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Thermodynamics
An Engineering Approach
Fourth Edition
Yunus A. engel
Michael A. Boles

Professor H.K. Ma
National Taiwan University
 CHAPTER
6

The Second Law of

Thermodynamics
6.1
6.1 Introduction
Introduction to
to The
The Second
Second Law
Law
THE SECOND LAW OF THERMODYNAMICS
-1

The direction of
physical processes
Constrained expansion-compression of
gases...
 The process
One kg of air, initially at 5 bar, 350 K and 3 kg of
carbon dioxide, initially at 2 bar and 450 K, are
confined to opposite sides of a rigid, well
insulated container.
The partition is free to move and allows heat
conduction from one gas to the other without
energy storage in the partition.
The air and carbon dioxide each behave as
ideal gases.
Determine the final equilibrium temperatures
and final pressures, assuming constant
specific heats.
 Adiabatic Boundary
Insulation (Q = 0)

The system

Air Partition Carbon Dioxide

1 kg Movement 3 kg
5 bar with Heat 2 bar
350 K Transfer 450 K
 Known Assume
Initial states of the Both gases are ideal with
two gases constant specific heats.
Closed system WS = 0.
Free motion of No heat stored in partition.
partition KE and PE effects negligible.
Heat flow between the No friction in partition.
two gases. Find
Final pressures
Final temperatures
 Comments

The process is inherently

transient, but can be treated as a
simple state change.
The final state will be such that
thermal (TA = TB ) and
mechanical (pA = pB ) will exist.
Initial State
TA TB A B

p A pB

Q AB 0
Final State
TA TB T2
A B
p A p B p2
 Solution

Apply First Law

Total energy of the combined system
is constant.
Apply Zeroth Law
Thermal equilibrium in the final
equilibrium state (TA2 = TB2).
 U 2 U1
(U A U B )1 (U A U B ) 2
m Au A,1 mB u B ,1 m Au A, 2 mB u B , 2
m A u A,1 u A, 2 mB u B ,1 u B , 2
m ACvA (TA,1 T2 ) mB CvB (TB ,1 T2 )
 Solution - Results

Solve for T2.

Specific heats: Evaluate from data tables.
Use a mean temperature of 400 K as an
estimated temperature.
Result: T2 = 425.6 K
 Solution - Results

Final Pressures: Use the ideal

gas equation of state to get total
volume.
VA,1 = (MRT/P)A,1
VA,1= 0.201 m3
Similarly, VB,1 = 1.275 m3
 Solution - Results

Total Volume = VA+VB

V = 1.476 m3
Final State
V = (mRT)A,2/p2 + (mRT)B,2/p2
 Solution - Results

Final pressure,
p2 = 2.462 bar
Total volume at State 2 is 1.476 m3.
Final volumes of gases A and B are
found employing the ideal gas
equation of state.
PA1 5 bar PA 2 2.462 bar
TA1 350 K TA 2 425.2 K
VA1 0.201 m 3
VA 2 ____ m 3

PB1 2 bar PB 2 2.462 bar

TB1 450 K TB 2 425.2 K
VB1 1.275 m 3
VB 2 ____ m 3
 Discussion

The constant specific heats aid in the

determination of the final
temperature. This is reasonable for
the small temperature changes here.
For each gas as a system, there are
heat and work transfers.
 Discussion

With no friction between the

partition and the boundary, there is
an infinite waiting time.
For the free moving partition, the
piston approaches to steady state in
an oscillatory manner.
Important questions...
 Once equilibrium has been reached
via this adiabatic process (overall),
can the system of A+B go back to
the initial state spontaneously?
Can we find a feature of this
process that characterizes the
impossibility of a spontaneous
return of the system to its initial
state?
 What characterizes the
equilibrium state apart from the
criteria already in hand?
What are the conditions under
which no process can occur at all
within the isolated system?
Is there a thermodynamic
property that provides a unique
answer all of the above questions?
 Everyone realizes that the reverse process
cannot happen. But why not? The total energy of
[the isolated] system would remain constant in
the reversed process as it did in the original, and
there would be no violation of the first law.
There must therefore be some other natural
principle, in addition to the first law and not
derivable from it, which determines the direction
in which a process can take place in an isolated
system.
(W. F. Sears, Thermodynamics, Addison Wesley,
Reading, 1953, pp. 110.)
Expansion of a gas with work transfer...
Air Supply
100 psi
80o F

Spring, k = 700 lbf/ft

 The process
A well insulated piston-cylinder assembly is
connected by a valve to an air supply at
100 psi, 80oF. The air inside the cylinder
is initially at 14.7 psi, 80 0F and occupies
a volume of 0.1 ft3.
Initially the piston face is a x = 0 and a
linear spring exerts no force on the
piston. The ambient air is 14.7 psia,
and the area of the piston face 0.22
ft2.
 The process

The valve is opened and air is

admitted slowly until the volume
of the air inside the cylinder 0.4
ft . During the process, the spring
3

exerts a force on the piston, in

proportion to displacement,
Fx = kx, where k = 700 lbf/ft).
 Find

(a) The final pressure in the

cylinder.

