 kJ/kg greater than that of air entering. Cooling water in the
compressor jacket absorbs heat from the air at the rate of 58 kW. (a) Compute the rate of
shaft work input to the air in kW. (b) Find the ratio of inlet pipe diameter to outlet pipe
diameter.
𝑚 𝑚3 𝑚
Given: 𝑉1 = 7 , 𝑃1 = 100 𝑘𝑃𝑎, 𝑣1 = 0.95 𝑘𝑔 , 𝑉2 = 5 , 𝑃2 = 700 𝑘𝑃𝑎,
𝑠 𝑠

𝑚3 𝑘𝐽 𝑘𝑔
𝑣2 = 0.19 , ∆𝑢 = 90 , 𝑚̇ = 0.5
𝑘𝑔 𝑘𝑔 𝑠
𝑑𝑊 𝑉1 2 −𝑉2 2 𝑑𝑄
Solution: = 𝑚̇ [(𝑢1 − 𝑢2 ) + (𝑝1 𝑣1 − 𝑝2 𝑣2 ) + ]+
𝑑𝑡 2 𝑑𝑡

𝑑𝑊 3 3 3
52 − 72
= 0.5 [−90 ∗ 10 + {(100 ∗ 10 ∗ 0.19) − (700 ∗ 10 ∗ 0.95)} + ] − 58000
𝑑𝑡 2
𝑑𝑊
= −122 𝑘𝑊
𝑑𝑡
𝐴1 𝑉1 𝐴2 𝑉2
𝑚̇ = =
𝑣1 𝑣2
𝜋 2
𝐴1 𝑉2 𝑣1 0.95 ∗ 5
= = 4 𝑑1
= 3.57 = 𝜋
𝐴2 𝑣2 𝑉1 0.19 ∗ 7 2
4 𝑑2
𝑑1
= √3.57 = 1.89
𝑑2
Example 2
In a steady flow apparatus, 135 kJ of work is done by each kg of fluid. The specific volume
of the fluid, pressure and velocity at the inlet are 0.37 m3/kg, 600 kPa and 16 m/s. The inlet is
32 m above the floor and the discharge is at the floor level. The discharge conditions are 0.62
m3/kg, 100 kPa and 270 m/s. The total heat loss between the inlet and discharge is 9 kJ/kg of
fluid. In flowing through this apparatus, does the specific internal energy increase or decrease
and by how much?
𝑚 𝑚3 𝑚
Given: 𝑉1 = 16 , 𝑃1 = 600 𝑘𝑃𝑎, 𝑣1 = 0.37 𝑘𝑔 , 𝑉2 = 270 , 𝑃2 = 100 𝑘𝑃𝑎,
𝑠 𝑠

𝑚3
𝑣2 = 0.62 𝑘𝑔 , 𝑧1 = 32 𝑚, 𝑧2 = 0, 𝑊 = 135 𝑘𝐽, 𝑄 = −9 𝑘𝐽

Solution:

𝑉1 2 𝑑𝑄 𝑉2 2 𝑑𝑊𝑥
𝑢1 + 𝑝1 𝑣1 + + 𝑧1 𝑔 + = 𝑢2 + 𝑝2 𝑣2 + + 𝑧2 𝑔 +
2 𝑑𝑚 2 𝑑𝑚
 (𝑉2 2 − 𝑉1 2 ) 𝑑𝑊𝑥 𝑑𝑄
(𝑢1 − 𝑢2 ) = (𝑝2 𝑣2 − 𝑝1 𝑣1 ) + + (𝑧2 − 𝑧1 )𝑔 + −
2 𝑑𝑚 𝑑𝑚
(2702 − 162 )
(𝑢1 − 𝑢2 ) = [(105 ∗ 0.62) − (600 ∗ 103 ∗ 0.37)] + + [(0 − 32) ∗ 9.81]
2
+ (135 ∗ 103 ) + (9 ∗ 103 ) = 𝟐𝟎. 𝟏𝟒 𝐤𝐉
Example 3
In a steam power station, steam flows steadily through a 0.2 m diameter pipeline from boiler
to the turbine. At the boiler end, the steam conditions are found to be: P = 4 MPa, T = 400⁰C,
h = 3213.6 kJ/kg and v = 0.073 m3/kg. At the turbine end, the conditions are found to be: P =
3.5 MPa, T = 392⁰C, h = 3202.6 kJ/kg and v = 0.084 m3/kg. There is a heat loss of 8.5 kJ/kg
from the pipeline. Calculate the steam flow rate.
Example 4
A certain water heater operates under steady flow conditions receiving 4.2 kg/s of water at
75⁰C, 313.93 kJ/kg. The water is heated by mixing with steam which is supplied to the heater
at 100.2 ⁰C and 2676 kJ/kg. The mixture leaves the heater as liquid water at 100⁰C and 419
kJ/kg. How much steam must be supplied to the heater per hour?
Example 5
In a gas turbine, gas enters at the rate of 5 kg/s with a velocity of 50 m/s and enthalpy of 900
kJ/kg and leaves the turbine with a velocity of 150 m/s and enthalpy of 400 kJ/kg. The loss of
heat from the gases to the surroundings is 25 kJ/kg. Assume R = 285 J/kgK and Cp=1004 J/kg
K. Determine the power output of the turbine and the diameter of inlet pipe. The inlet pipe
conditions are 100 kPa and 27⁰C.
Example 6
At the inlet to a CV nozzle the enthalpy of fluid passing is 3000 kJ/kg and the velocity is 60
m/s. At the discharge end, the enthalpy is 2757 kJ/kg, The nozzle is horizontal and the heat
loss during the flow is negligible. Find
a) Velocity of fluid at exit of the nozzle
b) If the inlet area is 0.1 m2 and the specific volume at the inlet is 0.187 m3/kg, find the
mass flow rate of fluid.
c) If the specific volume at the exit is 0.498 m3/kg, find the area at the exit of the nozzle.
Problems using first law of thermodynamics applied to closed systems
Example 1
Air initially at 60 kPa pressure, 800 K temperature and 0.1 m3 volume is compressed
isothermally until the volume is halved and subsequently the air is cooled at constant pressure
till the volume is halved again. Sketch the process on a p-v plane and Determine (a) total
work interaction (b) total heat interaction. Assume ideal gas behavior for air.
Given: 𝑃1 = 60 𝑘𝑃𝑎, 𝑇1 = 800 𝐾, 𝑉1 = 0.1 𝑚3 , 𝑇2 = 𝑇1 , 𝑉2 = 0.5𝑉1 = 0.05 𝑚3 ,
 𝑉3 = 0.5𝑉2 = 0.025 𝑚3
Solution:
Process 1-2 (Isothermal COMPRESSION)
𝑉2 0.05
𝑊12 = 𝑝1 𝑉1 𝑙𝑛 ( ) = 60 ∗ 103 ∗ 0.1 ∗ 𝑙𝑛 ( ) = −4.158 𝑘𝐽
𝑉1 0.1
𝑄12 = 𝑊12 = −4.158 𝑘𝐽
PROCESS 2-3 (ISOBARIC COMPRESSION)
𝑝2 𝑉2 = 𝑝1 𝑉1
𝑝1 𝑉1 60 ∗ 103 ∗ 0.1
𝑝2 = = = 120 𝑘𝑃𝑎
𝑉2 0.05
𝑊23 = 𝑝2 (𝑉3 − 𝑉2 ) = 120 ∗ 103 ∗ (0.025 − 0.05) = −3 𝑘𝐽
𝑝2 𝑉2 𝑝3 𝑉3
=
𝑇2 𝑇3
0.05 0.025
=
800 𝑇3
𝑇3 = 400 𝐾
𝑝1 𝑉1 60 ∗ 103 ∗ 0.1
𝑚= = = 0.0261 𝑘𝑔
𝑅𝑇1 287 ∗ 800
𝑄23 = 𝑚𝑐𝑝 (𝑇3 − 𝑇2 ) = 0.0261 ∗ 1005 ∗ (400 − 800) = −10.5𝑘𝐽

𝑊𝑛𝑒𝑡 = 𝑊12 + 𝑊23 = −4.158 − 3 = −7.158 kJ

𝑄𝑛𝑒𝑡 = 𝑄12 + 𝑄23 = −4.158 − 10.5 = −14.658 kJ
Example 2
1 kg of gas occupying 0.15 m3 at a pressure of 12 bar is heated at constant pressure until its
volume is 0.28 m3. The gas is then adiabatically expanded until its volume is 1.5 m3.
Calculate (a) temperature at the end of constant pressure heating and at the end of adiabatic
expansion (b) total work done. Take cv = 745 J/kg K and cp = 1068 J/kg K.
Given: 𝑚 = 1 𝑘𝑔, 𝑉1 = 0.15 𝑚3 , 𝑃1 = 12 𝑏𝑎𝑟, 𝑉2 = 0.28 𝑚3 , 𝑉3 = 1.5 𝑚3
Solution:
𝑅 = 𝑐𝑝 − 𝑐𝑣 = 1068 − 775 = 293 𝐽/𝑘𝑔𝐾

