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3 FUNDAMENTAL LAWS

AND BALANCE
EQUATIONS FOR MASS,
ENERGY, ENTROPY,
EXERGY, AND
MOMENTUM
The purpose of studying thermodynamics is to predict the behavior
of systems in terms of their states as they respond to interactions
with their surroundings. Classical thermodynamics is an axiomatic
science; that is, the behaviors of systems can be predicted by
deduction from a few basic axioms or laws, which are assumed to be
always true. A law is an abstraction of myriads of observations
summarized into concise statements that are self-evident and
certainly without any contradiction. e have already come across
the !eroth "aw of thermodynamics, which introduced temperature, a
thermodynamic property, as an arbiter of thermal e#uilibrium
between two ob$ects.
%n this chapter we will introduce the conservation of mass and
momentum principle, the &irst "aw and 'econd "aw of
thermodynamics and the concept of exergy. A uniform framewor( in
terms of balance e#uations will be developed. )ach fundamental
principle will be translated into a balance e#uation of a particular
property. *ust as e#uations of state are the starting point for a state
evaluation, analysis of engineering systems and processes in the
future chapters will begin with the balance e#uations. hile the
balance e#uations are derived in this chapter, their applications to
closed and open systems are delegated to Chapter + and ,
respectively. To gain a comprehensive insight into these e#uations
Chapters -, + and ,, therefore, should be iteratively studied.
.
Chapter
- &undamental "aws and /alance )#uations &or 0ass, )nergy,
)ntropy, )xergy, and 0omentum........................................................
-.. /alance )#uation......................................................................-
-.1 2eynolds Transport )#uation 32T)4.......................................,
-.- Classification of 'ystems .........................................................5
-.-.. 6pen vs. Closed 'ystems ..................................................7
-.-.1 'teady vs. 8nsteady 'ystems ............................................7
-.-.- 8nsteady 9rocess ..............................................................:
-.-.+ 'ystem Tree .....................................................................;
-.+ 0ass )#uation .........................................................................;
-.+.. &orms of 0ass /alance )#uation .....................................
-., )nergy )#uation .......................................................................
-.,.. &orms of )nergy /alance )#uation .................................+
-.5 )ntropy /alance )#uation ......................................................,
-.5.. &orms of )ntropy /alance )#uation ................................<
-.7 )xergy /alance )#uation .......................................................1;
-.7.. &orms of )xergy /alance )#uation ................................15
-.: 0omentum /alance )#uation ................................................1:
-.< /alance )#uations 'ummary..................................................-;
-.<.. =eneral &orm ..................................................................-;
-.<.1 Closed 'ystems ...............................................................-.
-.<.- Closed 9rocess ................................................................-.
-.<.+ Closed 'teady ..................................................................-1
-.<., 6pen 'teady ....................................................................-1
-.<.5 6pen 9rocess ...................................................................--
-..; 'ummary..............................................................................+-
-... %ndex....................................................................................+-
1
3.1 Balance Equation
)ach fundamental law that will be introduced in this chapter will be
shown to be associated with a certain global extensive property -
mass
m
, energy E , entropy S , or momentum
x
mV
,
y
mV
or
z
mV -
of the system. To develop a unified framewor(, we will represent
these extensive properties with the generic symbol B and the
corresponding specific property with b . &or a uniform system 3&ig.
-..4, as stated in )#. 31.<+4, B mb . &or a non-uniform system,
however, B has to be summed or integrated over the ensemble of
local systems, each represented by a differential element as shown in
&ig. -.1. &or a local system with a volume dV , )#. 3...14 has to be
written in a differential form.
-
-
unit of
unit of > m
(g m ?(g
b B
dB bdm b dV dV B
v

1

1

]
%ntegrating, [ ] unit of
b
B bdm dV B
v


The integration is carried out over the entire system, open or closed,
at a given instant. %n &ig. -.1, notice how the boundary is carefully
drawn to pass through the inlet and exit ports at right angles so that
two uni#ue uniform surface states, 'tate-i and 'tate-e, can describe
the inlet and exit conditions. 0oreover, situated inside the ports
slightly away from the main body of the system, these states are
more li(ely to be uniform than if they were chosen exactly at the
openings. Assuming uniformity across the inlet and exit surfaces, the
flow rates of the property B at the ports can be obtained from )#.
1.<+.
unit of / (g unit of /
; and >
s s (g
i i i e e e
B mb B m b
1

1
]
& &
& &
where,
(g
; and
s
i i e e
i i i i e e e e
i e
AV AV
m AV m AV
v v

1

1
]
& &
/eside mass transfer, a property can be transferred across the
boundary through other interactions @ energy, for instance, is carried
with heat and wor(. As will be stated shortly, entropy can not only
be transferred, but also generated spontaneously within a system.
Therefore, B can be expected to change with time, i.e., ( ) B B t
.
To use the image analogy introduced in section ..-.-, the snapshot of
the system ta(en with the state camera at time
t
provides us with the
distribution of b throughout the system at that thermodynamic
instant. The global property ( ) B t
, therefore, can be obtained by
-
&ig. -... A uniform
system does not have to
be closed.
&ig. -.1. The local
system used inside the
integral of )#. .
simply analyzing the picture. 'imilarly, a snapshot ta(en after an
interval t can be used to evaluate ( ) B t t +
, the global property B
at time t t + . 6n the other hand, if the causes for a change in ( ) B t

are accounted for, the change ( ) B t t +
- ( ) B t
can be deduced
entirely from a different angle. The e#uality between the two
expressed on a rate basis constitutes the balance equation.

EXAMPLE 3-1 Total 9roperty for a Aon-8niform 'ystem.
The temperature of air trapped in a vertical rigid tan( of diameter .
m and height . m increases linearly from -;; B at the bottom to +;;
B at the top. Cetermine the total mass of the stratified air if the
pressure inside can be assumed uniform at .;; (9a. 8se the perfect
gas model.
SOLUTION The global properties of a non-uniform system is to be
determined by treating it as an aggregate of uniform local systems.
Assumptions A differential slice of air of thic(ness dx 3&ig. -.-4
constitutes a local system in "T).
Analsis &rom Table C-., obtain the necessary material properties
of airD
M
> 1< (g?(mol,
p
c
>..;;, (*?(g

B. The gas constant and


v
c
are calculated 3see 'ection 1.,.-...14 as R >:.-.+?1<>;.1:7 (*?(g

B and
v
c
> ..;;,- ;.1:7 > ;.7.: (*?(g

B. The variable temperature


can be expressed as
. 1
T c c x +
with
.
-;; c
B and
1
.;; c
B?m.
8sing the ideal gas e#uation,
pv RT
, )#. can be simplified as
follows.
1 1
; ;
+ +
L L
b bp p bdx
B bdm dV dx dx
v RT R T



&or the evaluation of mass of the system, B m ; therefore, . b .
'ubstituting this and the linear temperature relation, )#. can be
integrated.
( )
1 1
. 1
;
. 1 1 ;
1
1
1 .
ln
+ +
l ;.<+: n
+
(g
L
L p dx p
m dx c c x
R c c x Rc
T p
Rc T

+ 1
]
+

TEST Solution T)'T can be used only for uniform systems or


binary non-uniform systems, which are made of two uniform
subsystems. Therefore, this problem, which involves an infinite
number of local systems, cannot be solved using T)'T.
+
&ig. -.-. A slice of air
acts as a uniform local
system.
!iscussion The evaluation of other properties such as energy is more
complicated since b as a function of
x
will complicate the integrand
of )#. . &or more complex systems, where variation can be in all
three directions and are not (nown in functional terms, integration of
)#. may be impossible. &ortunately, the global properties of non-
uniform systems are seldom necessary to evaluate. )xamples of
property evaluation for uniform systems, which are more common,
can be found in )x. 1..< and 1.1;.
3.2 Reynolds Transport Equation (RTE)
The fundamental laws are usually described with closed systems in
mind. &or instance, AewtonEs 'econd "aw which states that the net
external force on a particle e#uals its rate of change of momentum,
implicitly assumes the particle, the system in our case, to be closed.
'imilarly, the conservation of mass principle, and the &irst and
'econd "aw are also easier to state as applied to closed systems.
)ach of these laws expresses the rate of change of a particular
extensive property with respect to time in terms of other variables. %n
other words, a generic format for these laws can be written as
unit of
(nown 3from the fundamental "aw4
s
c
dB B
dt
1

