Unit II

Ideal Gas and Second law of Thermodynamics

Thermodynamics
Prof. V. H. Bansode
Department of Mechanical Engineering
Smt. Kashibai Navale College of Engineering, Pune-41
 Ideal and Real Gases
• Real Gas: The behavior of all gases at high
pressure and at low temperatures is different. All
these gases are called Real gases e.g. air, oxygen,
hydrogen etc.
• Ideal or Perfect Gas: The experimental results
have shown that all real gases tend to behave
similarly at very low pressures (as the pressure
approaches to zero) and at high temperatures
where the volume approaches to infinity.

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 Ideal Gases

Behave as described by the ideal gas equation;

no real gas is actually ideal
Within a few %, ideal gas equation describes
most real gases at room temperature and
pressures of 1 atm or less
In real gases, particles attract each other
reducing the pressure
Real gases behave more like ideal gases as
pressure approaches zero.

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 Boyle’s Law

 Pressure and volume are

inversely related at constant
temperature.

 PV = C

 As one goes up, the other

goes down.
“Father of Modern Chemistry”
Robert Boyle  P1V1 = P2V2
Chemist & Natural Philosopher
Listmore, Ireland
January 25, 1627 – December 30, 1690
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 Boyle’s Law

Boyle’s Law: P1V1 = P2V2

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 Boyle’s Law

Boyle’s Law: P1V1 = P2V2

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 Charles’ Law

 Volume of a gas varies

directly with the absolute
temperature at constant
pressure.

 V = CT

 V1 / T1 = V2 / T2
Jacques-Alexandre Charles
Mathematician, Physicist, Inventor
Beaugency, France
November 12, 1746 – April 7, 1823 7
 Charles’ Law

Charles’ Law: V1/T1 = V2/T2

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 Charles’ Law

Charles’ Law: V1/T1 = V2/T2

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 Avogadro’s Law

At constant temperature

and pressure, the volume of
a gas is directly related to
the number of moles.
V = C n
V1 / n1 = V2 / n2
Amedeo Avogadro
Physicist
Turin, Italy
August 9, 1776 – July 9, 1856
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 Avogadro’s Law

Avogadro’s Law: V1/n1=V2/n2

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 Gay- Lussac Law

 At constant volume,
pressure and absolute
temperature are
directly related.

 P = CT

 P1 / T1 = P2 / T2
Joseph-Louis Gay-Lussac
Experimentalist
Limoges, France
December 6, 1778 – May 9, 1850
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The Ideal Gas Equation of State
 The Ideal Gas Equation of State

Combine these relationships into a single fundamental equation

• We have four relationships
of state - the ideal gas equation of state
– V  1/P; Boyle’s Law
– V  T; Charles’ Law   J
– P  T Gay-Lussac's Law PV  n R T , R  8.314
K mole
– V  n; Avogadro’s Law Avagdro ' s dis cov ered that V
is same for all gases at the same pressure & temp.
 m
PV  n R T n 
M
 
m RT R
PV  R
M M

J
PV  mRT , R characteristic Gas Cons tan t 16
Kg K
 The Definition of an Ideal Gas

•An ideal gas is a gas that obeys totally the ideal

gas law over its entire P-V-T range

•Ideal gases – molecules have negligible

intermolecular attractive forces and they occupy a
negligible volume compared with the container
volume
 Standard Temperature and Pressure

STP (Standard Temperature and Pressure)

• Temperature - 0.00 °C = 273.15 K
• Pressure - 1.000 atm
• The volume occupied by 1.000 mole of an ideal
gas at STP is 22.41 L!
SATP (Standard Ambient Temperature and
Pressure)
• Temperature - 25.00 °C = 273.15 K
• Pressure - 1.000 bar (105 Pa)
• The volume occupied by 1.000 mole of an
ideal gas at SATP is 24.78 L!
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 Thermodynamic Processes

• States of a thermodynamic system can be changed by

interacting with its surrounding through work and heat. When
this change occurs in a system, it is said that the system is
undergoing a process.