𝑝1 𝑉1 12 ∗ 105 ∗ 0.15
𝑇1 = = = 614 𝐾
𝑚𝑅 1 ∗ 293
𝑝1 𝑉1 𝑝2 𝑉2
=
𝑇1 𝑇2
 𝑉2 𝑇1 0.28 ∗ 614
𝑇2 = = = 1146 𝐾
𝑉1 0.15
𝑐𝑝 1068
𝛾= = = 1.38
𝑐𝑣 775

𝑇3 𝑉3 1−𝛾
=( )
𝑇2 𝑉2

𝑉3 1−𝛾 1.5 1−1.38

𝑇3 = 𝑇2 ( ) = 1146 ∗ ( ) = 601.65 𝐾
𝑉2 0.28
Process 1-2 (isobaric expansion)
𝑊12 = 𝑝1 (𝑉2 − 𝑉1 ) = 12 ∗ 105 ∗ (0.28 − 0.15) = 156 𝑘𝐽
PROCESS 2-3 (ADIABATIC EXPANSiON)
𝑊23 = 𝑚𝑅(𝑇3 − 𝑇2 ) = 1 ∗ 293 ∗ (601.65 − 1146) = 419.72 𝑘𝐽
𝑊𝑛𝑒𝑡 = 𝑊12 + 𝑊23 = 156 + 419.72 = 575.72 𝑘𝐽
Example 3
0.5 kg of air is compressed reversibly and adiabatically from 80 kPa and 60°C to 0.4 MPa
and is then expanded at constant pressure to the original volume. Sketch the process on p-v
and t-s diagrams. Compute work transfer, heat transfer and change in entropy for whole path.
Take R = 287 J/kg K and γ = 1.4.
Given: 𝑚 = 0.5 𝑘𝑔, 𝑃1 = 80 𝑘𝑃𝑎, 𝑇1 = 60℃ = 333 𝐾, 𝑃2 = 0.4 𝑀𝑃𝑎
Solution:
𝛾−1
𝑇2 𝑝2 𝛾
=( )
𝑇1 𝑝1
𝛾−1 1.4−1
𝑝2 𝛾 0.4 ∗ 106 1.4
𝑇2 = 𝑇1 ( ) = 333 ( ) = 527.41 𝐾
𝑝1 80 ∗ 103
𝑝2 𝑉2 𝑝3 𝑉3
=
𝑇2 𝑇3
80 400
=
527.41 𝑇3
𝑇3 = 1665 𝐾
𝑚𝑅(𝑇2 − 𝑇1 ) 0.5 ∗ 287 ∗ (527.41 − 333)
𝑊12 = = = −69.74 𝑘𝐽
1−𝛾 1−𝛾
𝑊23 = 𝑝2 (𝑉3 − 𝑉2 ) = 𝑚𝑅(𝑇3 − 𝑇2 ) = 0.5 ∗ 287 ∗ (1665 − 527.41) = 163.24 𝑘𝐽
𝑊𝑛𝑒𝑡 = 𝑊12 + 𝑊23 = −69.74 + 163.24 = 93.5 𝑘𝐽
 𝑄12 = 0
𝑄23 = 𝑚𝑐𝑝 (𝑇3 − 𝑇2 ) = 0.5 ∗ 1005 ∗ (1665 − 527.41) = 571.44 𝑘𝐽

𝑄𝑛𝑒𝑡 = 𝑄12 + 𝑄23 = 0 + 571.44 = 571.44 𝑘𝐽

∆𝑆12 = 0
𝑇3 1665
∆𝑆23 = 𝑚𝑐𝑝 𝑙𝑛 ( ) = 0.5 ∗ 1005 ∗ ln ( ) = 0.578 𝑘𝐽/𝐾
𝑇2 527.41
∆𝑆𝑛𝑒𝑡 = ∆𝑆12 + ∆𝑆23 = 0 + 0.578 = 0.578 𝑘𝐽/𝐾
Example 4
0.2 m3 of a mixture of fuel and air at 1.2 bar and 60°C is compressed till its pressure becomes
12 bar and 270°C. Then it is ignited suddenly at constant volume and its pressure becomes
twice the pressure at the end of compression. Find the maximum temperature reached and
change in internal energy. Also find the heat transfer during the compression process.
Consider the mixture as a perfect gas.
Given: 𝑉1 = 0.2 𝑚3 , 𝑃1 = 1.2 𝑏𝑎𝑟, 𝑇1 = 60℃ = 333 𝐾, 𝑃2 = 12 𝑏𝑎𝑟, 𝑇2 = 270℃ =
543 𝐾,
𝑃3 = 2𝑃2 = 24 𝑏𝑎𝑟, 𝑉2 = 𝑉3
𝑛−1
𝑇2 𝑝2 𝑛
Solution: 𝑇 = (𝑝 )
1 1

𝑛−1
𝑇2 𝑝2 𝑛
ln ( ) = ln ( )
𝑇1 𝑝1
𝑇2 𝑛−1 𝑝2
ln ( ) = ln ( )
𝑇1 𝑛 𝑝1
543 𝑛−1 12
ln ( )= ln ( )
333 𝑛 1.2
𝑛 = 1.27
𝑐𝑝 𝑐𝑝 1050 𝐽 𝐽
𝛾= 𝑐𝑣 = = = 750 𝑘𝑔𝐾 𝑅 = 𝑐𝑝 − 𝑐𝑣 = 1050 − 750 = 300 𝑘𝑔𝐾
𝑐𝑣 𝛾 1.4

𝑝1 𝑉1 1.2 ∗ 105 ∗ 0.2

𝑚= = = 0.24 𝑘𝑔
𝑅𝑇1 300 ∗ 333
𝑝2 𝑉2 𝑝3 𝑉3
=
𝑇2 𝑇3
𝑝3
𝑇3 = 𝑇2 = 2 ∗ 543 = 1086 𝐾
𝑝2
∆𝑈1−3 = 𝑚𝑐𝑣 (𝑇3 − 𝑇1 ) = 0.24 ∗ 750 ∗ (1086 − 333) = 135.67 𝑘𝐽
 𝑄1−2 = 𝑚𝑐𝑛 (𝑇2 − 𝑇1 )
𝑐𝑝 − 𝑛𝑐𝑣 1050 − (1.27 ∗ 750) 𝑘𝐽
𝑐𝑛 = = = −0.36
1−𝑛 (1 − 1.27) 𝑘𝑔𝐾
𝑄1−2 = 𝑚𝑐𝑛 (𝑇2 − 𝑇1 ) = 0.24 ∗ (−0.36) ∗ (543 − 333) = −14.2 𝑘𝐽

Example 5
A certain mass of air initially at a pressure of 480 kPa and at a temperature of 190°C is
expanded adiabatically to a pressure of 94 kPa. It is then heated at constant volume until it
attains its initial temperature when the pressure is found to be 150 kPa. State the type of
compression necessary to bring the system back to its original pressure and volume.
Determine (a) index of adiabatic expansion (b) work done per kg of air (c) change in specific
entropy of air. Take R = 290 J/kg K
Given: 𝑃1 = 480 𝑘𝑃𝑎, 𝑇1 = 190℃ = 463 𝐾, 𝑃2 = 94 𝑘𝑃𝑎, 𝑉2 = 𝑉3 , 𝑇3 = 𝑇1 , 𝑃3 =
150 𝑘𝑃𝑎
𝑛−1
𝑇2 𝑝2 𝑛
Solution: 𝑇 = (𝑝 )
1 1

𝛾−1
𝑇2 𝑝2 𝛾
ln ( ) = ln ( )
𝑇1 𝑝1
𝑇2 𝛾−1 𝑝2
ln ( ) = ln ( )
𝑇1 𝛾 𝑝1
290.14 𝛾−1 94
ln ( )= ln ( )
463 𝛾 480
𝛾 = 1.4
𝑝1 𝑉1 𝑝2 𝑉2
=
𝑇1 𝑇2
𝑝2 94
𝑇2 = 𝑇1 = ∗ 463 = 290.14 𝐾
𝑝1 480
𝑅(𝑇2 − 𝑇1 ) 290(290.14 − 463)
𝑤12 = = = 125.32 𝑘𝐽/𝑘𝑔
1−𝑛 1 − 1.4
𝑤23 = 0
𝑝3 150
𝑤31 = 𝑅𝑇1 ln ( ) = 290 ∗ 463 ∗ ln ( ) = −156.17 𝑘𝐽/𝑘𝑔
𝑝1 480
𝑤𝑛𝑒𝑡 = 𝑤12 + 𝑤23 + 𝑤31 = 125.32 + 0 − 156.17 = −30.85 𝑘𝐽/𝑘𝑔
∆𝑠12 = 0
 𝑇3 463 𝑘𝐽
∆𝑠23 = 𝑐𝑣 ln ( ) = 723 ln ( ) = 0.337
𝑇2 290.14 𝑘𝑔𝐾
𝑝2 150 𝑘𝐽
∆𝑠31 = 𝑅 ln ( ) = 290 ln ( ) = −0.337
𝑝1 480 𝑘𝑔𝐾
∆𝑠𝑐𝑦𝑐𝑙𝑒 = ∆𝑠12 + ∆𝑠23 + ∆𝑠31 = 0 + 0.337 − 0.337 = 0

