Fundamentals of Thermodynamics

Part 2
Ashok Kumar Nallathambi, Prof.E.Specht
Institute of Fluid Dynamics and Thermodynamics
Otto-von-Guericke-University, Magdeburg 39106, Germany
April 28, 2008

Equivalence of Kelvin-Plank and Clausius statements

Kelvin-Planks and Clausiuss statements are two parallel statements of the second law and are
equivalent in all aspects. The violation of the one statement implies the violation of the second,
and vice-versa.

Reversibility and Irreversibility

A reversible process is one which is performed in such a way that at the conclusion of the process,
both the system and the surroundings may be restored to their initial states, without producing
any changes in the rest of the universe. A reversible process is carried out infinitely slowly (takes
infinite time) with an infinitesimal gradient, so that every state passed through by the system
is an equilibrium state. Any natural process carried out with a finite gradient is an irreversible
process. All spontaneous process are irreversible. If the time allowed for a process to occur is
infinitely large, even though the gradient is finite, the process becomes reversible.

2.1

Causes of irreversibility

Lack of equilibrium during the process : The lack of mechanical, thermal and chemical
equilibrium between the system and its surroundings,or between two systems, or tow parts
of the same system, causes a spontaneous change which is irreversible. eg: (a) heat transfer
through a finite temperature difference, (b) lack of pressure equilibrium within the interior
of the system or between the system and the surroundings, and (c) free expansion.
Involvement of dissipative effects: If the work done on the system without producing an
equivalent increase in the kinetic or potential energy of the system and it only increases
the molecular internal energy (U ), will increase the irreversibility of the system. eg: (a)
friction, (b) paddle wheel work transfer, and (c) transfer of electricity through a resistor.

2.2

PMM3

The continual motion of a movable device in the complete absence of friction is known as perpetual motion machine of the third kind. Unlike PMM2, PMM3 violates both the Kelvin-Plank
and Clausius statements.

2.3

Conditions for irreversibility

A process will be reversible when it is performed in such a way that the system is at all times
infinitesimally near a state of thermodynamic equilibrium and in the absence of dissipative effect
of any form. Reversible processes are, therefore, purely ideal, limiting cases of actual processes.

Carnot cycle

A Carnot cycle is an ideal hypothetical, reversible cycle in which following four reversible
processes occur:
1. A reversible isothermal heat addition(Q1 ) process
2. A reversible adiabatic work delivering (WT ) process
3. A reversible isothermal heat rejecting (Q2 ) process
4. A reversible adiabatic work consuming (WP ) process
From the 1st law,
Q1 Q2 = WT WP
= 1

Q2
Q1

(1)
(2)

A reversible Carnot engine (E) can also act as a reversed heat engine (). The reversed Carnot
engine is none other than the reversible heat pump of reversible refrigerator.

Carnots Theorem

Carnot theorem states that of all the heat engines operating between a given constant temperature source and a given constant temperature sink, none has a higher efficiency than a reversible
engine.
Corollary: The efficiency of all reversible heat engines operating between the same temperature levels is the same.
The efficiency of a reversible engine is independent of the nature or amount of working
substance undergoing the cycle.

Absolute thermodynamic temperature scale

Kelvin proposed a relation

Q1
T1
=
Q2
T2

(3)

where T is known as absolute thermodynamic temperature. The Kelvin temperature scale is

independent of the peculiar characteristics of any particular substance.

Fowler-Guggenheim statement of Third Law of Thermodynamics

It is impossible by any procedure, no matter how idealized, to reduce any system to the absolute
zero of temperature (0 K or -273.16o C) in a finite number of operations.

Efficiency of the reversible heat engine

Using Kelvin temperature relation, the efficiency of the reversible heat engine can be rewritten
as:
 
Q2
T2
rev = max = 1
= 1
(4)
Q1 rev
T1
Similarly, COP of the reversible refrigerator and heat pump can be given as:

[COPrefr ]rev =

T2
T1 T2

(5)

[COPHP ]rev =

T1
T1 T2

(6)

Types of Irreversibility

Two types of irreversibility can be given as:

1. Internal irreversibility : due to internal dissipative effects like friction, turbulence, electrical
resistance, magnetic hysteresis, etc. with in the system.
2. External irreversibility : refers to the irreversibility occurring at the system boundary
like heat interaction with the surroundings due to finite temperature gradient, pressure
gradient, etc.

Important points
Two constant property lines can never intersect each other in a thermodynamic property
plot.