• A thermodynamic cycle is a sequence of different processes that

begins and ends at the same thermodynamic state.

• Some sample processes:

 Constant-volume process, v=C
 Isobaric process: pressure is constant, P=C
Isothermal process: temperature is constant T=C
Isentropic process: entropy is constant, s=C
 Adiabatic process: no heat transfer, Q=0
 Process-1: Isothermal Process

 Isothermal process: T=constant

Energy balance U=Q-W, for ideal gas U=H=0
since both are functions of temperature only
mRT 2 dV
Q=W, W=  PdV   dV  mRT 
V 1 V

V  P 
 mRT ln  2   mRT ln  1 
 V1   P2 
 Isobaric process: P=constant
2
U=Q-W, W=  PdV=P  dV=P(V2  V1 )
1

Q  U  P (V2  V1 )  (U 2  U1 )  P (V2  V1 )
 (U 2  PV2 )  (U1  PV1 )  H 2  H1  H
Process-2: Constant volume process
Process-3: Adiabatic process
 Constant volume process: V=constant
Q-W=U, W=  PdV  0, no work done

Q=U=mu=m  c dT v

 Adiabatic process: Q=0

Q-W=U, -W=U
- W=dU (infinitesimal increment of work and energy)
 mRT 
dU+PdV=0, mc v dT    dV  0
 V 
 RT  cv dT dV
cv dT    dV  0,  , integrate and assume
 V  R T V
c v =constant
Rc k 1
cv  T2   V2  T2  V1  v  V1 
ln     ln   ,    
R  T1   V1  T1  V2   V2 
 Process-3: Adiabatic process

k 1
T2  V1 
  , from ideal gas relation
T1  V2 
 V1   T1  P2
PV=RT,      , substitute
 V2   T2  P1
k 1 k 1
T2   T1   P2    T2 
    , multiply   from both sides
T1   T2   P1    T1 
( k 1) k
T2  P2  k  P2   V1 
  , and   
T1  P1   P1   V2 
k k  cons tan t
k
Also PV
1 1  PV
2 2 and pV
For an ideal gas undergoing adiabatic process
 Process-4: Polytropic process

Polytropic Process: its P-V relation can be expressed as

PVn = constant, where n is a constant for a specific process
 Isothermal, T=constant, if the gas is an ideal gas then PV=RT=constant, n=1
 Isobaric, P=constant, n=0 (for all substances)
 Constant-volume, V=constant, V=constant(P)(1/n), n= (for all substances)
 Adiabatic process, n=k for an ideal gas

PV
1 1
n
 PV
2 2
n
 PV n

2 2
W   PdV   ( PV
1 1
n
)V n
dV
1 1
2
2 2  PV
n
( PV
1 1 ) PV
1 1 
n 1 n 1 n
 ( PV n
) V dV  (V2  V1 )  1 1

1
1  n 1 n
 1. Heating a gas at constant volume
( Isochoric Process)
Let 1 kg of gas be heated at constant
volume and let the change in entropy and
absolute temperature be from s1 to s2 and
T1 to T2 respectively.
Then
Q = cv (T2 – T1)
Differentiating to find small increment of
heat dQ corresponding to small rise
in temperature dT
dQ  cv dT
2. Heating a gas at constant pressure ( Isobaric Process)

Let 1 kg of gas be heated at constant

pressure and let the change in entropy and
absolute temperature be from s1 to s2 and
T1 to T2 respectively.
Then

Q = cp (T2 - T1)
Differentiating to find small increment of heat
dQ corresponding to small rise in temperature dT

dQ  cpdT
3.Constant Temperature (Isothermal Process)
4. Adiabatic Process (Reversible)
Isentropic process
s = constant
 Ideal Gas Properties
Processes Isobaric Isochoric Isothermal Adiabetic
Quantity Constant δP = 0 δV = 0 δT = 0 δQ = 0

n 0 ͚ 1 n=γ=Cp/Cv

First Law δU = Q - W δU = Q δU = 0 δU = -W
W=0 Q=W Q=0

Work W P1(V1-V2) 0
P1.V1.ln(V2/V1) (P1V1-P2V2) / (γ-1)