Example 6
3 kg of air at a pressure of 150 kPa and temperature 360 K is compressed polytropically to
750 kPa and according to 𝑝 𝑣 1.2 = 𝑐. The gas is then cooled to initial temperature at p=c. The
air is then expanded at T = C, till it reaches original pressure of 150 kpa. Draw p-v diagram
and determine the net work and heat transfer.
Given: 𝑚 = 3 𝑘𝑔, 𝑃1 = 150 𝑘𝑃𝑎, 𝑇1 = 360 𝐾, 𝑃2 = 750 𝑘𝑃𝑎, 𝑇3 = 𝑇1 , 𝑝3 = 𝑝2 , 𝑝4 = 𝑝1
𝑛−1
𝑇2 𝑝2 𝑛
Solution: 𝑇 = (𝑝 )
1 1

𝑛−1 1.2−1
𝑝2𝑛 750 1.2
𝑇2 = 𝑇1 ( ) = 360 ( ) = 470.75 𝐾
𝑝1 150
𝑚𝑅(𝑇2 − 𝑇1 ) 3 ∗ 287 ∗ (470.75 − 360)
𝑊12 = = = −476.8 𝑘𝐽
1−𝑛 1 − 1.2
𝑊23 = 𝑝2 (𝑉3 − 𝑉2 ) = 𝑚𝑅(𝑇3 − 𝑇2 ) = 3 ∗ 287 ∗ (360 − 470.75) = −95.36 𝑘𝐽
𝑝3 750
𝑊31 = 𝑚𝑅𝑇1 ln ( ) = 3 ∗ 287 ∗ 360 ∗ ln ( ) = 494.86 𝑘𝐽
𝑝1 150
𝑊𝑛𝑒𝑡 = 𝑊12 + 𝑊23 + 𝑊31 = −476.8 − 95.36 + 494.86 = −73.5 𝑘𝐽
𝛾−𝑛 1.4 − 1.2
𝑄12 = 𝑊𝑝𝑜𝑙𝑦 = (−476.8) = −234.4 𝑘𝐽
𝛾−1 1.4 − 1
𝑄23 = 𝑚𝑐𝑝 (𝑇3 − 𝑇2 ) = 3 ∗ 1005 ∗ (360 − 470.75) = −334 𝑘𝐽

𝑄31 = 𝑊31 = 494.86 𝑘𝐽

𝑄𝑛𝑒𝑡 = 𝑄12 + 𝑄23 + 𝑄31 = −234.4 − 334 + 494.86 = −73.5 𝑘𝐽
Example 7
1 kg of gas expands reversibly according to linear law from 4.2 bar to 1.4 bar. The initial and
final volumes are 0.004 m3 and 0.02 m3 respectively. The gas is then cooled at constant
pressure and finally compressed isothermally back to its initial state of 4.2 bar and 0.004 m3.
Calculate the work done in each process stating its direction. Sketch the cycle on a p-V
diagram.
Given: 𝑚 = 1𝑘𝑔, 𝑃1 = 420 𝑘𝑃𝑎, 𝑃2 = 140 𝑘𝑃𝑎, 𝑉1 = 0.004 𝑚3 , 𝑉2 = 0.02 𝑚3 , 𝑃3 =
𝑃2 , 𝑇3 = 𝑇1
Solution: 𝑝 = 𝑎𝑉 + 𝑏 𝑃1 = 𝑎𝑉1 + 𝑏 𝑃2 = 𝑎𝑉2 + 𝑏
 0.004𝑎 + 𝑏 = 420000
0.02𝑎 + 𝑏 = 140000
On solving the above 2 equations
𝑎 = −17500 𝑘𝑃𝑎/𝑚3
𝑏 = 490 𝑘𝑃𝑎
𝑝 = −17500000 𝑉 + 490000

(𝑉2 2 − 𝑉1 2 )
𝑊12 = ∫(−17500000 𝑉 + 490000)𝑑𝑉 = [−17500000 + 490000(𝑉2 − 𝑉1 )]
2
= 4.48 𝑘𝐽
𝑝1 𝑉1 𝑝3 𝑉3
=
𝑇1 𝑇3
𝑝1 𝑉1 420
𝑉3 = = ∗ 0.004 = 0.012 𝑚3
𝑝3 140
𝑊23 = 𝑝2 (𝑉3 − 𝑉2 ) = 140 ∗ 103 ∗ (0.012 − 0.02) = −1.12 𝑘𝐽
𝑉1 0.004
𝑊31 = 𝑝1 𝑉1 ln ( ) = 420 ∗ 103 ∗ 0.004 ∗ ln ( ) = −1.845 𝑘𝐽
𝑉3 0.012
Example 8
A perfect gas undergoes a cycle comprises of three processes. It is first compressed
isothermally from 1 bar and 27⁰C to one eighth of its original volume. The energy is then
added at constant pressure increasing the temperature of gas and the cycle is completed by
𝐽 𝐽
isentropic expansion to original conditions. Take 𝑐𝑝 = 1250 𝑘𝑔𝐾 𝑎𝑛𝑑 𝑅 = 500 𝑘𝑔𝐾.
Calculate the maximum cycle temperature and pressure. Also find the net work transfer per
kg.
1
Given: 𝑝1 = 1 𝑏𝑎𝑟, 𝑇1 = 27℃ = 300 𝐾 = 𝑇2 , 𝑉2 = 8 𝑉1 , 𝑝2 = 𝑝3 , 𝑠1 = 𝑠3

Solution: 𝑐𝑣 = 𝑐𝑝 − 𝑅 = 1250 − 500 = 750 𝐽/𝑘𝑔𝐾

𝑐𝑝 1250
𝛾= = = 1.667
𝑐𝑣 750
𝑉2 1 𝑉1
𝑤12 = 𝑅𝑇1 ln ( ) = 500 ∗ 300 ∗ ln ( ) = − 312 𝑘𝐽/𝑘𝑔
𝑉1 8 𝑉1
𝑝1 𝑉1 𝑝2 𝑉2
=
𝑇1 𝑇2
𝑝1 𝑉1 1 ∗ 105 ∗ 8𝑉1
𝑝2 = = = 8 𝑏𝑎𝑟
𝑉2 𝑉1
 𝛾−1
𝑇3 𝑝3 𝛾
=( )
𝑇1 𝑝1
𝛾−1 1.667−1
𝑝3 𝛾 8 1.667
𝑇3 = 𝑇1 ( ) = 300 ∗ ( ) = 689.4 𝐾
𝑝1 1
𝑤23 = 𝑅(𝑇3 − 𝑇2 ) = 500 ∗ (689.4 − 300) = 194.6 𝑘𝐽/𝑘𝑔
𝑅(𝑇1 − 𝑇3 ) 500(300 − 689.4)
𝑤31 = = = 291.75 𝑘𝐽/𝑘𝑔
1−𝛾 1 − 1.667
𝑤𝑛𝑒𝑡 = 𝑤12 + 𝑤23 + 𝑤31 = −312 + 194.6 + 291.75 = 174.35 𝑘𝐽/𝑘𝑔
Example 9
Process 1: Air initially at 100 kPa and 50⁰C undergoes reversible adiabatic compression such
that its volume is reduced to one fifth of its initial volume
Process 2: 940 kJ/kg of heat is added to air at constant volume
Process 3: Process 2 is followed by a reversible adiabatic expansion upto initial volume
Process 4: Finally heat is rejected at constant volume so as to reach its initial condition
Draw the four processes on a p-V diagram. Determine the maximum temperature, net work
done and heat rejected per kg of air. Assume index of compression and expansion as 1.4 and
𝐽
𝑐𝑣 = 717 𝑘𝑔𝐾

1 𝑘𝐽
Given: 𝑃1 = 1 𝑏𝑎𝑟, 𝑇1 = 50℃ = 323 𝐾, 𝑉2 = 5 𝑉1 , 𝑉2 = 𝑉3 , 𝑠3 = 𝑠4 , 𝑉4 = 𝑉1 , 𝑞23 = 940 𝑘𝑔

𝑉 1−𝛾 1𝑉 1−1.4
Solution: 𝑇2 = 𝑇1 (𝑉2 ) = 323 (5 𝑉1 ) = 614.88 𝐾
1 1

𝑞23 = 𝑐𝑣 (𝑇3 − 𝑇2 ) = 717(𝑇3 − 614.88) = 940 ∗ 103

𝑇3 = 1925.9 𝐾

Unit 3 – Second law of thermodynamics

Heat Vs Work
 Joule’s experiment – conversion of work into heat.
 Conversion of entire heat into work – not possible
 When work is converted into heat W = Q
 When heat is converted into work, Q > W
 Work – high grade energy
 Heat – low grade energy
Cyclic heat engine

Energy Reservoirs
 Thermal energy reservoirs (TER)
 Source – where heat is received from
 Sink – where heat is rejected
 Mechanical Energy reservoirs (MER)
 Where work is stored (flywheel)
Kelvin Planck statement
It is impossible for a heat engine to produce net work in a complete cycle if it exchanges heat
only with the bodies at a single fixed temperature.
PMM2
If 𝑄2 = 0, the heat engine will produce net work in a complete cycle by exchanging heat with
only one reservoir, thus violating the Kelvin Planck statement. Such an engine is PMM2.
PMM2 is impossible.
Clausius’ statement
It is impossible to construct a device which, operating in a cycle, will produce no effect other
than the transfer of heat from a cooler to a hotter body.

