ENTROPY

Classsius Inequality
To develop a relation for the definition of entropy, let us examine Eq. 7–2 more closely. Here
we have a quantity whose cyclic integral is zero.
To perform the integration in Eq. 7–5, one needs to know the relation between Q and T during a
process. This relation is often not available, and the integral in Eq. 7–5 can be performed for a
few cases only. For the majority of cases we have to rely on tabulated data for entropy. Note
that entropy is a property, and like all other properties, it has fixed values at fixed states.
Therefore, the entropy change S between two specified states is the same no matter what path,
reversible or irreversible, is followed during a process .Also note that the integral of dQ/T gives
us the value of entropy change only if the integration is carried out along an internally reversible
path between the two states. The integral of dQ/T along an irreversible path is not a property,
and in general, different values will be obtained when the integration is carried out along
different irreversible paths. Therefore, even for irreversible processes, the entropy change
should be determined by carrying out this integration along some convenient imaginary
internally reversible path between the specified states.
A Special Case: Internally Reversible Isothermal Heat
Transfer Processes
Entropy is an extensive property, and thus the total
entropy of a system is equal to the sum of the
entropies of the parts of the system. An isolated
system may consist of any number of subsystems (Fig.
7–6). A system and its surroundings, for example,
constitute an isolated system since both can be
enclosed by a sufficiently large arbitrary boundary
across which there is no heat, work, or mass transfer
(Fig. 7–7). Therefore, a system and its surroundings
can be viewed as the two subsystems of an isolated
system, and the entropy change of this isolated system
during a process is the sum of the entropy changes of
the system and its surroundings, which is equal to the
entropy generation since an isolated system involves
no entropy transfer.
The increase of entropy principle does not imply
that the entropy of a system cannot decrease.
The entropy change of a system can be negative
during a process but entropy generation cannot.
The increase of entropy principle can be
summarized as follows:
EXAMPLE 7–2 Entropy Generation during
Heat Transfer
Processes
A heat source at 800 K loses 2000 kJ of heat
to a sink at (a) 500 K and (b) 750 K.
Determine which heat transfer process is
more irreversible.

dS=(δQ)/T + Sgen
dS=Entropy change, (δQ)/T=Entropy Transport
Sgen=Entropy generation
δQ>0 when heat is added to the system
δQ<0 when system loses heat
δQ=0 There is no heat transfer(adibatic process)
Sgen=0 (internal reversible process)
Sgen>0 (irreversible process)
dS can be Positive ,negative or zero
dS=0 S=C (isentropic process)
 Determination of Entropy for closed system
when working fluid is air.
• dS=((δQ)/T)int rev or TdS= δQ for internal reversible Process
• δQ=dU+PdV (For closed stationary Compressible system)
• TdS=dU+PdV
• TdS=mCvdT+PdV
• dS=mCv(dT/T)+(P/T)dV
• Now PV=mRT or P/T=mR/V
• dS=mCv(dT/T)+mR(dV/V)
• Integrating between state 1 and state 2
• S2-S1=mCv ln(T2/T1) +mR ln(V2/V1)
• For Isothermal Process (T2=T1)
• S2-S1=mR ln(V2/V1)
dS=((δQ)/T)int rev or TdS= δQ for internal reversible Process
Now H=U+PV dH=dU+PdV+VdP dH= δQ+VdP
dH=TdS+VdP TdS=dH-VdP TdS=CpdT-VdP
dS=Cp(dT/T)-(V/T)dP dS=Cp(dT/T)-R(dP/P)
For Constant Pressure Process P=Constant dP=0
S2-S1=Cpln(T2/T1)
For Throttling Process H=Constant and dH=0
TdS=0-VdP
dS=-(V/T)dP dS=-(R/P)dP S2-S1=-Rln(P2/P1)
For Polytrophic Process

δQ=CndT here Cn=polytropic specific heat Cn=(γ-n)/(1-n)*Cv

TdS=(γ-n)/(1-n)*CvdT dS=(γ-n)/(1-n)*Cv(dT/T)