Heat transfer Q m.Cp.(T2-T1) m.Cv.(T2-T1) 0

P1.V1.ln(V2/V1)

Internal Energy m.Cv.(T2-T1) m.Cv.(T2-T1) m.Cv.(T2-T1)

dU o

Enthalpy dH m.Cp.(T2-T1) m.Cp.(T2-T1) 0 m.Cp.(T2-T1)

Entropy Change m.Cp.ln(T2/T1) m.Cv.ln(T2/T1) 0
dS m.R.ln(v2/v1) 30
 IInd Law Of Thermodynamics

• Heat reservoir:
• A body of infinite heat capacity which is capable of
absorbing or rejecting an unlimited quantity of heat
without suffering its temperature.
• E.g. large bodies of water such as ocean, lakes or rivers, ponds
• The atmosphere
• A two phase mixture where it can absorb or reject its latent heat
Heat source or heat sink:
• A heat reservoir which supplies heat to a system is
called the heat source.
• A heat reservoir which absorbs heat from the system is
called heat sink. 31
Heat Engines:

• A cyclic device which can produce the work

continuously (i.e. which operates on cyclic
processes) at the expense of heat input is called a
heat engine.
• E.g. Steam engine, steam turbine, petrol and
diesel engines, gas turbines, etc,..

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 IInd Law Of Thermodynamics

Heat Engine
T1=source

Qs
boundary

Work
(W)

Qr Qs- Qr = W
T2Sink
thermal = Net work
output/(total heat input) 33
REFRIGERATOR:

• Refrigerator is a cyclic device which removes

heat from a body at low temperature and reject
to a body at high temperature usually
atmosphere at the expense of input energy.

• E.g. Refrigerator, Cold storages, Car Air

conditioning system etc,..
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REFRIGERATOR:

Atmosphere
Q1 T1

Wnet=Q1- Q2

Ref
Q2

Q2 Heat leakage in to
refrigerator
SinceT1>T2
T2 Evaporator 35
 REFRIGERATOR:

Coefficient of Performance
Refrigerators/Air conditioners

Cooling Effect
COPR / AC 
Work Input

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HEAT PUMP:
• Heap pump is a cyclic device which transfers
heat from a body at low temperature to a body
at high temperature at the expense of input
energy.

• E.g. Air conditioning system etc,..

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HEAT PUMP:

Room Atmosphere
Heat leaks from
T1
Room to atm.
SinceT1>T2
Q1
Wnet=Q1- Q2

Q2

Atmosphere
T2
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 IInd Law Of Thermodynamics

HEAT PUMP:

Coefficient of Performance for

Heat Pumps
Heating Effect
COPhp 
Work Input

1 1

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 Statements of IInd Law Of
Thermodynamics

1) Kelvin Planks Statement:

1) Kelvin Planks Statement:

“ It is impossible for a heat engine to produce net
work in a complete cycle, if it exchanges heat with
single reservoir”
PMM II: Perpetual Motion M/C of IInd Kind

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 Statements of IInd Law Of
Thermodynamics
1) Clausius Statement:

“ Heat cannot flow from lower temperature body to a

body at higher temperature . Some work must be
spend to achieve this.”
PMM II: Perpetual Motion M/C of IInd Kind

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 Carnot Cycle

• Composed of four internally reversible

processes.
– Two isothermal processes
– Two adiabatic processes

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 Carnot Cycle

Assumption:
• Working medium is perfect gas & has
const. specific heat
• All processes are reversible
•Piston & Cylinder does not create any
friction during motion
•Heat transfer does not affect the temp. of
source & sink

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Carnot cycle

1 2
H

L 4 3

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Thermal efficiency of Carnot cycle is,

TH – TL T1 – T3
th = or
TH T1
TL
= 1–
TH

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