Refrigerator
HEAT PUMP

Equivalence of Kelvin Planck and Clausius’ statements

Carnot cycle

Reversed Carnot Cycle

Example 1
A cyclic heat engine operates between a source temperature of 800⁰C and a sink temperature
of 30⁰C. What is the least rate of heat rejection per kW net output of the engine?
Given: 𝑇1 = 800℃ = 1073 𝐾, 𝑇2 = 30℃ = 303 𝐾, 𝑊 = 1 𝑘𝑊
𝑇2 303
𝜂 = 1− =1− = 0.718
𝑇1 1073
 𝑊 1000
𝜂=𝑄 = = 0.718
1 𝑄1

1000
𝑄1 = = 1392.76 𝑊
0.718
𝑊 = 𝑄1 − 𝑄2
1000 = 1392.76 − 𝑄2
𝑄2 = 392.76 𝑊
Example 2
A domestic food freezer maintains a temperature of -15⁰C. The ambient temperature is 30⁰C.
If heat leaks into the freezer at the continuous rate of 1.75 kJ/s, what is the least power
necessary to pump this heat out continuously?

Given: 𝑇2 = −15℃ = 258 𝐾, 𝑇1 = 30℃ = 303 𝐾, 𝑄2 =

1.75 𝑘𝐽/𝑠
Solution:
𝑇2 258
𝐶𝑂𝑃𝑅 = = = 5.73
𝑇1 − 𝑇2 303 − 258
𝑄2 1750
𝐶𝑂𝑃𝑅 = = = 5.73
𝑊 𝑊
1750
𝑊= = 305.41 𝐽/𝑠
5.73

Example 3
An engine manufacturer claims he has manufactured an engine which will produce 210 kW
of power, while taking in 0.5 kg/min of fuel of calorific value of 42000 kJ/kg. Further, he
states that the engine receives heat at 527⁰C and rejects heat at a temperature of 77⁰C. Find if
the claim of the manufacturer is true or false.

𝑘𝑔 0.5 𝑘𝑔 𝑘𝐽
Given: 𝑊 = 210 𝑘𝑊, 𝑚̇ = 0.5 𝑚𝑖𝑛 = 60
= 0.0083 𝑠
, 𝐶𝑉 = 42000 𝑘𝑔 ,

𝑇1 = 527℃ = 800 𝐾, 𝑇2 = 77℃ = 350 𝐾

Solution: 𝑄1 = 𝑚̇ ∗ CV = 0.0083 ∗ 42000 = 348.6 kW
𝑊 210
𝜂𝐻𝐸 = = = 0.6024 = 60.24 %
𝑄1 348.6
𝑇2 350
𝜂𝐶 = 1 − =1− = 0.5625 = 56.25 %
𝑇1 800
𝜂𝐶 < 𝜂𝐻𝐸
Since, the efficiency of Carnot engine is lesser than the efficiency of actual engine, the
manufacturer’s claim is FALSE.
Example 4
A reversed carnot cycle operating as a refrigerator has a refrigerating capacity of 100 kJ/s
while operating between temperature limits of -20⁰C and 35⁰C. Determine (a) power input
and (b) COP.If the system is used for heating purpose only, find its COP.What would be its
efficiency if it runs as an engine?

(a) Refrigerator: 𝑇1 = 35℃ = 308 𝐾, 𝑇2 = −20℃ = 253 𝐾, 𝑄2 =

100 𝑘𝐽/𝑠
𝑇2 253
Solution: 𝐶𝑂𝑃𝑅,𝑐𝑎𝑟 = 𝑇 −𝑇 = 308−253 = 4.6
1 2

𝑄2
𝐶𝑂𝑃𝑅,𝑐𝑎𝑟 =
𝑊
𝑄2 100 ∗ 1000
𝑊= = = 21.74 𝑘𝑊
𝐶𝑂𝑃𝑅,𝑐𝑎𝑟 4.6

(b) Heat Pump:

𝑇1 308
𝐶𝑂𝑃𝐻𝑃,𝑐𝑎𝑟 = = = 5.6
𝑇1 − 𝑇2 308 − 253
(c) Heat Engine:
𝑇2 253
𝜂 =1− =1− = 0.179 = 17.9 %
𝑇1 308

Example 5
A reversible heat engine operates between two reservoirs at 600⁰C and 40⁰C. The engine
drives a reversible refrigerator which operates between the same 40⁰C reservoir and a
reservoir at -18⁰C. The heat transfer to the engine is 2100 kJ and there is a net work output of
370 kJ from the combined plant. Evaluate the heat transfer to the refrigerator and the net heat
transfer to the 40⁰C reservoir.
Given: 𝑇1 = 600℃ = 873 𝐾, 𝑇2 = 40℃ = 313 𝐾, 𝑇3 = −18℃ = 255 𝐾, 𝑄1 = 2100 𝑘𝐽 𝑊𝑛𝑒𝑡 = 370 𝑘𝐽
𝑇 313 𝑊1 𝑊
Solution: 𝜂 = 1 − 𝑇2 = 1 − 873 = 0.642 = 64.2 % 𝜂= 𝑄1
1
= 2100 = 0.642 𝑊1 = 1348.2 𝑘𝐽
1

𝑊𝑛𝑒𝑡 = 𝑊1 − 𝑊2 = 1348.2 − 𝑊2 = 370 𝑊2 = 978.2 𝑘𝐽

𝑊1 = 𝑄1 − 𝑄2 𝑄2 = 𝑄1 − 𝑊1 = 2100 − 1348.2 = 751.8 𝑘𝐽
3 𝑇 255 𝑄
𝐶𝑂𝑃𝑅 = 𝑇 −𝑇 = 313−255 = 4.4 𝐶𝑂𝑃𝑅 = 𝑊3 𝑄3 = 𝐶𝑂𝑃𝑅 𝑊2 = 4.4 ∗ 978.2 = 4304.08 𝑘𝐽
2 3 2

𝑊2 = 𝑄4 − 𝑄3 𝑄4 = 𝑄3 + 𝑊2 = 4304.08 + 978.2 = 5282. 28 𝑘𝐽

Total heat supplied to the reservoir at 40⁰C,

𝑄𝑛𝑒𝑡 = 𝑄2 + 𝑄4 = 751.8 + 5282.28 = 6034.08 kJ

Causes of Irreversibility
 Lack of equilibrium during the process
 Heat transfer through a finite temperature difference
 Lack of pressure equilibrium within the interior of the system or
between system and surroundings
 Free expansion
 Involvement of dissipative effects
 Friction
 PMM3 – The continual motion of a movable device in the
complete absence of friction is known as PMM3
 Paddle wheel work transfer
 Transfer of electricity through a resistor
Heat Transfer through a finite temperature difference
Free Expansion

Friction

Paddle wheel Work Transfer

Transfer of electricity through a wire

Carnot’s Theorem

Corollary of Carnot’s Theorem

The efficiency of all reversible heat engines operating between the same
temperature levels is the same.
Absolute Thermodynamic Temperature Scale
Third Law of Thermodynamics
It is impossible by any procedure, no matter how idealized, to reduce any system to
the absolute zero of temperature in a finite number of operations.
Example 6
A reversible heat engine supplied heat from two constant temperature sources at 800 K and
400 K and rejects heat at a constant temperature sink at 200 K. If the engine executes a
number of cycles, while developing 100 kW and rejecting 3500 kJ of heat per minute.
Determine the heat supplied by each source per minute and efficiency of the engine.
Given: 𝑇1𝐴 = 800 𝐾, 𝑇1𝐵 = 400 𝐾, 𝑇2 = 200 𝐾,
𝑘𝐽
𝑊𝑛𝑒𝑡 = 100 𝑘𝑊 = 6000 𝑚𝑖𝑛 , 𝑄2 = 3500 𝑘𝐽/𝑚𝑖𝑛

Solution: 𝑄1 = 𝑊𝑛𝑒𝑡 + 𝑄2 = 6000 + 3500 = 9500 𝑘𝐽/𝑚𝑖𝑛

𝑄1𝐴 + 𝑄1𝐵 = 𝑄1
𝑄1𝐴 + 𝑄1𝐵 = 9500
𝑄1𝐴 𝑄1𝐵 𝑄2
+ =
𝑇1𝐴 𝑇1𝐵 𝑇2
𝑄1𝐴 𝑄1𝐵 3500
+ =
800 400 200
𝑄1𝐴 + 2𝑄1𝐵 = 14000
𝑘𝐽 𝑘𝐽
Solving these 2 equations, 𝑄1𝐴 = 5000 𝑚𝑖𝑛, 𝑄1𝐵 = 4500 𝑚𝑖𝑛
 𝑊𝑛𝑒𝑡 6000
𝜂= = = 0.631 = 63.1%
𝑄1 9500
Example 7
0.5 kg of air executes a Carnot cycle with thermal efficiency of 50%. The heat transfer to air
during isothermal expansion is 40 kJ. At the beginning of isothermal expansion, the pressure
and volume of air are 7 bar and 0.12 m3 respectively. Find the maximum and minimum
𝑘𝐽 𝑘𝐽
temperature of the cycle. Take 𝑐𝑝 = 1.008 𝑘𝑔𝐾 𝑎𝑛𝑑 𝑐𝑣 = 0.721 𝑘𝑔𝐾.