(b) The final temperature in

the cylinder.
The system
Gas in the cylinder
Air Supply
100 psi p, T i ( p, T ) f
800 F

Spring, k = 700 lbf/ft

pa, Ta
x
 Known

State of air supply (p, T, and large V)

Initial state of system(P,V, T)i
Final volume of the system cylinder (V f
= 0.4 ft3).
Ambient conditions (pa, Ta)
Ideal gas: pV = MRT
 Assumptions

The gas is an ideal gas.

No friction between piston and
cylinder wall
No heat transfer (i.e., adiabatic
process).
 Assumptions

Air supply is a pressure and

temperature reservoir (p = const., T =
const.).
KE and PE effects are negligible.
Air is admitted slowly; therefore there
is no acceleration of the piston, i.e., a
quasistatic process.
 Solution - overview

The cylinder fills with a gas at the known

enthalpy, h0, of the high pressure reservoir.
Filling is accompanied by an expansion against
the ambient gas and a varying force due to the
spring.
Thus there is work done by the system.
The assumption of no friction and no heat
transfer greatly simplify the problem.
 Solution - Step 1

Determine final pressure by applying a force

balance to the piston, which is a free body.

0 p ( x) A p a A kx
 0 p ( x) A p a A kx

(V Vi )
p (V ) p a k 2
A
2 2
(V f Vi )
p(V f ) p a k 2
44.8 psi
A
 Solution - Step 2

dmCV
m
CS
dt
Solution - Step 3

dU CV
Q CS W CS m CS h0
dt
W CS m CS h0
 Solution - Step 4

dU CV
WCS m CS h0
dt
dmCV
m CS m
dt
dU CV dm
W CS hi
dt dt

dU CV dm
W CS hi
dt dt
t

t
dU cv

W CS dt hi
t

t
dm

U f U i WCS hi m f mi
 Vf Vf
kVi kV

WCS PdV
Vi Vi
Pa 2 2 dV
Solution - Step 5

A A

WCS

Pa 2 V f Vi k
kVi
2
V f Vi 2

A 2A 2

WCS

Pa
kVi
V f Vi k V 2
f Vi 2
A2 2 A2

1.653 BTU
 Solution - Step 6
PV
m
RT
mi
PVi

14.7 14.7 144 0.1
RTi 1545 29 80 460
0.00457 lbm

mf
pfVf

44.8 14.7 (144) 0.4
RT f 1545 29 540
0.2875 lbm
 Summary of results

Final state
Initial state p = 59.5 psia
p = 14.7 psia T = 540 R
T = 540 R V = 0.4 ft3
V = 0.1 ft3 m = 0.288 lbm
m = 0.0046 lbm
 Solution - Step 7

U f U i WCS h0 m f mi
m f u f mi ui WCS h0 m f mi

m f u f h0 WCS mi (ui ho )
m f u f h0 WCS mi (ui ho )
u f h0 R
WCS mi ui h0
Tf P V
f f
From the property tables,
u1 = 92.04 Btu/lbm and h0 = 129.06 Btu/lbm.

u f h0 0.0396
Tf
 u f h0 0.0396
Tf
Solve iteratively to get

T2 = 614 0R = 154 0F
 An important question

Once the gas has expanded, could

the work be recovered?
If so, how could this be done?
What would be the maximum
amount of work that the system
could do?
 Natural processes

Spontaneous processes
How do they use energy?
Inefficiencies
How do they arise?
 Natural processes

Water flows down hill.

Objects fall to the earth and never rebound
to their original elevation.
Power plants eject hot fluid into streams
that cannot be recovered to do useful work.
Refrigerators eject heat into the
surroundings that cannot be recovered to do
useful work.
 Natural processes

Power plants eject hot fluid into

streams that cannot be recovered to do
useful work.
Refrigerators eject heat into the
surroundings that cannot be recovered
to do useful work.
 A conjecture...

There must therefore be some

other natural principle, in addition
to the first law and not derivable
from it, which determines the
direction in which a process can
take place in an isolated system.
W. F. Sears, Thermodynamics, Addison Wesley,
(

Reading, 1953, pp. 110. )

 Key concepts and terms

The Second Law

Reverse processes
Spontaneous processes