S2-S1=(γ-n)/(1-n)*Cvln(T2/T1)

For Incompressible solid V=Constant dV=0 Cp=Cv=C

S2-S1=Cln(T2/T1)
 Some Important Points with regard to
Entropy
• System always move in that direction in which Energy get degraded
Quality wise or Entropy of Universe increase.This is also known as law of
degradation of energy.
• Entropy of system may decrease but entropy of Isolated system as well as
entropy of Universe always increase.
• Entropy change of system=Entropy transport(due to heat transfer)
+Entropy Generation(due to internal factors like Friction,Free expansion
and mixing of two or more fluids)
• There is no formula to calculate Entropy Generation but effect of entropy
generation is on the property change of system either volume change,
pressure change or Temperature Change.
• So Irreversible process is substituted by hypothetical reversible process
and Entropy Change is computed for this hypothetical reversible process
and this is the entropy change for irreversible Process.
Hint S2-S1=Cpln(T2/T1)=4.187ln((273+37)/(273+35))

=0.027100 KW/Kg k
Entropy change due to heat transfer due to
finite temperature difference.
Mixing of two fluids
Q-W=dU
During Mixing Q=0 W=0 dU=0 U(initial)=U(final)
U1+U2=U3 m1+m2=m3 m1CvT1+m2CvT2=(m1+m2)CvTf
m1(T1-Tf)=m2(Tf-T2) Tf=(m1T1+m2T2)/(m1+m2)
For m1=m2=m Tf=m(T1+T2)/2m Tf=(T1+T2)/2
(ΔS)universe= (ΔS)A+ (ΔS)B
(ΔS)A=mCvln(Tf/T1) (ΔS)B=mCvln(Tf/T2)
(ΔS)Universe=mCvln(Tf/T1) +mCvln(Tf/T2)
(ΔS)Universe=mCvln(Tf*Tf)/(T1*T2) (ΔS)Universe=mCvln(Tf2)/(T1*T2)
(ΔS)Universe=mCvln(Tf2/(Sqrt(T1*T2))2
(ΔS)Universe=2mCvln(Tf/(Sqrt(T1*T2))
(ΔS)Universe=2mCvln(T1+T2)/2*(Sqrt(T1*T2))
(ΔS)Universe>0 as arithmetic mean is always greater than Geometric mean
Isothermal disipatation of Work
Adibatic dissipatation of Work
Numericals
•A thermally insulated cylinder closed at both ends is fitted with a leak proof
frictionless diathermic piston which divides the cylinder into two parts. Initially the
piston is clamped in the centre with 1L of air at 300K and 3 bar on one side (Part-A)
and 1L of air at 300K and 1 bar on the other side (Part-B). The piston is released and
reaches equilibrium in pressure and temperature at a new position. Compute the final
pressure, temperature and work done by part-A on part-B.Compute also heat transfer
during the process by considering part A system(ii)by considering part B as system (iii)
by considering Part A and Part B together as system.Find the entropy change of the
universe.
Second law analysis of engineering
system(exergy analysis)
A system is said to be in the dead state when it is in thermodynamic equilibrium
with the environment it is in (Fig. 8–1). At the dead state, a system is at the temperature and
pressure of its environment (in thermal and mechanical equilibrium); it has no kinetic or
potential energy relative to the environment (zero velocity and zero elevation above a
reference level); and it does not react with the environment (chemically inert). Also, there are
no unbalanced magnetic, electrical, and surface tension effects between the system and its
surroundings, if these are relevant to the situation at hand. The properties of a system at the
dead state are denoted by subscript zero, for example, P0, T0, h0, u0, and s0. Unless specified
otherwise, the dead-state temperature and pressure are taken to be T0 25°C (77°F) and P0 1
atm (101.325 kPa or 14.7 psia). A system has zero exergy at the dead state
The useful work potential of a system at the specified state is
called exergy. Exergy is a property and is associated with the
state of the system and the environment. A system that is in
equilibrium with its surroundings has zero exergy and is said
to be at the dead state. The exergy of the thermal energy of
thermal reservoirs is equivalent to the work output of a Carnot
heat engine operating between the reservoir and the
environment.