Given: 𝑚 = 0.5 𝑘𝑔, 𝜂 = 0.5, 𝑄1 = 40 𝑘𝐽, 𝑝1 = 7 𝑏𝑎𝑟, 𝑉1 = 0.12 𝑚3

Solution: 𝑅 = 𝑐𝑝 − 𝑐𝑣 = 1008 − 721 = 287 𝐽/𝑘𝑔𝐾

𝑝1 𝑉1 = 𝑚𝑅𝑇1
𝑝1 𝑉1 7 ∗ 105 ∗ 0.12
𝑇1 = = = 585.36 𝐾
𝑚𝑅 0.5 ∗ 287
𝑇2
𝜂 =1−
𝑇1
𝑇2
0.5 = 1 −
585.36
𝑇2 = 292.68 𝐾
Example 8
The efficiency of a Carnot engine is 20%. The efficiency gets doubled when the sink
temperature is reduced by 60⁰C. Estimate the source and sink temperatures.
Given: 𝜂1 = 0.2, 𝜂2 = 2𝜂1 = 0.4, 𝑇𝐿2 = 𝑇𝐿1 − 60
𝑇𝐿1
𝜂1 = 1 −
𝑇𝐻
𝑇𝐿1
1− = 0.2
𝑇𝐻
𝑇𝐿1 = 0.8𝑇𝐻
𝑇𝐿2
𝜂2 = 1 −
𝑇𝐻
𝑇𝐿1 − 60
𝜂2 = 1 −
𝑇𝐻
𝑇𝐿1 − 60 = 0.6𝑇𝐻
From the above 2 equations, 0.2𝑇𝐻 = 60
𝑇𝐻 = 300 𝐾
𝑇𝐿1 = 240 𝐾
 UNIT 4 – ENTEOPY AND EXERGY
Entropy
Two reversible Adiabatics cannot intersect

Any reversible path can be replaced by 2 reversible adiabatics and a reversible isotherm

Clausius’ Theorem
Entropy – a property

Clausius’ Inequality
Applications of Increase in entropy principle
• Every irreversible process is accompanied by increase in entropy
• This entropy increase quantifies the extent of irreversibility of the process
• Higher the entropy, higher the irreversibility
Transfer of heat through a finite temperature difference

Mixing of two fluids

• 𝑡2 < 𝑡𝑓 < 𝑡1

• 𝑚1 𝑐1 (𝑡1 − 𝑡𝑓 ) = 𝑚2 𝑐2 (𝑡𝑓 − 𝑡2 )

• 𝑚1 𝑐1 𝑡1 − 𝑚1 𝑐1 𝑡𝑓 = 𝑚2 𝑐2 𝑡𝑓 − 𝑚2 𝑐2 𝑡2
𝑚1 𝑐1 𝑡1 +𝑚2 𝑐2 𝑡2
• 𝑡𝑓 = 𝑚1 𝑐1 +𝑚2 𝑐2

𝑡 𝑑𝑄𝑟𝑒𝑣 𝑡 𝑚1 𝑐1 𝑑𝑇 𝑡
• ∆𝑆1 = ∫𝑡 𝑓 = ∫𝑡 𝑓 = 𝑚1 𝑐1 ln (𝑡𝑓 ) negative
1 𝑇 1 𝑇 1

𝑡 𝑑𝑄𝑟𝑒𝑣 𝑡 𝑚2 𝑐2 𝑑𝑇 𝑡
• ∆𝑆2 = ∫𝑡 𝑓 = ∫𝑡 𝑓 = 𝑚2 𝑐2 ln (𝑡𝑓 )
2 𝑇 2 𝑇 2

𝑡 𝑡
• ∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆1 + ∆𝑆2 = 𝑚1 𝑐1 ln (𝑡𝑓 ) + 𝑚2 𝑐2 ln (𝑡𝑓 )
1 2

𝑡1 +𝑡2
𝑡 2
If 𝑚1 = 𝑚2 = 𝑚 and 𝑐1 = 𝑐2 = 𝑐, ∆𝑆𝑢𝑛𝑖𝑣 = 𝑚𝑐 𝑙𝑛 (𝑡 𝑓𝑡 ) = 2𝑚𝑐 ln ( 2
)
1 2 √𝑡1 𝑡2
Maximum work obtainable from two finite bodies at temperatures T 1 and T2
• If two bodies are brought into thermal contact with no work output,
𝑇1 + 𝑇2
𝑇𝑓 =
2
• Lowest attainable final temperature will deliver the maximum possible work.
• When both bodies attain 𝑇𝑓 , the engine stops operating.

• 𝑄1 = 𝐶𝑝 (𝑇1 − 𝑇𝑓 )

• 𝑄2 = 𝐶𝑝 (𝑇𝑓 − 𝑇2 )

• 𝑊 = 𝑄1 − 𝑄2 = 𝐶𝑝 (𝑇1 + 𝑇2 − 2𝑇𝑓 )
𝑇 𝑑𝑇 𝑇
• ∆𝑆1 = ∫𝑇 𝑓 𝐶𝑝 = 𝐶𝑝 ln ( 𝑇𝑓 )
1 𝑇 1

𝑇 𝑑𝑇 𝑇
• ∆𝑆2 = ∫𝑇 𝑓 𝐶𝑝 𝑇
= 𝐶𝑝 ln ( 𝑇𝑓 )
2 2

• ∆𝑆𝑢𝑛𝑖𝑣 ≥ 0
𝑇 𝑇
• 𝐶𝑝 ln ( 𝑇𝑓 ) + 𝐶𝑝 ln ( 𝑇𝑓 ) ≥ 0
1 2

𝑇 2
• 𝐶𝑝 𝑙𝑛 (𝑇 𝑓𝑇 ) ≥ 0
1 2

𝑇 2
• For 𝑇𝑓 to be minimum, 𝐶𝑝 𝑙𝑛 (𝑇 𝑓𝑇 ) = 0
1 2

• 𝐶𝑝 ≠ 0
𝑇 2
• 𝑙𝑛 (𝑇 𝑓𝑇 ) = 0 = ln (1)
1 2

𝑇𝑓 2
• =1
𝑇1 𝑇2

• 𝑇𝑓 2 = 𝑇1 𝑇2

• 𝑇𝑓 = √𝑇1 𝑇2
2
• 𝑊𝑚𝑎𝑥 = 𝐶𝑝 (𝑇1 + 𝑇2 − 2√𝑇1 𝑇2 ) = 𝐶𝑝 (√𝑇1 − √𝑇2 )

Maximum work obtainable from a finite body and a TER

𝑇 𝑑𝑇 𝑇
• ∆𝑆𝑏𝑜𝑑𝑦 = ∫𝑇 0 𝐶𝑝 = 𝐶𝑝 ln ( 𝑇0)
𝑇
𝑄−𝑊
• ∆𝑆𝑇𝐸𝑅 = 𝑇0

𝑇 𝑄−𝑊
• ∆𝑆𝑢𝑛𝑖𝑣 = 𝐶𝑝 ln ( 𝑇0) + 𝑇0
 • ∆𝑆𝑢𝑛𝑖𝑣 ≥ 0
𝑇 𝑄−𝑊
• 𝐶𝑝 ln ( 𝑇0) + ≥0
𝑇0

𝑇 𝑄−𝑊
• 𝐶𝑝 ln ( 𝑇0) ≥ 𝑇0

𝑊−𝑄 𝑇
• ≤ 𝐶𝑝 ln ( 𝑇0)
𝑇0

𝑇
• 𝑊 ≤ 𝑄 + 𝑇0 𝐶𝑝 ln ( 𝑇0)
𝑇 𝑇 𝑇
• 𝑊𝑚𝑎𝑥 = 𝑄 + 𝑇0 𝐶𝑝 ln ( 𝑇0 ) = 𝐶𝑝 (𝑇 − 𝑇0 ) + 𝑇0 𝐶𝑝 ln ( 𝑇0) = 𝐶𝑝 [(𝑇 − 𝑇0 ) + 𝑇0 ln ( 𝑇0)]