1
]
The superscript
c
reminds us that this e#uation cannot be applied to
open system as is. The right hand side 32F'4 is prescribed by the
specific laws to be introduced shortly. ith the help of 2T) the
fundamental laws, which are (nown in the closed system format of
)#. , are expanded into balance e#uations applicable to any (ind of
system, open or closed.
e begin the development of the 2T) by considering a very
general open system at time
t
and t t + as s(etched in &ig. 1.+. The
minor restriction of a single inlet and exit will be lifted as the last
step of this derivation. The system, defined by the dotted blac(
boundary, is allowed to have all possible interactions @ mass, heat
and wor( @ with its surroundings. As shown in the s(etch, even the
shape of the system is allowed to change. As the wor(ing substance
passes through the system, we identify a closed system mar(ed by
the red boundary at time
t
, which occupies the entire open system
plus a little region % near the inlet. The closed system becomes
deformed as it flows through the open system. After a small period
t , it still occupies the entire open system; however, the region-%
completely disappears and a new region, region-%%%, not necessarily
e#ual in size to region-%, appears near the exit. This is not a
coincidence since for any given t , the region-% is carefully chosen
so that the entire fluid inside that region flows into the system during
that interval. 6f course, t has to be sufficiently small so as not to
,
allow the closed system to loose its identity through disintegration,
and regions % and %% can be considered uniform so that
% %
t t t
i
B m b , and
%%% %%%
t t t t t t
e
B m b
+ + +

/ecause B is an extensive property, an inventory of B for a system


can be obtained by combining contributions from different sub-
regions comprising the system. 2eferring to &ig. -.-, the change in
B for the closed system as it passes through the open system 3region
%%4 can be written as
( ) ( )
, ,
%%% %
c t t c t t t t t t t
B B B B B B
+ + +
+ +
Ao special superscript is necessary for the open system because it is
the system by default. 2earranging and substituting )#.
( )
, ,
%%% %
c t t c t t t t t t t t t t
e i
B B B B m b m b
+ + + +
+
Cividing both side by t and ta(ing a limit
, ,
%%% %
; ; ; ;
lim lim lim lim
t t t t t t t t t c t t c t
e i
t t t t
m b m b B B B B
t t t t
+ + + +


+

The "F' and the first term on the 2F' of this e#uation are clearly
derivatives of the extensive property B with respect to time for the
closed and open system respectively. Also, as ; t ,
t t t
e e
b b
+
,
and the last two terms approach
e e
m b &
and
i i
mb &
, where the
superscript
t
is not necessary anymore since each term in this
instantaneous expression refers to time
t
. The above e#uation, thus,
reduces to
c
e e i i
dB dB
m b mb
dt dt
+ & &
=eneralizing for multiple inlets and exits, the "enol#s T$anspo$t
Equation 32T)4 or the %ene$al balance equation can be written as
i e
2ate of increase of 2ate of increa
Aet flow rate of Aet flow rate of
for an open system
into the system out of the system

c
i i e e
B
B B
dB dB
mb m b
dt dt
+

& &
1 4 2 4 3
1 4 2 4 3 1 4 2 4 3
se of
for a closed system.
B
1 4 2 4 3
%t relates the rate of change of an extensive property B of an open
system at a given instant to that of a closed system which happens to
pass through with the boundaries of the two systems aligning on top
of each other at that particular instant.
3.3 Classification of Systems
%n practical applications, thermodynamic systems or their behavior
are restricted in certain ways. Therefore the general template of the
5
&ig. -... A very general
system at two
neighboring
macroscopic instants.
balance e#uation, )#. , can be simplified when applied to specific
systems. &or instance, if a system is closed, the mass transfer terms
on the 2F' drops out. %n this section we will discuss, in general
terms, patterns that repeat across the entire spectrum of
thermodynamic devices and processes. 2ecognizing these patterns
will help us simplify a system, classify its behavior and reduce the
governing set of balance e#uations into custom forms. This
systematic approach will be cultivated throughout this boo( in favor
of the hit-and-miss approach of matching balance e#uations to
specific systems that gives thermodynamics a bad name among the
uninitiated.
3.3.1 Open vs. C!se" S#s$e%s
Classification of any system begins with the #uestion, G%s there any
mass transfer across the boundaryHI %f there is no mass transfer, the
system is called closed. 6therwise, by default, is considered open.
6bviously a system can only be open or closed, there is no other
alternative. %t should be stressed here that heat or wor( transfer has
nothing to do with whether a system is open or closed.
&or a closed system, the mass transfer terms drop out of )#. .
i
dB
m
dt
&
;
i e
i
b m

&
;
;
c c
e
e
dB dB dB
b
dt dt dt
+

The open system e#uation, thus, reduces to the fundamental laws


from which they are derived. The usefulness of such an obvious
e#uation will become clear when we introduce the individual balance
e#uations.
3.3.& S$e'"# vs. Uns$e'"# S#s$e%s
A system, by default, is unstea#; that is, its global state can change
with time. hen the global state of a system remains frozen in time,
it is said to be in stea# state. %n terms of our image analogy, the
snapshot of a steady system does not change whether or not the
system interacts with its surroundings. Fot and pressurized steam
flowing into a steam turbine exits at a much lower pressure and
temperature. 'haft wor(, flow wor( and even heat transfer from the
turbine may occur. Jet, the turbine is most li(ely to operate in a
steady state. At steady state all global properties, the total property
B included, must remain constant since the global image does not
change. Therefore, the time derivative of the "F' of )#. summarily
drops out ma(ing the general balance e#uation an algebraic one.
dB
dt
;, 'teady 'tate
c
i i e e
i e
dB
mb m b
dt
+

& &
7
&ig. -.,. 'ystem
classificationD 6pen vs.
Closed systems.
&ig. -.5. 'ystem
classificationD 'teady vs.
8nsteady systems.
6bviously this simplification is applicable to both open and closed
systems giving rise to four types of systems already. A closed system
passing through a steady open system need not be steady. %f you
follow a control mass of steam as a closed system entering the
turbine, it will surely undergo changes. That is why the last term in
)#. , which trac(s the changes in the closed system flowing through,
cannot be set to zero.
%n the classification process, the second #uestion to as( is,
GCoes the image of the system ta(en with a state camera change with
timeHI Although the answer is a simple yes or no, sometimes it
depends on the resolution or precision with which one answers the
#uestion. %nside a turbine 3ta(e a virtual tour of turbine in the T)'T
web site4 the rotors spins at a very high 290. Therefore,
instantaneous snapshots at two different times cannot be identical.
Fowever, if the thermodynamic instant 3see 'ection ..-.14 is
stretched by increasing the camera exposure to a few milliseconds,
the pictures at two different times will be almost identical as all the
fluctuations would average out in those few milliseconds. %n a
similar way, a car engine can be considered steady, as long as the
time resolution is large enough for the piston to execute several
cycles of stro(es. 6n the other hand if we are interested in a single
stro(e of the piston, the picture obviously changes and the system
must be considered unsteady.
3.3.3 Uns$e'"# P(!)ess
The time derivative of B is non-zero for an unsteady system. The
"F' of the balance e#uations cannot be simplified any further if
instantaneous rate of change of B is important. &or example, if we
are interested in the rate of change of temperature of a cup of coffee
at a specific instant as it cools down, we have an instantaneous!
unsteady! closed problem. The general balance e#uations, by default,
apply to instantaneous, unsteady, open systems.
6ften, in unsteady systems, the change of system properties
over a finite interval is of greater interest than an instantaneous rate
of change. &or instance, in the compression stro(e of an automobile
engine cycle, we are interested in the state of the gas mixture at the
beginning and end of the stro(e rather than at any intermediate state.
'imilarly, in the charging of a propane tan(, another unsteady
phenomenon, the instantaneous rates maybe of less significance than
the overall changes during the entire process. The balance e#uations
under such situations can be simplified by integrating with respect to
time.
An unsteady system is said to execute a p$ocess if it
undergoes changes from a beginning global state, called the b-state
or begin-state, to a final global state, called the &-state or final-state.
:
&ig. -.7. As water flows
through the constriction,
its pressure changes.
Fowever the open
system is a steady one if
the global picture does
not change.
&ig. -.:. 'ystem
classificationD 9rocess
vs. %nstantaneous rate.
&ig. -.<. %n this closed
process, a gas is
compressed from a b-
'tate to a f-'tate.
&ig. -..;. %nflating a tire
is an open process.
The begin and finish states are also (nown as the anc'o$ states of a
process. The anchor states must be in e#uilibrium for a process;
however, as the system moves from the b-state to f-state it does not
have to pass through a succession of e#uilibrium for the balance
e#uations to be simplified. &or system which is uniform at the
beginning and end of the process, the anchor states can be spotted on
the familiar
p v
diagram as s(etched for a compression process in
&ig. -.<. Aote that without a thorough (nowledge of the process, we
cannot select a path between the anchor states.
To identify if an unsteady system is undergoing a process, the
appropriate #uestion to as( is, GCoes the unsteady system move from
a clear beginning to a clear finish stateHI %f the answer is yes, we
have a process.
The simplification for a process is achieved by multiplying
)#. with dt and integrating from the b-state to the f-state.
c
i i e e
i e
dB
dB mb dt m b dt dt
dt
+