 Through one point in a thermodynamic property plot, there can pass only one reversible
adiabatic.
Any reversible path may be substituted by a reversible zigzag path, between the same end
states, consisting of a reversible adiabatic followed by a reversible isotherm and then by
a reversible adiabatic, such that the heat transferred during the isothermal process is the
same as that transferred during the original process.

10

Clausius theorem

It states that the cyclic integral of dQ/T for a reversible cycle is equal to zero.
I
dQ
= 0
R T

(7)

For a single reversible process,

Z

Q
d
= dS
R T
where S is the entropy which is an extensive property of a system.
Definition for Entropy:

(8)

1. Simplistic: Entropy is the portion of heat that can not be converted into useful mechanical
work.
2. Entropy is a measure of the degree of molecular disorder existing in the system.
Entropy is a point function. Therefore, entropy change in an any irreversible process can be
determined from the reversible process. The area under the T S plot gives the heat transfer
in a process.

11

Clausius Inequality

Cyclic integral of d
Q/T for any irreversible or reversible cycle is less less than or equal to zero.
ie,
I
dQ
0
(9)
T
H
If dQ = 0, the cycle is reversible.
T

H
If dTQ < 0, the cycle is irreversible and possible.
H
If dTQ > 0, the cycle is impossible because it will violate 2n d Law.
Clausius inequality for a process process can be given as
dS

Q
d
T

for a reversible process, dS = dTQ and for an irreversible process, dS > dTQ
4

(10)

12

Entropy principle

Entropy of an isolated system always increases, it never decrease. Entropy of an isolated system
/ universe can be given as
dSuniv 0 = dSsys + dSsurr 0

(11)

When the system reaches equilibrium, the entropy of the system reaches its maximum. some of
the applications of the entropy principle can be given as
1. Heat transfer through a finite temperature difference:
T1 T2
Suniv = Q12
T1 T2
2. Mixing of two fluids :

Suniv = m1 c1 ln

Tf
T1


+ m2 c2 ln

Tf
T2

if m1 = m2 = m and c1 = c2 = c,

Suniv = 2 m c ln

T1 + T2

2 T1 T2

3. Maximum work obtainable from two finite bodies at temp. T1 and T2 as

p
p 2
Wmax = cp
T1 T2
4. Maximum work obtainable from a finite body (at T ) and thermal energy reservoir (TER)
at (To ) as

 
T
Wmax = cp (T To ) To ln
To

13

Entropy generation in a closed system

If the system and surrounding interact through heat transfer, the entropy change of the system
can be given as
dQ
dS = de S + di S =
+ di S
(12)
T
where de S is the entropy increase due to external irreversibility and di S is due to internal irreversibility and also called as internal entropy generation. But di S 0.
The second law states that, in general, any thermodynamic process is accompanied by entropy
generation.
Z 2
dQ
S2 S1
=
Sgen
(13)
| {z }
|{z}
T
1
| {z }
entropy change
entropy production
entropy transfer

Heat transfer is always accompanied with an en entropy transfer. And also, Sgen 0.
Even though entropy is a point function, entropy generation is not a point function. Entropy
generation is a path function and it is not a property of a system. The amount of entropy
generation quantifies the irreversibility of the process.
5

14

Free energy

The part of the low grade energy which is available for conversion is referred as available energy (exergy) and the part which, according to the second law, must be rejected, is known as
unavailable energy (anergy). The maximum available energy is known as free energy.
Helmholtz free energy function: = U T S
Gibbs free energy function: G = H T S

15

Ideal gas equation

T at all pressures and temperatures is called

A hypothetical gas which obeys the law p v = R
can be determined from
as an ideal gas. The universal gas constant (R)

=
=

1.01325 105 N/m2 22.4 m3 /Kg mol

273.15 K
8.3143 KJ/Kg mol K

(14)

The molar volume (

v ) can be replaced by the total volume (V ) using v = V /n, therefore
T
pV = nR

(15)

where n is the number of moles and it is defined as the ratio between the mass of the gas (m)
and the molecular weight of the gas (). using n = m/, Eq. 15 becomes
pV

R
T

mRT

(16)

where R is the characteristic gas constant and R = R .

The total number of molecules (N ) in the gas can be given as N = n A. where A is the
Avogadros number and is equal to 6.023 1026 molecules/Kg mol.
The Boltzmann constant(K) is defined as the ratio between the universal gas constant and
Avogadros number.

R
K =
= 1.38 1023 J/molecule K
(17)
A
Finally,
pV

=
=

mRT
NKT

(18)

The specific heat and gas constant and related as

cp =

R
,
1

cv =

R
1

and =

cp
cv

(19)