Processes exhibiting external mechanical irreversibility

• Isothermal dissipation of work
𝑄=𝑊
𝑄 𝑊
∆𝑆𝑠𝑢𝑟𝑟 = =
𝑇 𝑇
∆𝑆𝑠𝑦𝑠 = 0
𝑊
∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑢𝑟𝑟 + ∆𝑆𝑠𝑦𝑠 =
𝑇

• Adiabatic Dissipation of work

∆𝑆𝑠𝑢𝑟𝑟 = 0
𝑓 𝑓 𝑐 𝑑𝑇 𝑇𝑓
𝑑𝑄 𝑝
∆𝑆𝑠𝑦𝑠 = ∫ =∫ = 𝑐𝑝 ln ( )
𝑖 𝑇 𝑖 𝑇 𝑇𝑖
𝑇𝑓
∆𝑆𝑢𝑛𝑖𝑣 = ∆𝑆𝑠𝑢𝑟𝑟 + ∆𝑆𝑠𝑦𝑠 = 𝑐𝑝 ln ( )
𝑇𝑖
Entropy transfer
• Entropy transfer in the form of heat transfer and mass flow.
• Energy transfer in the form of heat transfer, mass flow and work transfer.
• Entropy transfer is recognized at the system boundary.
• Entropy interaction in a closed system is only because of heat transfer.
• For an adiabatic closed system, entropy transfer is zero.
• Heat transfer – increases the internal energy of the system, as a result of
which the kinetic energy of the molecules increases – and disorder of the
system increases.

No entropy transfer with work

• Work delivered to flywheel where energy is stored in fully recoverable form.
• Flywheel molecules are put into rotation around the axis in a perfectly
organized manner
• Work is “entropy free”.
• First law makes no distinction between work and heat transfer – treated as
EQUALS.
• Second law makes the distinction clear –
• Energy interaction accompanied by entropy transfer is heat transfer
and energy interaction not accompanied by entropy transfer is work
transfer
• Only energy is exchanged during work interaction whereas both energy
and entropy are exchanged during heat interaction.
Entropy transfer associated with mass flow
• Mass contains entropy as well as energy.
• When mass is doubled, so is entropy and energy.
• Entropy and energy are carried into or out of the system by streams of matter
and is therefore proportional to the mass flow rate.
• Entropy of the system increases by “ms” when “m” amount of mass enters it
Entropy generation in a closed system
• Entropy of a closed can be increased by
• Heat interaction in which there is entropy transfer
• Internal irreversibility's or dissipative effects in which work is dissipated
into internal energy increase
𝑑𝑄
• 𝑑𝑆 = 𝑑𝑒 𝑆 + 𝑑𝑖 𝑆 = + 𝑑𝑖 𝑆
𝑇
𝑑𝑄
• 𝑑𝑆 ≥ 𝑇

• 𝑑𝑖 𝑆 ≥ 0
𝑑𝑄
• 𝑑𝑆 = + ∆𝑆𝑔𝑒𝑛
𝑇

• ∆𝑆𝑠𝑦𝑠 = ∆𝑆𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 + ∆𝑆𝑔𝑒𝑛

• For a reversible process, 𝑑𝑄𝑅 = 𝑑𝑈𝑅 + 𝑝 𝑑𝑉

• For an irreversible process, 𝑑𝑄𝐼 = 𝑑𝑈𝐼 + 𝑑𝑊
• 𝑑𝑈𝑅 = 𝑑𝑈𝐼
• 𝑑𝑄𝑅 − 𝑝 𝑑𝑉 = 𝑑𝑄𝐼 − 𝑑𝑊
𝑑𝑄 𝑑𝑄 𝑝 𝑑𝑉−𝑑𝑊
• (𝑇) =(𝑇) +
𝑅 𝐼 𝑇

Entropy generation in an open system

Example 1
Water flows through a turbine in which friction causes the water temperature to rise
from 35⁰C to 37⁰C. If there is no heat transfer, how much does the entropy of water
change in passing through the turbine?
Given: 𝑇1 = 35℃ = 308 𝐾, 𝑇2 = 37℃ = 310 𝐾
𝑇
Solution: 𝑑𝑆 = 𝑚𝑐𝑣 ln (𝑇2 )
1

310
𝑑𝑆 = 1 ∗ 4187 ∗ ln ( ) = 0.0243 𝑘𝐽/𝐾
308
Example 2
(a) 1 kg of water at 273 K is brought into contact with a heat reservoir at 373 K.
When the water has reached 373 K, find the entropy change of the water, of
the heat reservoir and of the universe.
(b) If water is heated from 273 K to 373 K by first bringing it in contact with a
reservoir at 323 K and then with a reservoir at 373 K, what will the entropy
change of the universe be?
(c) Explain how water might be heated from 273 K to 373 K with almost no
change in the entropy of the universe.
Example 3
1 kg of ice at -5⁰C is exposed to the atmosphere which is at 20 ⁰C. The ice melts and
comes into thermal equilibrium with the atmosphere.
Determine the entropy increase of the universe.
cp of ice is 2.093 kJ/kg K and the latent heat of ice is 333.3 kJ/kg.
Example 4
A system has a capacity at constant volume 𝐶𝑣 = 𝐴𝑇 2 where 𝐴 = 0.042 𝐽/𝐾 3 . The
system is originally at 200 K, and a thermal reservoir at 100 K is available. What is
the maximum amount of work that can be recovered as the system is cooled down to
the temperature of the reservoir?
 Unit 5 – Thermodynamic relations and Ideal gas mixtures
IDEAL GAS MIXTURES
Mass & mole fractions
Consider a closed system of gas, which is composed of ‘k’ components, each of
which is a pure substance.
𝑖=𝑘

𝑚 = 𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘 = ∑ 𝑚𝑖
𝑖=1

Mass Fraction: The ratio of the mass of a component to the mass of the mixture is
referred to as mass fraction. (x)
𝑚𝑖 𝑚𝑖
𝑥𝑖 = = 𝑖=𝑘
𝑚 ∑𝑖=1 𝑚𝑖

Total number of moles of a mixture

𝑖=𝑘

𝑛 = 𝑛1 + 𝑛2 + 𝑛3 + 𝑛4 +. . . +𝑛𝑘 = ∑ 𝑛𝑖
𝑖=1

Mole Fraction: The ratio of the number of moles of a component to the total number
of moles of the mixture is referred to as mole fraction. (y)
𝑛𝑖 𝑛𝑖
𝑦𝑖 = = 𝑖=𝑘
𝑛 ∑𝑖=1 𝑛𝑖
𝑖=𝑘

∑ 𝑥𝑖 = 1
𝑖=1
𝑖=𝑘

∑ 𝑦𝑖 = 1
𝑖=1

Relation connecting mass, mole number and molecular mass,

𝑚
𝑛=
𝑀
Mass of each component can be expressed as, 𝑚𝑖 = 𝑛𝑖 𝑀𝑖
𝑖=𝑘

𝑚 = ∑ 𝑛𝑖 𝑀𝑖
𝑖=1

𝑚 ∑𝑖=𝑘
𝑖=1 𝑚𝑖 ∑𝑖=𝑘
𝑖=1 𝑛𝑖 𝑀𝑖
Apparent or Average molecular weight of the mixture, 𝑀 = = = =
𝑛 𝑛 𝑛
∑𝑖=𝑘
𝑖=1 𝑦𝑖 𝑀𝑖
Dalton’s law of partial pressures
 Partial pressure of ith component in a gas mixture is defined as
𝑛𝑖 𝑅𝑢 𝑇
𝑝𝑖 =
𝑉
𝑛𝑅𝑢 𝑇
𝑉=
𝑝
𝑛𝑖 𝑅𝑢 𝑇 𝑛𝑖
𝑝𝑖 = 𝑝 = 𝑝 = 𝑦𝑖 𝑝
𝑛𝑅𝑢 𝑇 𝑛
 Total pressure of the mixture is defined as
(𝑛1 + 𝑛2 + 𝑛3 + 𝑛4 +. . . +𝑛𝑘 )𝑅𝑢 𝑇
𝑝=
𝑉
𝑛1 𝑅𝑢 𝑇 𝑛2 𝑅𝑢 𝑇 𝑛3 𝑅𝑢 𝑇
𝑝= + + +⋯
𝑉 𝑉 𝑉
𝑝 = 𝑝1 + 𝑝2 + 𝑝3 + ⋯ + 𝑝𝑘