& &
finish finish finish finish
begin begin begin begin

c
i i e e
i e
dB
dB mb dt m b dt dt
dt
+


& &
finish finish finish
begin begin begin

c
" b i i e e
i e
dB
B B mb dt m b dt dt
dt
+


& &
&or an open unsteady system, the inlet and exit states are often
assumed to remain uniform across the cross-section and invariant
with time. The assumption, (nown as the uni&o$m state an#
uni&o$m &lo( assumption; can considerably simplify the above
e#uation as
i
b
and
e
b
, being independent of time, can be pulled out
of the integrals. The general balance e#uation for an open p$ocess
reduces to
finish
begin
finish finish
begin begin
where, , and
c
" b i i e e
i e
i i e e
dB
B B B mb m b dt
dt
m mdt m m dt
+




& &
The e#uation still loo(s #uite formidable with an integral of a
derivative as one of its term. Fowever, when we discuss specific
balance e#uations, say, mass or energy e#uation, this term will be
shown to simplify much farther.
<
3.3.* S#s$e% T(ee
The classification of systems introduced until now can be organized
in a tree structure as shown in &ig. -..., called the sstem t$ee. The
next two chapters will be devoted exclusively to the discussion of
closed and open systems respectively. &urther classification of
closed process and open steady systems will be deferred until then.
%n T)'T start at the daemons page, by using the Caemons
lin( on the Tas( /ar, to classify a system. A simplification table
provides lin(s to all possible branches one can follow depending on
the answer to the #uestion posed at the table header. At any stage of
simplification, a system schematic and the customized set of balance
e#uations appear below the simplification table. 6nce you gain
expertise in this step-by-step procedure, you can use the 0ap,
arranged li(e the tree of &ig. -... and lin(ed from the Tas(-/ar in
T)'T, to $ump to a specific category of systems by clic(ing on its
node.
e now begin the development of fundamental laws into
balance e#uations and customize these e#uations for different classes
of systems.
3.4 ass Equation
The conse$)ation o& mass p$inciple can be stated through the
following simple postulate.
Mass cannot be created or destroyed#
&or a closed system the total mass
c
m must remain constant;
therefore, the time derivative of
c
m must be zero, i.e.,
;
c
dm
dt

'ubstitute )#. into the 2T), )#. , with B m and . b , to
formulate the mass balance equation for an open unsteady system.
2ate of increase of mass
Aet mass flow rate Aet mass flow rate of
for an open system.
into the system. out of the system.
(g

s
i e
i e
dm
m m
dt
1

1
]

& &
1 4 2 4 3
1 4 2 43 1 4 2 43
The meaning of the three terms is explained with the help of a &lo(
#ia%$am in &ig. -..1. The difference between the inflow and
outflow is accumulated in the balloon. 'imilar flow diagrams will be
constructed for other balance e#uations.
.;
&ig. -... The system
classification tree. The
0ap in T)'T displays a
similar clic(able tree.
&ig. -..1 &low diagram
for the mass balance
e#uation..
3.*.1 F!(%s !+ M'ss B''n)e E,-'$.!n
The general form of the mass balance e#uation can be simplified for
different categories of systems classified in &ig. -....
*lose# Sstem Simpli&ication &or a closed system the mass transfer
terms drop out. &or both steady and unsteady closed systems,
therefore,
;
dm
dt
or, constant m
This is almost a trivial result; therefore, a constant mass can be
implicitly assumed for a closed system without having to refer to this
e#uation.
Open Stea# Simpli&ication As explained in section -.-.1, at steady
state the total mass, li(e all other global properties, remains constant.

dm
dt
;, steady state
i e
i e
m m

& & ; or,
(g

s
i e
i e
m m
1

1
]

& &
This form of mass conservation is often referred as Gwhat goes in
comes outI. %f there is a single flow, i.e., only one inlet and one exit,
the e#uation can be further simplified using )#. .

i e
m m m & & &
; or,
i i i e e e
m AV AV &
, or
i i e e
i e
AV AV
m
v v
&
Open P$ocess Simpli&ication &or a process involving an open
system )#. can be integrated or, alternatively, )#. can be used to
produce
finish finish
begin begin
where, , and
" b i e
i e
i i e e
m m m m m
m mdt m m dt




& &
This form is further simplified if there is only a single inlet or a
single exit as in the case of charging a propane tan( or a whistling
pressure coo(er. Ciscussion of such specific cases, however, is
postponed until Chapter ,.
3.! Ener"y Equation
The conse$)ation o& ene$% p$inciple also (nown as the +i$st La(
of thermodynamics can be stated through the following postulates.
i4 The internal energy
u
o" a system is a thermodynamic property#
..
&ig. -..- &low diagram
for the mass balance
e#uation, open steady
system.
&ig. -..+ &low diagram
for the mass balance
e#uation, open process.
ii4 Energy E $ %E &E + + cannot be created or destroyed! only
trans"erred through heat or 'or(# )n a rate basis this can be
expressed as
(*
>(
s
c
c c
dE
* +
dt
1

1
]
& &
'here!
c
*
&
is the net rate o" heat trans"er into the system and
c
+
&
is
the net rate o" 'or( or po'er trans"er out o" the system#
'ubstituting E ,
e
and
c
E
for B , b and
c
B
respectively in the 2T)
and using the second postulate
Aet 2ate of
2ate of increase hea
Aet energy flow rate Aet energy flow
of for an
into the system. rate out of the system.
open system.

i i e e
i e
E
dE
me m e *
dt
+

&
& &
14 2 43
1 4 2 4 3 1 4 2 4 3
[ ]
Aet 2ate of
heat transfer
t transfer
into the system.
into the system.
( +
&
14 2 43
14 2 43
where, *
&
and +
&
, evaluated based on the open system boundary, are
substituted for
c
*
&
and
c
+
&
respectively since the boundaries of the
closed and open systems become coincident as ; t . The energy
flow rates at the inlet and exit can be also be expressed through the
symbol E me
&
& , which is used in the flow diagram of &ig. -..5.
)#uation is now completely decoupled from the original closed
system and will be labeled the conse$)ati)e &o$m of the energy
e#uation.
Cifferent modes of heat and wor( transfer, shown in the flow
diagram of &ig. -..5, will be #uantitatively discussed in the next
chapter. As explained in 'ection ..1.1.1, the transfer of heat through
the ports can be neglected compared to the transfer through the rest
of the boundary. The same, however, is not true about wor( transfer
through the system ports, called the "lo' 'or(. As explained in
'ection ..1.1.+ different types of wor( transfer can be classified into
two ma$or categories, flow and external wor(, to distinguish open
and closed systems.
, , sh el
Aet 2ate of
'haft or( )lectrical
or( transfer
6ut or( 6
Aet &low Aet &low
out of the system.
or( 6ut or( %n
&low or(,

