Department of Mechanical Engineering

ME 322 Mechanical Engineering

Thermodynamics

Lecture 20

Entropy Balance Equation

 The Second Law of Thermodynamics
Entropy is a balanced quantity. Therefore,
Entropy Entropy Entropy Entropy
transported - transported out + produced = gained within
into a system of a system within a system a system

ST SP SG

ST + S P = SG Total Entropy Form

ST + S P = SG Entropy Rate Form

Something to think about ... We have already seen that

entropy production occurs due to irreversibility. But, how is
entropy transported across a system boundary?

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 The Second Law of Thermodynamics
First, consider a closed system. For this
system, we know that the Second Law is, Q W

ST + SP = SG dST + dSP = dSG

Recall that Clausius discovered entropy

analyzing a Carnot cycle as a closed system. TH
His discovery was,
dQ
dS =
T rev
T in this expression is the boundary TL
temperature where Q is being transferred.

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 The Second Law of Thermodynamics
For a reversible process, we know that
the entropy production is zero. Therefore, Q W
for a reversible process, the Second Law
says,
dST = dSG
dQ
Now, consider Clausius discovery again, dS =
T rev
For the closed system that we are analyzing, it is clear that
heat and work cross the system boundary. Therefore, we
can say that,
dQ
dST = and dSG = dSsys
T rev
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 The Second Law of Thermodynamics
We have just discovered that that the
entropy is transported into the system Q W
by heat, but NOT by work!

For any closed system process, we can write,

dQ
+ dSP = dSsys
T

This expression can now be integrated between any two states,

dQ

2 2 2

+ dS P = dSsys
1 T 1 1

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 The Second Law of Thermodynamics
Analyzing each integral ...
dQ

2 2 2

+ dS P = dSsys
1 T 1 1

dQ

2
Qk Assumption: The system boundary is isothermal.
= The summation sign accounts for all heat transfer.
1 T k
Tk

2
dS sys = S2 - S1 = m s2 - s1 The entropy change of the system.
1

This is the integral of the entropy production in an

2
dS P = ??? irreversible process. But ... how do we evaluate the
1
integral???

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 The Second Law of Thermodynamics
Entropy production is caused by irreversibilities. Consider
two piston-cylinder assemblies. They are identical in every
way except that one of them operates reversibly and the
other is irreversible.
Questions ...
Wrev Wirr 1. Which system has zero
entropy production?
2. Which system delivers
Q Q more work?
3. Is work a property?
reversible irreversible 4. Is entropy production a
property?

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 The Second Law of Thermodynamics
Entropy production is NOT a property. It is a function of
path, just like heat and work!

dQ
+ dSP = dSsys
T

Now, we can integrate the entropy production term!

> 0 means that the process is irreversible

2
dS P = S P ,12 = 0 means the process is reversible
1
< 0 means the process is impossible

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 The Second Law of Thermodynamics
For a closed system, the Second Law of Thermodynamics
can be written as,
ST + S P = SG

Qk
+ S P,12 = m s2 - s1
k
Tk

This can be written on a per unit mass basis by dividing

both sides of the equation by the mass of the system,

Qk / m + S P,12

qk
= s2 - s1 + sP,12 = s2 - s1
k
Tk m k
Tk

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 The Second Law of Thermodynamics
Incorporating the net entropy transport into the system due to
the mass flows gives the complete form of the Second Law of
Thermodynamics!
Qk dS sys
k T + i mi si - e me se + SP = dt
k

Notice that if the system is closed,

Qk dSsys
k T + SP = dt
k

Qk
k T + SP,12 = m s2 - s1
k

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 The Laws of the Universe
Conservation of Mass The Continuity Equation
dmsys
mi - m e =
i e dt

Conservation of Energy The First Law of Thermodynamics

Vi 2 g Ve2 g dEsys
Q - W + m i hi + + zi - m e he + + ze =
i 2 gc gc e 2 gc gc dt

The Entropy Balance The Second Law of Thermodynamics

Qk dS sys
k T + i mi si - e me se + SP = dt
k

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 Special Application Closed Systems
Consider a closed system that is reversible and adiabatic.
The second law for such a system is,
0
0
Qk
k T + SP,12 = m s2 - s1
k

s2 - s1 = 0 s2 = s1

We have just learned that a reversible and adiabatic

process for a closed system is isentropic!

Notice: Reversible does not mean isentropic

Adiabatic does not mean isentropic
Reversible and adiabatic means isentropic!
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 Special Application Open Systems
Consider an open system that is operating in steady state
and is reversible and adiabatic with one flow in and one flow
out. The second law for such a system is,
0 0
0
Qk dS sys
k T + i mi si - e me se + SP = dt
k

m si - se = 0 si = se

We have just learned that a reversible and adiabatic

process for a system of this type is isentropic!

Entropy is the gate keeper of the Second Law!

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 Ideal Gases w/constant cp
We previously derived the following expressions for an ideal
gas from the Gibbs Equations,

T2 T2
dT v2 dT P2
s2 - s1 = cv +R ln s2 - s1 = cp - R ln
T1 T v1 T1 T P1

If the gas is undergoing a process where the heat capacity

can be assumed to be constant,
T2 P
s2 - s1 = c p ln - R ln 2
T1 P1

Consider a case where the process is also isentropic. Then,

T2 P
c p ln - R ln 2 = 0
T1 P1

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 Ideal Gases w/constant cp
Algebra time ...
T2 P2 T2 P T2 R P2
c p ln - R ln = 0 c p ln = R ln 2 ln = ln
T1 P1 T1 P1 T1 c p P1
R
T2 P2 cp
=
T1 P1

Rearrange the exponent,

R c p - cv c p / cv - cv / cv k - 1 cp
= = = k
cp cp c p / cv k cv

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 Ideal Gases w/constant cp
k -1
T2 P2 k
Substitution gives, =
T1 P1

If we consider an isentropic process with the other Ds equation,

1- k
T2 v2 T2 v2
s2 - s1 = 0 = cv ln + R ln =
T1 v1 T1 v1

Therefore, for an ideal gas with constant heat capacity

undergoing an isentropic process,
k -1
1- k
T2 P2 k v
= = 2
T1 P1 v1

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 Ideal Gases w/constant cp
But wait ... theres more!!
k -1 k -1
1- k 1- k
T2 P2 k v2 P2 k v2
= = =
T1 P1 v1 P1 v1

Rearranging ... k -1 k -1
k 1- k k 1- k
P 2 1 v =P 1 v2

k -1 k -1
k -1 k -1
P 2
k
v
2 =P 1
k
v1

k -1
k
k -1
k

P2v2 k -1
= Pv
1 1
k -1

P2v2k = Pv k
1 1 Does this look familiar?

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 Polytropic Process Relations
Pv n = constant
n 1/ n
P2 v1 v2 P1
= = Any fluid model
P1 v2 v1 P2

1- n n -1 / n
T2 v2 T2 P2 Ideal Gas Model
= =
T1 v1 T1 P1

1- k k -1 / k
T2 v2 T2 P2 Ideal Gas Model Isentropic
= =
T1 v1 T1 P1 process, constant heat capacity

n = k = c p /cv (ideal gas with constant heat capacity - isentropic process)

n = 0 (isobaric) n = (isochoric) n = 1 (ideal gas, isothermal)

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