𝑝 = ∑ 𝑝𝑖

Amagat’s law of additive volumes

 Partial volume of ith component in a gas mixture is defined as
𝑛𝑖 𝑅𝑢 𝑇
𝑉𝑖 =
𝑝
𝑛𝑅𝑢 𝑇
𝑝=
𝑉
𝑛𝑖 𝑅𝑢 𝑇 𝑛𝑖
𝑉𝑖 = 𝑉 = 𝑉 = 𝑦𝑖 𝑉
𝑛𝑅𝑢 𝑇 𝑛
 Total volume of the mixture is defined as
(𝑛1 + 𝑛2 + 𝑛3 + 𝑛4 +. . . +𝑛𝑘 )𝑅𝑢 𝑇
𝑉=
𝑝
𝑛1 𝑅𝑢 𝑇 𝑛2 𝑅𝑢 𝑇 𝑛3 𝑅𝑢 𝑇
𝑉= + + +⋯
𝑝 𝑝 𝑝
𝑉 = 𝑉1 + 𝑉2 + 𝑉3 + ⋯ + 𝑉𝑘

𝑉 = ∑ 𝑉𝑖
Density of gas mixture
𝑉 𝑉
Specific volume of gas mixture is defined as, 𝑣 = 𝑚 = 𝑚
1 +𝑚2 +𝑚3 +𝑚4 +...+𝑚𝑘

1 𝑚1 𝑚2 𝑚3 𝑚𝑘
= + + +⋯+
𝑣 𝑉 𝑉 𝑉 𝑉
1 1 1 1 1
= + + + ⋯+
𝑣 𝑣1 𝑣2 𝑣3 𝑣𝑘
1
𝜌=
𝑣

𝜌 = 𝜌1 + 𝜌2 + 𝜌3 + ⋯ + 𝜌𝑘 = ∑ 𝜌𝑖

Gas constant of gas mixture

𝑝𝑖 𝑉 = 𝑛𝑖 𝑅𝑢 𝑇
𝑚𝑖
𝑛𝑖 =
𝑀𝑖
𝑚𝑖
𝑝𝑖 𝑉 = 𝑅 𝑇
𝑀𝑖 𝑢
𝑅𝑢
𝑅𝑖 =
𝑀𝑖
𝑝𝑖 𝑉 = 𝑚𝑖 𝑅𝑖 𝑇
Therefore, for each constituent,
𝑝1 𝑉 = 𝑚1 𝑅1 𝑇
𝑝2 𝑉 = 𝑚2 𝑅2 𝑇
𝑝𝑘 𝑉 = 𝑚𝑘 𝑅𝑘 𝑇
𝑝𝑉 = (𝑚1 𝑅1 + 𝑚2 𝑅2 +. . +𝑚𝑘 𝑅𝑘 )𝑇
𝑝𝑉 = 𝑚𝑅𝑇
(𝑚1 𝑅1 + 𝑚2 𝑅2 +. . +𝑚𝑘 𝑅𝑘 )
𝑅= = ∑ 𝑥𝑖 𝑅𝑖
𝑚
Example 1
A vessel of volume 0.4 m3 contains 0.45 kg of carbon monoxide and 1 kg of air at 15⁰C.
Calculate the partial pressure of each constituents and the total pressure in the vessel. The
air contains 23.3% oxygen and 76.7% nitrogen by mass.
Example 2
A volumetric analysis of gaseous mixture gives the following results:
𝐶𝑂2 = 12.0% 𝑂2 = 4.0%
𝑁2 = 82.0% 𝐶𝑂 = 2.0%
Determine the analysis of gas mixture on the mass basis, the molecular weight and the gas
constant on the mass basis for the gas mixture.

Example 3
The gravitational analysis of air is 23.14% oxygen, 75.53% nitrogen, 1.28% argon
and 0.05% carbon dioxide. Calculate the volumetric analysis and the partial pressure
of each constituent in the mixture, when the total pressure is 1 bar.
Example 4
A vessel contains a gaseous mixture of composition by volume 80% hydrogen, 20%
carbon monoxide. It is designed that the mixture should be made in the proportion
50% hydrogen and 50% carbon monoxide by removing some of the mixture and
adding some carbon monoxide. Calculate per kmol of mixture the mass of the
mixture to be removed and the mass of carbon monoxide to be added. The pressure
and temperature in the vessel remain constant during the procedure.

Example 5
A mixture of gases contains 1.2 kg of oxygen and 1.8 kg of nitrogen. The pressure
and temperature of the mixture are 350 kPa and 300 K. Determine for mixture,
(a) Mass and mole fraction of each constituent gas
(b) Average molecular weight
 (c) The partial pressures
(d) The specific gas constant
(e) The volume and
(f) The density

Properties of gas mixture – gibbs theorem

“The internal energies, enthalpies and specific heats etc. of a gas mixture are
respectively equal to sum of internal energies, enthalpies and specific heats etc. of
individual components, each at temperature and volume of the mixture.”

U = 𝑈1 + 𝑈2 + 𝑈3 + 𝑈4 +. . . +𝑈𝑘 = ∑ 𝑈𝑖

𝑚𝑢 = 𝑚1 𝑢1 + 𝑚2 𝑢2 + 𝑚3 𝑢3 + ⋯ + 𝑚𝑘 𝑢𝑘 = ∑ 𝑚𝑖 𝑢𝑖

𝑚1 𝑢1 + 𝑚2 𝑢2 + 𝑚3 𝑢3 + ⋯ + 𝑚𝑘 𝑢𝑘
𝑢=
𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘
𝑚1 𝑢1 𝑚2 𝑢2 𝑚3 𝑢3 𝑚𝑘 𝑢𝑘
𝑢= + + + ⋯+ = ∑ 𝑥𝑖 𝑢𝑖
𝑚 𝑚 𝑚 𝑚

𝑢̅ = ∑ 𝑦𝑖 𝑢̅𝑖

H = 𝐻1 + 𝐻2 + 𝐻3 + 𝐻4 +. . . +𝐻𝑘 = ∑ 𝐻𝑖

𝑚ℎ = 𝑚1 ℎ1 + 𝑚2 ℎ2 + 𝑚3 ℎ3 + ⋯ + 𝑚𝑘 ℎ𝑘 = ∑ 𝑚𝑖 ℎ𝑖

𝑚1 ℎ1 + 𝑚2 ℎ2 + 𝑚3 ℎ3 + ⋯ + 𝑚𝑘 ℎ𝑘
ℎ=
𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘
 𝑚1 ℎ1 𝑚2 ℎ2 𝑚3 ℎ3 𝑚𝑘 ℎ𝑘
ℎ= + + + ⋯+ = ∑ 𝑥𝑖 ℎ𝑖
𝑚 𝑚 𝑚 𝑚

ℎ̅ = ∑ 𝑦𝑖 ℎ̅𝑖

S = 𝑆1 + 𝑆2 + 𝑆3 + 𝑆4 +. . . +𝑆𝑘 = ∑ 𝑆𝑖

𝑚𝑠 = 𝑚1 𝑠1 + 𝑚2 𝑠2 + 𝑚3 𝑠3 + ⋯ + 𝑚𝑘 𝑠𝑘 = ∑ 𝑚𝑖 𝑠𝑖

𝑚1 𝑠1 + 𝑚2 𝑠2 + 𝑚3 𝑠3 + ⋯ + 𝑚𝑘 𝑠𝑘
𝑠=
𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘
𝑚1 𝑠1 𝑚2 𝑠2 𝑚3 𝑠3 𝑚𝑘 𝑠𝑘
𝑠= + + +⋯+ = ∑ 𝑥𝑖 𝑠𝑖
𝑚 𝑚 𝑚 𝑚

𝑠̅ = ∑ 𝑦𝑖 𝑠̅𝑖

𝑚𝑐𝑣 = 𝑚1 𝑐𝑣1 + 𝑚2 𝑐𝑣2 + 𝑚3 𝑐𝑣3 + ⋯ + 𝑚𝑘 𝑐𝑣𝑘 = ∑ 𝑚𝑖 𝑐𝑣𝑖

𝑚1 𝑐𝑣1 + 𝑚2 𝑐𝑣2 + 𝑚3 𝑐𝑣3 + ⋯ + 𝑚𝑘 𝑐𝑣𝑘

𝑐𝑣 =
𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘
𝑚1 𝑐𝑣1 𝑚2 𝑐𝑣2 𝑚3 𝑐𝑣3 𝑚𝑘 𝑐𝑣𝑘
𝑐𝑣 = + + + ⋯+ = ∑ 𝑥𝑖 𝑐𝑣 𝑖
𝑚 𝑚 𝑚 𝑚