,
, e , i
i i
+
+ + + + + + +

&
& & & & &
14 2 43
1 2 3
14 2 43 14 2 43
1 4 44 2 4 4 43
ext
/oundary
or( 6ut ut
6ther or(,
ext
)xternal or(,


)
B
+
, ) B ,
+
+
+ + + + +
+
+ + +
&
&
&
1 2 3 1 2 3
1 4 4 2 4 4 3
& & & & &
1 4 2 4 3
.1
&ig. -..5 &low diagram
explaining various
modes of heat and wor(
transfer.
&ig. -.., &low diagram
for the conservative
form of the energy
balance e#uation, open
unsteady system.
&or a closed system ;
,
+
&
and there is no distinction between +
&

and
ext
+
&
.
To evaluate the flow wor(, consider the small fluid element
of length
e
x
in the simplified system of &ig.-..7 that is pushed out
of the system by the pressure force from the left against the pressure
from the right. The pressure force
e e e
, p A
does a wor( of
e e
, x

3see 'ection ..1.1.-4 in t . According to the sign convention, the
exit wor( must be positive since wor( is done by the system. %n a
similar manner, as a fluid element is pushed into the system against
the resistance of the inlet pressure, a negative wor( transfer with a
magnitude of
i i
, x
ta(es place in time t at the inlet. As ; t ,
the net flow wor( rate or flow power can be written with the help of
)#. as
, ,

e e i i e e e i i i
, , e , i
e e i i
e e e i i i e e i i e e e i i i
e i
, x , x p A x p A x
+ + +
t t t t
AV AV
p AV p AV p v p v m p v m p v
v v




& & &
& &
A port with a very small area still can have very large
pv
and, thus,
transfer a relatively significant amount of flow wor(.
)#uation can be generalized for multiple inlets and exits.
, e e e i i i
e i
+ m p v m p v

&
& &
)ach term on the 2F' resembles flow rate of properties discussed in
'ection 1.:. The flow wor( too, therefore, can be regarded as a flow
property. 'ubstituting the above expression for flow wor( after
separating it from all other wor( terms, the conservative form of the
energy e#uation, )#. , can be rewritten as
( ) ( )
ext i i i i e e e e
i e
dE
m e p v m e p v * +
dt
+ + +

& &
& &
%n this modified form the mass flow can be seen to carry a
combination property consisting of energy
e
and a term that
represents the flow wor( performed per unit mass of the flow. e
call this combination property the speci&ic &lo( ene$% and represent
it with the symbol
-
in the absence of any universally accepted
symbol for this important convenience property.
- e pv u (e pe pv h (e pe + + + + + +
'ubstituting the symbol
-
for the specific flow energy, we obtain
the balance equation &o$ ene$% in its most general form.
.-
&ig. -..: The flow of
flow energy
.
&
is
e#uivalent to the flow of
energy
E
&
and the
transfer of flow wor(
,
+
&
across a control
surface.
&ig. -..7 A fluid
element at the exit being
expelled by the system
against an external
pressure.
2ate of increase
Aet flow rate of flow Aet flow rate of flow
of for an
energy into the system. energy out of the system.
open system.

i i e e
i e
E
dE
m - m - *
dt
+

&
& &
14 2 43
1 4 2 4 3 1 4 2 4 3
[ ]
ext
Aet 2ate of Aet 2ate of
heat transfer wor( transfer
into the system. into the system.
1
ext
(
where, , and
1;;; .;;;
B )
+
V gz
- h (e pe h + + +

+ + + + +
&
14 2 43 14 2 43
& & &
The energy carried by the flow E me
&
& in the conservative form,
)#. , is replaced in this e#uation by the "lo' energy carried by the
flow, . m-
&
& . The advantage of this form is that only the readily
recognizable external wor( appears in this e#uation and the hidden
wor( of flow can be completely ignored since it is already accounted
for in the use of the property
-
. %t may seem that this form of energy
e#uation is meant only for open systems. To the contrary, if we
substitute ;
,
+
&
and
,
+ +
& &
;
ext ext
+ + +
& &
into )#. , the second
postulate of the &irst "aw is immediately recovered ma(ing )#. the
most general form from which all other forms should be derived.
The meaning of various terms in this e#uation is explained through
the flow diagram of &ig. -..:.
3./.1 F!(%s !+ Ene(0# B''n)e E,-'$.!n
As we did with the mass balance e#uation, the energy e#uation is
customized for the particular classes of systems introduced in the
system tree of &ig. -....
*lose# Sstem Simpli&ication &or a closed system the mass transfer
terms drop out and
ext
+ +
& &
as there is no possibility of any flow
wor(. The energy balance e#uation, )#. , reduces to the second
postulate of the &irst "aw.
dE
* +
dt

& &
6bviously, this forms suits any instantaneous unsteady closed
system. There is no need for the superscript c anymore because we
are deriving a restricted form from a more general form applicable to
both open and closed systems.
*lose# P$ocess Simpli&ication &or an unsteady closed system going
through a process, )#. can be integrated from the b-state to the f-
state as outlined in section -.-.- producing
.+
&ig. -..< /y using
specific flow energy
-

instead of specific
energy e , the
cumbersome flow wor(
can be forgotten.
&ig. -.1; &or a closed
system there is no flow
wor(; therefore,
ext
+ +
& &
.
finish finish finish
begin begin begin
where, , and
" b
B ) B )
E E E * +
* *dt + + dt + dt + +

+ +

& & &
This is an algebraic e#uation that relates two anchor states through
two process variables
*
and + .
*lose# Stea# Simpli&ication &or a steady system, open or closed,
the time derivative of any global property must be zero. The energy
e#uation, thus, simplifies to
* +
& &
The net rate of heat transfer to a steady closed system must be
exactly e#ual to the net rate of wor( delivered by the system.
Open Stea# Simpli&ication The time derivative of all global
properties of the system must be zero at steady state as the global
picture remains frozen at steady state. The energy e#uation
simplifies to what is commonly called the stea# &lo( ene$%
equation 3'&))4.
ext
;
i i e e
i e
m - m - * + +

& &
& &
/y rearranging the e#uation, it can be shown that the sum total of the
rate of flow of "lo' energy and heat into a steady open system must
be e#ual to the rate at which energy leaves the system through flow
energy and external wor(. "i(e the steady state mass balance
e#uation, it expresses 'hat goes in! comes out in terms of energy.
Open P$ocess Simpli&ication &or a process involving an open
system )#. can be integrated from the begin to the finish state as
outlined in section -.-.- for a generic property. 8sing the uniform
flow uniform state assumption, the energy e#uation reduces to
ext
finish finish
ext
begin begin
where, , and
" b i i e e
i e
ext
E E E m - m - * +
* *dt + + dt
+