• Reversible work Wrev is defined as the maximum amount

of useful work that can be produced (or the minimum work
that needs to be supplied) as a system undergoes a
process between the specified initial and final states. This
is the useful work output (or input) obtained when the
process between the initial and final states is executed in
a totally reversible manner.
Reversible work Wrev is defined as the maximum amount of useful work
that can be produced (or the minimum work that needs to be supplied) as a system
undergoes a process between the specified initial and final states. This is the useful work
output (or input) obtained (or expended) when the process between the initial and final
states is executed in a totally reversible manner. When the final state is the dead state, the
reversible work equals exergy. For processes that require work, reversible work represents
the minimum amount of work necessary to carry out that process. For convenience in
presentation, the term work is used to denote both work and power throughout this
chapter.Any difference between the reversible work Wrev and the useful work Wu is due to
the irreversibilities present during the process, and this difference is called irreversibility I.

The work done by work-producing devices is not always entirely in a usable form. For
example, when a gas in a piston–cylinder device expands, part of the work done by the gas
is used to push the atmospheric air out of the way of the piston (Fig. 8–8). This work, which
cannot be recovered and utilized for any useful purpose, is equal to the atmospheric
pressure P0 times the volume change of the system,
Irreversibility is the Difference Between Reversible Work and
Actual Useful Work
A 500-kg iron block shown in Fig. 8–12 is initially at 200°C and is allowed to cool to 27°C by
transferring heat to the surrounding air at 27°C. Determine the reversible work and the
irreversibility for this process.
EXAMPLE 8–13 Dropping a Hot Iron Block into Water
A 5-kg block initially at 350°C is quenched in an insulated tank that
contains 100 kg of water at 30°C (Fig. 8–40). Assuming the water that
vaporizes during the process condenses back in the tank and the
surroundings are at 20°C and 100 kPa, determine (a) the final
equilibrium temperature, (b) the exergy of the combined system at the
initial and the final states, and (c) the wasted work potential during this
process.
EXAMPLE 8–7 Work Potential of Compressed Air in a Tank
A 200-m3 rigid tank contains compressed air at 1 MPa and 300 K.
Determine how much work can be obtained from this air if the
environment conditions
Analysis We take the air in the rigid tank as the system (Fig. 8–24). This
is a closed system since no mass crosses the system boundary during the
process. Here the question is the work potential of a fixed mass, which is
the nonflow exergy by definition. Taking the state of the air in the tank
to be state 1 and noting that T1 T0 300 K, the mass of air in the tank is
are 100 kPa and 300 K.
The second-law efficiency is a measure of the performance of
a device relative to the performance under reversible
conditions for the same end states and is given by

for heat engines and other work-producing devices and

for refrigerators, heat pumps, and other work-consuming

devices.
• for refrigerators, heat pumps, and other work-consuming devices. In general,
the second-law efficiency is expressed as

=Exergy recovered/Exergy Supplied

Second Law of Efficiency
The second law of efficiency is a measure of the performance of a
device relative to its performance under reversible conditions
 Exergy of kinetic energy: xke = ke =

Exergy of potential energy: xpe = pe = gz

Exergy of internal energy:

xu = (u - uo) + Po(v - vo) - To(s - so)

Exergy of flow energy: xpv = Pv - Pov = (P - Po)v

Exergy of enthalpy: xh = (h - ho) - To(s - so)

The exergies of a fixed mass (nonflow exergy) and of a flow stream are
expressed as Non flow exergy

Flow Exergy
• The exergy change of a fixed mass or fluid stream as it undergoes a process from
state 1 to state 2 is given by