𝑐̅𝑣 = ∑ 𝑦𝑖 ̅̅̅̅
𝑐𝑣 𝑖

𝑚𝑐𝑝 = 𝑚1 𝑐𝑝1 + 𝑚2 𝑐𝑝2 + 𝑚3 𝑐𝑝3 + ⋯ + 𝑚𝑘 𝑐𝑝𝑘 = ∑ 𝑚𝑖 𝑐𝑝𝑖

𝑚1 𝑐𝑝1 + 𝑚2 𝑐𝑝2 + 𝑚3 𝑐𝑝3 + ⋯ + 𝑚𝑘 𝑐𝑝𝑘

𝑐𝑝 =
𝑚1 + 𝑚2 + 𝑚3 + 𝑚4 +. . . +𝑚𝑘
𝑚1 𝑐𝑝1 𝑚2 𝑐𝑝2 𝑚3 𝑐𝑝3 𝑚𝑘 𝑐𝑝𝑘
𝑐𝑝 = + + + ⋯+ = ∑ 𝑥𝑖 𝑐𝑝 𝑖
𝑚 𝑚 𝑚 𝑚

𝑐̅𝑝 = ∑ 𝑦𝑖 ̅̅̅̅
𝑐𝑝 𝑖

Example 6
A mixture of ideal gases consists of 5 kg of nitrogen and 6 kg of carbon dioxide at a
pressure of 4 bar and a temperature of 27⁰C. Find
(a) The mole fraction of each constituents
(b) The equivalent molecular weight of the mixture
(c) The equivalent gas constant of the mixture
(d) The partial pressures and partial volumes
(e) The volume and density of mixture
 (f) The cp and cv of the mixture
If the mixture is heated at constant volume to 60⁰C, find the change in internal
energy, enthalpy and entropy of the mixture. Take 𝛾 for carbon dioxide as 1.286 and
that for nitrogen as 1.4.
(a) Mole fraction of each constituent
𝑚𝑖
𝑛𝑖 =
𝑀𝑖
𝑚𝑁2 5
𝑛𝑁2 = = = 0.178
𝑀𝑁2 28
𝑚𝐶𝑂2 6
𝑛𝐶𝑂2 = = = 0.136
𝑀𝐶𝑂2 44

𝑛 = 𝑛𝑁2 + 𝑛𝐶𝑂2 = 0.178 + 0.136 = 0.312

𝑛𝑁2 0.178
𝑦𝑁2 = = = 0.57
𝑛 0.312
𝑛𝐶𝑂2 0.136
𝑦𝐶𝑂2 = = = 0.43
𝑛 0.312
(b) Equivalent Molecular weight of mixture,
𝑀 = ∑ 𝑦𝑖 𝑀𝑖 = 𝑦𝑁2 𝑀𝑁2 + 𝑦𝐶𝑂2 𝑀𝐶𝑂2 = (0.57 ∗ 28) + (0.43*44)=34.88 kg/kmol
𝑅𝑢 8314.4
(c) Apparent gas constant of the mixture, 𝑅 = = = 238.37 𝐽/𝑘𝑔𝐾
𝑀 34.88

(d) Partial pressures and partial volumes,

𝑝𝑁2 = 𝑦𝑁2 𝑝 = 0.57 ∗ 4 = 2.28 𝑏𝑎𝑟

𝑝𝐶𝑂2 = 𝑦𝐶𝑂2 𝑝 = 0.43 ∗ 4 = 1.72 𝑏𝑎𝑟

𝑚𝑅𝑇 11 ∗ 238.37 ∗ 300
𝑉= = = 1.967 𝑚3
𝑝 4 ∗ 105
𝑉𝑁2 = 𝑦𝑁2 𝑉 = 0.57 ∗ 1.967 = 1.121 𝑚3

𝑉𝐶𝑂2 = 𝑦𝐶𝑂2 𝑉 = 0.43 ∗ 1.967 = 0.846 𝑚3

(e) Volume and density of the mixture

𝑉 = 1.967 𝑚3
𝑚 11
𝜌= = = 5.59 𝑘𝑔/𝑚3
𝑉 1.967
(f) cp and cv of the mixture
𝑅𝑢 8314.4
𝑐𝑣𝑁2 = = = 742.36 𝐽/𝑘𝑔𝐾
𝑀𝑁2 (𝛾𝑁2 − 1) 28(1.4 − 1)
 𝑅𝑢 8314.4
𝑐𝑣𝐶𝑂2 = = = 660.71 𝐽/𝑘𝑔𝐾
𝑀𝐶𝑂2 (𝛾𝐶𝑂2 − 1) 44(1.286 − 1)
𝑚𝑁2 𝑐𝑣𝑁2 + 𝑚𝐶𝑂2 𝑐𝑣𝐶𝑂2 (5 ∗ 742.36) + (6 ∗ 660.71)
𝑐𝑣 = = = 697.82 𝐽/𝑘𝑔𝐾
𝑚𝑁2 + 𝑚𝐶𝑂2 11

𝑐𝑝𝑁2 = 𝛾𝑁2 𝑐𝑣𝑁2 = 1.4 ∗ 742.36 = 1039.3 𝐽/𝑘𝑔𝐾

𝑐𝑝𝐶𝑂2 = 𝛾𝐶𝑂2 𝑐𝑣𝐶𝑂2 = 1.286 ∗ 660.71 = 849.67 𝐽/𝑘𝑔𝐾

𝑚𝑁2 𝑐𝑝𝑁2 + 𝑚𝐶𝑂2 𝑐𝑝𝐶𝑂2 (5 ∗ 1039.3) + (6 ∗ 849.67)

𝑐𝑝 = = = 935.87 𝐽/𝑘𝑔𝐾
𝑚𝑁2 + 𝑚𝐶𝑂2 11

(g) Change in internal energy, ∆𝑈 = 𝑚𝑐𝑣 ∆𝑇 = 11 ∗ 697.82 ∗ (333 − 300) = 253.31 𝑘𝐽

(h) Change in enthalpy, ∆𝐻 = 𝑚𝑐𝑝 ∆𝑇 = 11 ∗ 935.87 ∗ (333 − 300) = 339.72 𝑘𝐽
𝑇 333
(i) Change in entropy, ∆𝑆 = 𝑚𝑐𝑣 ln (𝑇2) = 11 ∗ 697.82 ∗ ln (300) = 801.07 𝐽/𝐾
1

Example 7
In an engine cylinder, a gas has volumetric analysis of 13% CO2, 12.5% O2 and
74.5% N2. The temperature at the beginning of expansion is 1050⁰C and gas mixture
expands reversibly through a volume ratio 8:1 according to the law 𝑝𝑣 1.2 = 𝑐.
Calculate per kg of gas:
(a) The work done
(b) The heat flow
(c) The change of entropy per kg of mixture
The value of cp for constituents CO2, O2 and N2 are 1.235 kJ/kg K, 1.088 kJ/kg K and
1.172 kJ/kg K respectively.

Constituen 𝒏𝒊 𝑴𝒊 , 𝒌𝒈 𝒎𝒊 = 𝒙𝒊 Cpi Ri 𝒙𝒊 Cpi 𝒙𝒊 𝐑i

ts /𝒌𝒎𝒐𝒍 𝒏𝒊 𝑴𝒊(k = 𝒎𝒊 (kJ/kg (J/kg (kJ/kg (J/kg
g) /𝒎 K) K) K) K)

CO2 0.13 44 5.72 0.18 1.235 188.9 0.231 35.34

7 6

O2 0.12 32 4.00 0.13 1.088 259.8 0.143 34.04

5 1 3

N2 0.74 28 20.86 0.68 1.172 296.9 0.799 202.5

5 2 4 1

𝑇𝑜𝑡𝑎𝑙 1 - 30.58 1 - - 1.173 271.8

9
 𝑘𝐽
𝑐𝑝 = ∑ 𝒙𝒊 Cpi = 1.173
𝑘𝑔𝐾
𝐽
𝑅 = ∑ 𝒙𝒊 Ri = 271.89
𝑘𝑔𝐾
𝑘𝐽 𝐽
𝑐𝑣 = 𝑐𝑝 − 𝑅 = 1.173 − 0.27189 = 0.90111 = 901.11
𝑘𝑔𝐾 𝑘𝑔𝐾

𝑣1 𝑛−1 1 1.2−1
𝑇2 = 𝑇1 ( ) = 1323 ( ) = 872.85 𝐾
𝑣2 8

𝑅(𝑇2 − 𝑇1 ) 271.89(872.85 − 1323) 𝑘𝐽

𝑤= = = 611.74
1−𝑛 1 − 1.2 𝑘𝑔
𝑘𝐽
∆𝑢 = 𝑐𝑣 (𝑇2 − 𝑇1 ) = 0.90 ∗ (872.85 − 1323) = −405.13
𝑘𝑔
kJ
𝑞 = ∆𝑢 + w = −405.13 + 611.74 = 206.60
kg
𝑇2 𝑣2 872.85 𝑘𝐽
∆𝑆 = 𝑐𝑣 ln ( ) + 𝑅 ln ( ) = [0.90 ∗ ln ( )]+= [0.2713 ∗ ln(8)] = 0.1896
𝑇1 𝑣1 1323 𝑘𝑔𝐾

Adiabatic mixing at constant volume

Adiabatic mixing of 2 gas streams