& &
The mass transfers in such a process has already been examined in
section -.+...
3.# Entropy Balance Equation
The Secon# La( of thermodynamics can be stated through the
following postulates.
.,
&ig. -.1. )nergy flow
diagram for a closed
process.
&ig. -.11 )nergy flow
diagram for a closed
steady system.
&ig. -.1- )nergy flow
diagram for an open
steady system.
&ig. -.1+ )nergy flow
diagram for an open
process.
i4 Entropy S is an extensive property that measures the degree o"
disorder in a system# The speci"ic entropy
s
is a thermodynamic
property#
ii4 Entropy can be trans"erred across a boundary through heat but
not through 'or(# The rate o" entropy trans"er by *
&
crossing a
boundary at a temperature
B
T is given as ?
B
* T
&
#
iii4 Entropy cannot be destroyed# /t can be generated by natural
processes, i#e#!
gen
; S
&
.
iv4 An isolated system achieves thermodynamic e0uilibrium 'hen
the entropy o" the system reaches a maxima#
"et us go over these statements one at a time. &rom our
experience of chaos, we would tend to agree with the first postulate
that entropy, being a measure of total amount of chaos or disorder in
a system, is an extensive property; that is, doubling the size of a
uniform system will double its entropy.
Feat transfer to a system can be expected to increase the
molecular disorder and, hence, entropy. %f a uniform system is at a
high temperature and, therefore, pretty chaotic to start with, addition
of heat cannot be expected to add as much entropy to the system as
would be the case for a cooler, less chaotic system. This provides
$ustification as to why the boundary temperature, which is same as
the system temperature for a local system, occurs in the denominator
of the entropy transfer term in postulate-%%. 6bserve that transfer of
wor( does not seem to affect entropy of a system. or( involves
organized motion such as the rotation of a shaft, motion of a
boundary, and, in the case of electricity, directed movement of
electrons, etc. The chaotic motion of the system, therefore, remains
unaffected by the transfer of organized motion.
The third postulate states that every system has a natural
tendency towards generating entropy. /ecause entropy cannot be
destroyed, the generated entropy is a permanent signature of the
process. hen heat radiates from the 'un to earth, the coffee in the
stirred cup gradually comes to rest, electrons flow across a voltage
difference, a drop of in( dissipates in a buc(et of water, rubbing one
hand against another ma(e them warm, natural gas burns in air
forming hot flames, a volcano erupts @ there is one thing that is
common in all these apparently unrelated phenomena; they all tend
to destroy a gradient of some (ind while generating entropy as
dictated by postulate-%%. %n the next chapter we will devote an entire
section going after these sources of spontaneous entropy generation.
&or the time being, we will refer to all these gradient destroying
natural phenomena as %ene$ali,e# &$iction.
.5
&ig. -.1, CA2T66A
Are you saying that the
'econd "aw left those
footprintsH
=eneralized friction leave an indelible footprint in the form
of entropy generation. Any process involving generalized friction,
therefore, cannot be completely reversed and are called i$$e)e$sible,
the degree of i$$e)e$sibilit being proportional to the entropy
generation. =eneralized friction due to system surroundings
interactions sometimes extends beyond the system into the
immediate surroundings. Cepending on the location where the
entropy is generated with respect to the system boundary, the
associated irreversibilities are called inte$nal if within the system
and exte$nal if outside or at the boundary. &or instance, entropy is
generated inside and in the immediate surroundings of a turbine
operating in a steady state. The sstem-s uni)e$se enclosed by the
outer boundary of &ig. -.15 includes both the internal and external
generation of entropy. %n the limiting situation of no entropy
generated in the systemEs universe as a result of a particular process,
the system can be completely restored bac( to its original state
without leaving any clue that the original process ever too( place.
The system or process is said to be $e)e$sible under that ideal
situation. The concept of entropy generation will be lin(ed in the
next chapter with the design of more efficient engines, refrigerators
and various other thermal devices.
The third postulate 3not to be confused with the Third "aw of
thermodynamics to be introduced in Chapter-:4 has tremendous
implications in predicting e#uilibrium, which will be discussed in
more details in Chapter : and .;. &or the time being, consider two
closed insulated systems, initially at two different temperatures,
brought in diathermal contact by removing insulations from two
walls and pressing the two bloc(s against each other on their un-
insulated faces. The entropy of the combined system will start to
increase as entropy is generated due to heat transfer from the hotter
bloc( to the colder one. e (now from our experience that at
e#uilibrium temperatures of the two bloc(s will become e#ual, at
which point entropy will cease to increase any further, all the
temperature gradient having been completely destroyed. Thus
entropy has been maximized as the isolated system, consisting of the
two bloc(s, comes to e#uilibrium. As a matter of fact, we will show
in Chapter-:, that starting from the second law, the e#uality of
temperature at e#uilibrium can be predicted. Although this may seem
li(e a trivial exercise, the same principle will help us deduce in
Chapter @.;, the emissions from combustion, something far from
trivial.
=etting bac( to our tas( of translating the fundamental laws
into balance e#uations, the second postulate can be written as.
gen gen
(
; ;
B
c c
c c
B
dS *
S S
dt T
1
+
1
]
&
& &
.7
&ig. -.15 The
interactions between the
system and its
surroundings causes
entropy generation
inside and in the
immediate surroundings
of a system.
&ig. -.15 )ntropy is
generated in the shaded
area which extends
beyond the system
boundary.
where,
gen
S
&
is the rate of entropy generation within the closed
system boundary and
c
*
&
is the rate of heat transfer into the closed
system of &ig. -.+. 'ubstituting S and
s
for B and b respectively
in the 2T), we obtain the %ene$al ent$op balance equation.
2ate of increase
Aet flow rate of Aet flow rate of Aet 2ate of
of for an
entropy into entropy out of
open system.
the system. the system.

i i e e
i e
B
S
dS *
ms m s
dt T
+

&
& &
14 2 43
1 4 2 43 14 2 43
gen
Aet 2ate of
generation of
entropy inside entropy transfer
the system. through heat.
gen
(

B
where, ;
S
S
1
+
1
]

&
14 2 43
1 4 2 43
&
As mentioned before, the boundary of the closed system passing
through the open system of &ig. -.+ is almost identical to that of the
open system as t goes to zero. Therefore,
c
* *
& &
and
gen gen
c
S S
& &
.
The comments under each term are (eyed to the open system of &ig.
-.+ as this general entropy e#uation completely stands on its own
without any reference to the closed system to which it owes its
origin. The flow diagram of &ig. -.17 also explains the various terms
of the entropy e#uation. An arrow with dots inside is used to signify
the generation of entropy.
&or most systems on earth, the heat interaction ta(es place
with the surrounding atmosphere. %f the system boundary is carefully
drawn to pass through the surrounding air, atmospheric temperature
can be used for
B
T . 6bviously the precise location of the boundary
does not affect *
&
or +
&
, which are flow rates of energy; however,
being a cumulative #uantity,
gen
S
&
depends entirely on the selection
of boundary. The total rate of entropy generation in the turbine of
&ig. -.15, for instance, can be expressed as the sum of the entropy
generation inside the system and in the immediate surroundings
external to the system.
gen,univ gen,int gen,ext
(

B
S S S
1
+
1
]
& & &
where the subscript univ is used to signify the system1s universe.
%f a system exchanges heat with different segments of the
surroundings at different temperatures as shown in &ig. -.1:, the
boundary of the extended system can be made to pass through (
segments each at a uniform temperature
(
T
. The entropy balance
e#uation for the systemEs universe modifies as follows
gen,univ
(

B
(
i i e e
i e (
(
* dS
ms m s S
dt T
1
+ +
1
]

&
&
& &
.:
&ig. -.17 )ntropy is
accumulated due to
generation and transfer
through mass and
energy.
&ig. -.1:
gen,univ gen gen,ext
S S S +
& & &
includes all sources of
entropy generation
inside and outside the
system.
&ig. -.1< &low diagram
of entropy for an
extended system with
surroundings at two
different temperatures.
The total entropy S , the mass flow rates
i
m&
or
e
m&
and the heat
transfer rate
(
*
&
are assumed not affected significantly by extending
the system to include the thin layer of immediate surroundings. The
entropy generation, however, can be huge outside the system, even
in a very thin layer. This will be discussed with examples in the next
chapter.
3.1.1 F!(%s !+ En$(!p# B''n)e E,-'$.!n
As we did with the mass and energy balance e#uations, we will
customize the entropy e#uation in a similar manner for different
classes of systems. Although the following e#uations are written for
a system with a fixed boundary temperature
B
T
, they can be modified
for an extended system by replacing
gen
S
&
with
gen,univ
S
&
and
B
*
T
&
with
(
(
(
*
T

&
.
*lose# Sstem Simpli&ication &or a closed system the mass transfer
terms drop out and )#. reduces to
gen
B
dS *
S
dt T
+
&
&
6bviously, this form suits any instantaneous unsteady closed system.
*lose# P$ocess Simpli&ication &or an unsteady closed system going
through a process, )#. can be integrated from the b-state to the f-
state as outlined in section -.-.- producing
gen
finish finish
gen gen
begin begin
where, , and
" b
B
*
S S S S
T
* *dt S S dt
+


& &
This is an algebraic e#uation that relates two anchor states through
two process variables
*
and
gen
S
. 6bviously
gen
; S
since
gen
; S
&
*lose# Stea# Simpli&ication &or a steady system, the time
derivative of any global property must be zero. )#. simplifies to

;
gen
B
*
S
T
+
&
&
A number of 'econd "aw statements can be deduced from this
e#uation in the next two chapter.
.<
&ig. -.-; )ntropy flow
diagram for a closed,
instantaneously
unsteady system.
&ig. -.-. )ntropy flow
diagram for a closed,
process.
&ig. -.-1 The default
direction of heat flow is
inconsistent with the
direction of entropy
transfer.
Open Stea# Simpli&ication ith the time derivative of S
disappearing at steady state, the entropy e#uation, )#. , simplifies to
a form similar to the steady flow energy e#uation.
gen
;
i i e e
i e
B
*
ms m s S
T
+ +

&
&
& &
Aote that unli(e the mass or energy e#uation, the entropy e#uation
cannot be rearranged in the what-goes-in-must-come-out format.
/ecause of entropy generation, what comes out is often more that
what goes in.
Open P$ocess Simpli&ication &or a process involving an open
system, )#. can be integrated from the begin to the finish state as
outlined in section -.-.-. 8sing the uni"orm "lo' uni"orm state
assumption, the entropy e#uation reduces to
gen
finish finish
gen gen
begin begin
where, , and
" b i i e e
i i B
*
S S S ms m s S
T
* *dt S S dt
+ +



& &
The mass transfers in such a process has already been examined in
section -.+...
3.$ E%er"y Balance Equation
'tagnant air and wind both have energy. Jet it is much easier to
extract useful wor( out of the wind than stagnant air at atmospheric
conditions. 6ne of the ma$or #uests for engineers at all times has
been delivery of useful wor( in the form of shaft or electrical power
out of any source of available energy - wind, ocean waves, river
streams, geo-thermal reserves, solar radiation, fossil fuels, nuclear
materials, etc. ith the help of the mass, energy and entropy
balance e#uation we are about to predict the maximum possible
useful wor( that can be extracted from a system. %n fact
manipulation of these e#uations will be shown to lead to a new
balance e#uation for a new property called exe$%, which measures
the useful energy content of a system. The ocean or the atmosphere
may have tremendous amount of energy due to their huge mass
alone, but very little exergy; that is why, a ship or an airplane cannot
extract any useful wor( out of these reservoirs of energy. )xergy,
thus, can be loo(ed upon as a measure of the #uality of energy. An
exergy analysis not only helps in comparing two alternative sources
of energy - or should we say exergy @ but also in rating the
performance of any device that consumes or delivers useful wor(.
1;
&ig. -.-- hat comes
out may be more than
what goes in since
gen
; S
&
.
&ig. -.-+ )ntropy
diagram for an open
process.
&ig. -.-, CA2T66A @
A ship stuc( in an ocean
or a car stuc( in a
desert. )nergy )nergy,
every where but not a
drop of exergy to drin(.
/ecause exergy is a derived concept, we must develop the balance
e#uation first before identifying the different mechanisms of its
storage, transfer and generation, if any. 6nly then can we precisely
define exergy as a property.
Consider the system schematic s(etched in &ig. -.-,. "i(e
&ig. -.+, it has only one inlet and one exit, a restriction that will be
readily removed towards the end of our derivation. The
surroundings, however, is divided into two thermal energy reservoirs
or TE"S @ a t'e$mal ene$% $ese$)oi$ is a large system whose
temperature is assumed not affected by heat transfer @reservoir ;,
which is atmospheric air at a standard temperature
;
T
and reservoir
( , say, a furnace at a temperature
(
T
. Aote that a T)2 is sometime
called a 'eat $ese$)oi$, an oxymoron for a form of energy which
can only be transferred and not stored. 6bviously, the number of
T)2' can be extended $ust the same way as the number of inlets or
exits.
&or the extended system enclosed by the boundary of &ig.
-.-,, the energy and entropy e#uations can be written as
ext i i e e o (
dE
m - m - * * +
dt
+ +
& & &
& &
gen,univ
o (
i i e e
o (
* * dS
ms m s S
dt T T
+ + +
& &
&
& &
/y including the immediate surroundings, we capture the entire
amount of entropy generation
gen,univ
S
&
3see )#. 4due to the
interactions between the system and its surroundings; moreover, the
choice of the boundary temperature is simplified as it passes through
the T)2Es with constant temperatures
;
T
and
(
T
. Aote that
variables,
i
m&
,
e
m&
,
i
-
,
e
-
,
i
s
,
e
s
,
o
*
&
,
(
*
&
, or
ext
+
&
are unaffected by
the choice of the extended system. %f the mass 3or thermal capacity4
of the added layer of immediate surroundings can be considered
small compared to the internal system, E and S also can be
assumed identical between a system and its extended version. The
only difference, therefore, comes from the entropy generation
contributed by the immediate surroundings.
0ultiplying )#. by
;
T
, a constant, and subtracting the
resulting e#uation from )#. we get
1.
( )
( ) ( )
;
; ;
;
ext ; gen,univ
.
i i i e e e
(
(
d E T S
m - T s m - T s
dt
T
* + T S
T


_
+

,
& &
& & &
/efore we proceed further, let us ta(e a closer loo( at the external
wor( transfer. Cifferent modes of wor( transfer have been
introduced in a #ualitative manner in 'ection ..1.1.+ and through a
flow chart in &ig. -..5, which is further modified in &ig. -.-7. 0ost
components of the external wor( transfer, electrical, shaft or power
transfer through a piston into the cran( shaft are readily useful. The
only exception is the part of boundary wor( transfer that involves the
atmosphere. The wor( done by the piston in pushing the atmospheric
air in &ig. -.-5 cannot be used for any practical purpose. 'imilarly if
the piston is pushed downward, the atmospheric wor( comes free
and does not cost anything as does any other form of useful wor(.
The external wor( term in )#. , therefore, can be separated into an
useful and atmospheric components as shown by the flow diagram of
&ig. -.-7.
ext atm u
+ + + +
& & &
Although evaluation of boundary wor( is a topic for the next
chapter, we can evaluate the atmosp'e$ic (o$. transfer due to the
displacement x of the piston in time t as shown in &ig. -.-: by
recalling the definition of wor( 3see 'ection ..1.1.-4 and the sign
convention.
( ) ( )
; ; ;
atm ;
; ;
lim lim
t t
p A x d p V p V dV
+ p
t t dt dt




&
The inner negative sign accounts for the fact that the atmospheric
force and the displacement of its point of application are in opposite
direction. The outer negative sign converts the wor( done by the
atmosphere into wor( done by the system. The expression derived
for a single piston can be shown to remain valid even if the entire
boundary of a system is non-rigid. The boundary, in that case, can be
divided into a large number of discrete pistons-cylinder
arrangements and the contributions from individual elements when
integrated can be shown to produce the same result as )#. . 6f
course, the expression derived for the atmospheric wor( is valid for
both expansion or contraction of the system.
8sing )#s. and , )#. can be rearranged as
11
&ig. -.-7 Cifferent
modes of external wor(
in the energy flow for
the system in &ig. -.-5.
&ig. -.-: )valuation of
atmospheric wor(
transfer.
( )
( ) ( )
[ ]
; ;
; ;
/
;
; gen,univ
C
)
C

. (
i i i e e e
A
( u
(
d E T S p V
m - T s m - T s
dt
T
* + T S
T
+

_
+

,
& &
1 4 4 4 4 4 2 4 4 4 4 4 3
1 4 44 2 4 4 43
& & &
14 2 43
14 2 43
1 44 2 4 43
/efore we manipulate this e#uation any further, let us introduce the
concept of the dead state. or( is generally extracted during
gradient destroying natural process @ a hydraulic power plant needs a
difference in water height, a wind turbine re#uires a velocity
difference between the wind and the rotor blades, a thermal power
plant re#uires a temperature difference between the boiler and the
atmosphere, to name a few. hen a system comes to thermodynamic
e#uilibrium with #uiescent atmospheric air at sea level, there is no
mechanical, thermal or chemical driving force left for it to interact
with the surroundings. %n other words, there is no $uice or exergy left
in the system to extract useful wor( out of. 'uch a state with ; V ,
; z ,
;
T T
and
;
p p
is said to be at its #ea# state.
=etting bac( to the )#. , if the stream flowing through the
system is brought to e#uilibrium with the surrounding air at
;
p
and
;
T
, the combination property
;
- T s
carried by the stream reduces
to
( )
; ; ; ; ; ;
;
(e - T s - T s h +
;
;
pe +
;
; ; ; ; ;
T s h T s
%t should be emphasized that at the dead state the wor(ing substance
that ma(e up the system is at
;
p
and
;
T
with no (inetic or potential
energies. Fowever, other specific properties such as
;
h
,
;
s
, etc., are
properties of the wor(ing substance of the system, and are not
necessarily e#ual to that of the surrounding air.
ith the help of )#. , the term / of )#. can be modified by
using the dead state as a reference state for the combination property
( )
;
- T s
.
( ) ( ) ( ) ( )
( ) ( ) [ ]
; ; ; ; ; ; ; ;
& =
; ; ;
F
A
C C ) (
i i i e e e
i e
m - T s - T s m - T s - T s
- T s m m
1 1
] ]
+ +
& &
1 4 4 4 4 4 2 4 4 4 4 43 1 4 4 4 4 4 2 4 4 4 4 43
& &
1 4 4 44 2 4 4 4 43
The combination property carried by the mass flows
i
m&
and
e
m&
in
this e#uation is called the speci&ic &lo( exe$% and is represented by
the symbol

. Cefined in terms of intensive property


;
T
, and
1-
&ig. -.-< CA2T66A
Jou got a dead battery,
0adamK
A system in e#uilibrium
with the #uiescent
ambient atmosphere is
said to be at its dead
state.
specific properties
-
and
s
, ( ) ( )
; ; ; i
- T s - T s
must be an
extrinsic specific property since
-
is an extrinsic property. %t has a
zero value at the dead state and has the same unit as
-
, i.e., (*?(g.
The physical meaning of flow exergy will be discussed shortly and
plenty of examples will be covered in Chapter 5. Term F in the
above e#uation can be further simplified by employing )#. and the
mass balance e#uation, )#. .
( ) ( ) ( )
( ) ( )
( ) ( )
( )
; ; ; ; ; ;
; ;
; ; ; ;
; ; ; ; ; ; ; ;
; ; ; ;
F



i e
dm
- T s m m h T s
dt
d2 dS d d
mh T ms T
dt dt dt dt
d d
2 T S $ p V T S
dt dt
d
E T S p V
dt


+
+
& &
Ta(ing the term F into the "F' of )#. ,
( ) ( ) { }
; ; ; ; ; ; ;
A-F
d
E T S p V E T S p V
dt
+ +
The combination extensive system property that appears inside the
time derivative is now referenced at the dead state, i.e., its value at
the dead state is zero. This is called the exe$% of the system and has
the same unit as E , i.e., (*. The total exergy is represented by the
symbol 3pronounced phi4 and the corresponding specific property
by

, and are defined in )#. . hile is a total extensive property,

is an extrinsic property because it has extrinsic components such


as (e and pe.
'ubstituting )#. into )#. , and generalizing the number of
inlets, exits and T)2Es, we obtain the %ene$al exe$% balance
equation .
1+
2ate of increase of
Aet flow rate of Aet flow rate of
total exergy of
flow exergy into flow exergy out of
an open system.
the system. the system.

i i e e
i e
d
m m
dt

+

& &
1 4 2 4 3
1 4 2 43 1 4 2 43
;
Aet 2ate of exergy
transfer through heat.
u
2ate of irreversiblities
2ate of exergy transfer
through useful
external wor(.
.

(
(
(
T
*
T
+ /
_

&
1 44 2 4 43
& &
14 2 43
[ ]
( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( )
or exergy destruction
due to entropy generation.
; ; ; ; ; ; ;
; ; ; ; ;
; ; ; ; ;
;
(
where,
B) 9)
(e pe

sys
dV E T S p V E T S p V
$ $ T S S p V V
u u T s s p v v
- T s

+ +
+ + +
+ + +

1 44 2 4 43

( )
( ) ( )
; ; ;
1
; ; ;
; gen,univ

1;;; .;;;

- T s
V gz
h h T s s
/ T S

+ +

& &
Although the e#uation loo(s formidable at first sight, it lends
itself to interpretation $ust li(e all other balance e#uations derived so
far. The "F', as is usual, represents the time rate of increase of an
extensive property, the system exergy in this case. "i(e any other
total property of a non-uniform system 3see )#. 4 it can be obtained
by integrating or summing up the specific exergy

over the local


systems comprising the global system.
The 2F' lists all possible ways that affect the stored exergy
of a system. &low exergy, $ust li(e flow energy
-
, is carried by the
flow in and out of the system. Feat transferred into the system from
a T)2 at
; (
T T >
carries a fraction,
;
. ?
(
T T
, of itself as exergy.
Aote that for reservoir ; ( , i.e., the ambient atmosphere, this
fraction reduces to zero. That is, there is no exergy is transferred
through heat transfer between the system and the ambient
atmosphere. The implication of a cold reservoir, i.e.,
; (
T T <
, will be
discussed in 'ection +.-.-.+.
The exergy delivered by the system as useful wor(,
u
+
&
,
appears with a negative sign as it drains the system of its stored
exergy.
&inally, the entropy generation can be seen to produce a term
that must be always non-positive since
gen,univ
; S
&
3'econd "aw4. %t
is called the $ate o& exe$% #est$uction or the $ate o& i$$e)e$sibilit
and is represented by the symbol
/
&
.
1,
&ig. -.+; &low diagram
of exergy for an
extended system.
)ach term of this e#uation s(etched in the flow diagram of
&ig. -.+; will be explained with plenty of examples in the next two
chapters. A comparison of the flow diagrams for energy 3&ig. -..,4,
entropy 3&ig. -.174 and exergy 3-.+;4 can be helpful in understanding
the similarities and differences in the inventory of the three
properties in terms of a common framewor(.
3.2.1 F!(%s !+ E3e(0# B''n)e E,-'$.!n
As we did with the mass, energy and entropy balance e#uations, we
will customize the exergy e#uation in a similar manner for different
classes of systems.
*lose# Sstem Simpli&ication &or a closed system the mass transfer
terms drop out and )#. reduces to
;
.
( u
(
(
T d
* + /
dt T
_


,

& & &


6bviously, this form suits any instantaneous unsteady closed system.
*lose# P$ocess Simpli&ication &or an unsteady closed system going
through a process, )#. can be integrated from the b-state to the f-
state as outlined in 'ection -.-.- producing
;
finish finish
; gen,univ
begin begin
.
where, , and,
" b ( u
(
(
( ( u u
T
* + /
T
* * dt + + dt / T S
_


,


& &
The simplified form of the exergy e#uation for a closed process can
be used to explore the physical meaning of some of its terms. &or
instance, when a closed system, say, a warm cup of coffee cools
down from a temperature
b
T
to the room temperature
;
T
by re$ecting
loss
*
amount of heat, no useful wor( is produced. Fowever, the
exergy e#uation can be used to see if it is possible to construct a
clever device to extract useful wor( out of this cooling process. ith
; (
T T
, )#. simplifies as
u b "
+ /
Clearly it is possible to convert some of the exergy in a coffee mug
into useful wor(. %f the final state is the dead state, i.e., the coffee in
the mug reaches e#uilibrium with the environment,
;
"

. /eing a
non-negative #uantity, the irreversibility / can be seen to reduce the
useful wor( output. %n fact for a regular coffee cup, the exergy is
15
&ig. -.+- )nergy flow
diagram for )#. . The
direction of the heat
arrow is reversed since
loss
* * 3
loss
* is a
positive #uantity4.
&ig. -.+. A smart
coffee mug that
produces electricity as
the coffee cools down to
room temperature.
&ig. -.+1 The exergy of
a warm coffee mug is
the maximum possible
useful wor( that can be
extracted as the coffee
comes to e#uilibrium
with the surrounding air.
completely destroyed by / . %f the irreversibility can be eliminated -
and the 'econd "aw does permit
gen,univ
; S
as a limiting ideal case
- the wor( produced is maximized.
,max u b "
+
;
/
;
The exergy of a system, therefore, has the simple interpretation of
the maximum possible useful wor( that can be extracted out of it by
transferring heat with only the atmospheric T)2.
6ne may naturally as(, why cannot we use an energy
analysis instead to predict the maximum wor( transferH The next
chapter will be devoted to analysis such as this for closed system. As
a preview let us see what the energy and entropy e#uation predict
about the system at hand. 8sing the solid?li#uid model for the coffee,
the energy e#uation, )#. , can be simplified as
( )
B)
" b
E $ $ +
;
9) + ( )
( ) ( )
;
loss
loss ; loss

b " v b
* + * +
+ $ $ * mc T T *


/y eliminating
loss
*
completely it seems that the change in internal
energy can be completely converted into wor(, i.e.,
( )
max ; v b
+ mc T T
. The 'econd "aw however has been completely
disregarded in arriving at this conclusion. %n fact, an entropy
e#uation for the process, )#. , yields
( )
loss
gen gen,univ
;
; loss
gen,univ
;
ln
" b
B
v
b
* *
S S S S S
T T
T *
S mc
T T

+ +
+
The first term on the 2F' being negative, an elimination of
loss
*

would result in a negative
gen,univ
S
, which is a direct violation of the
'econd "aw. Any conclusions from the energy e#uation, therefore,
must be tested for compliance with the 'econd "aw. Conclusions
derived from the exergy balance e#uation, on the other hand, do not
run into these types of difficulty as the exergy e#uation is firmly
rooted in the combination of mass, energy and entropy e#uations.
*lose# Stea# Simpli&ication &or a steady system, the time
derivative of , a global property, is set to zero and )#. simplifies
to
;
; .
( u
(
(
T
* + /
T
_


,

& & &


17
&ig. -.++ The change in
$ and S according to
the solid?li#uid model as
the temperature goes
from
b
T to
;
T . 0ass of
the cup is neglected in
these expressions.
Open Stea# Simpli&ication The steady state exergy e#uation,
similarly, can be expressed in an algebraic form as the time
derivative drops out.
;
; .
i i e e ( u
i e (
(
T
m m * + /
T

_
+

,

& & &
& &
The destruction of exergy term ma(es it impossible to express this
e#uation in the what-comes-in-must-go-out format.
To explore the physical meaning of flow exergy, consider a
steady stream of fluid flowing through a system which has heat
interactions with only the atmospheric reservoir. The power
delivered by this device can be obtained from )#. as
( )
u i i e e i i e
+ m m / m /
& & &
& & &
The useful wor( is maximized when the exergy destruction is
eliminated and the flow exits at its dead state.
,max u i i e e
+ m m
&
& &
;
/
&
;
i i i
m
&
&
The flow exergy, therefore, can be interpreted as the maximum
possible useful wor( delivered per unit mass of the flow if the flow
is brought to dead state by exchanging heat with the atmospheric
T)2. Complete analysis of open systems will be carried out in
Chapter , at which point this will be a simple exercise to show that a
&irst "aw analysis alone cannot be used for predicting the maximum
wor( transfer since the 'econd "aw may be violated.
Open P$ocess Simpli&ication &or a process involving an open
system )#. can be integrated from the begin to the finish state.
8sing the uni"orm "lo' uni"orm state assumption, the exergy
e#uation reduces to
;
.
" b i i e e (
i i (
(
T
m m * /
T

_
+

,

where many of the symbols have been explained in connection with
the corresponding form of the energy and entropy e#uations.
3.& omentum Balance Equation
The momentum e#uation will not be used until chapter 7, where we
will discuss modern $et engines. Fowever, this is the appropriate
place to cast AewtonEs law into our common framewor( of a balance
e#uation that applies to all systems, open or closed.
1:
&ig. -.+, &low diagram
of exergy simplified for
an open steady system.
Ne(ton-s Secon# La( o& Motion for a closed system can be stated
as
The rate o" change o" momentum o" a closed system is e0ual to the
net external "orce applied on the system#
/ecause momentum and force are vectors, the momentum e#uation
can be split into three independent e#uations along
x
,
y
, and
z

directions in the Cartesian coordinates. Along the
x
direction,
AewtonEs 'econd "aw can be written as
[ ]
-
(A (g.m
(A ; where, (A.s> s
.;;; A s
c
c x x
x x
dM mV
, M
dt
1

1
]

6bserve that in this e#uation the unit of force is (A to be consistent


with all other balance e#uations and the unit of pressure, a deviation
from the standard use of A in mechanics.
'ubstituting
x
M
and
?.;;;
x
V
for B and b respectively in
the 2T), )#. , we obtain the %ene$al momentum balance equation.
, ,
2ate of increase
Aet -momentum flow rate Aet -momentum flow rate
of -momentum
into the system. out of the system.
of an open system.
?.;;; ?.;;; L
x
i x i e x e x
i i
x x
x
dM
mV mV ,
dt


& &
1 4 2 43
1 4 4 2 4 43 1 4 4 2 4 4 3
[ ]
Aet 2ate of
generation
of -momentum.
(A
x
1 2 3
As in the energy and entropy e#uation, the superposition of the
closed and open system is exploited to substitute
c
x x
, , . "i(e any
other extensive property, momentum can be transported in and out of
the system with mass. "i(e the entropy generation term in the
entropy e#uation, the net external force acts as a source of
momentum.
&or closed systems, AewtonEs law of motion is recovered.
( ) ?.;;;
or, or,
.;;;
x x x
x x x
d mV dM ma
, , ,
dt dt


where,
x
a
is the acceleration in the
x
direction.
&or an open steady system )#. reduces to
, ,
.
;
.;;;
i x i e x e x
i i
mV mV ,
_
+

,

& &
These are the only forms of the momentum e#uation that will be
used in Chapter 7 and .., although other forms can be derived as
easily.
1<
&ig. -.+5 An external
force is necessary to
balance the momentum
flow.
The momentum e#uation in the
y
or
z
directions can be written by
simply changing the subscript
x
into
y
and
z
respectively.
3.' Balance Equations Summary
The complete set of governing balance e#uations are summarized
below for selected categories of systems that will be fre#uently
encountered in the rest of the chapters. Although momentum
e#uation is also included, often the MEEE equations -the mass,
energy, entropy and exergy e#uations -constitute the core governing
balance e#uations in thermodynamic problems.
3.4.1 Gene(' F!(%
The following are the balance e#uations for open and unsteady
systems. All other forms can be derived from this e#uation set.
Mass 3)#. 4

(g

s
i e
i e
dm
m m
dt
1

1
]

& &
Ene$% 3)#. 4
[ ]
ext
1
ext
(
where, ;
1;;; .;;;
i i e e
i e
B )
dE
m - m - * +
dt
V gz
- h (e pe h + + +
+
+ + + + +

& &
& &
& & &
Ent$op 3)#. 4
gen
(

B
i i e e
i e
B
dS *
ms m s S
dt T
1
+ +
1
]

&
&
& &
Exe$% 3)#. 4
[ ]
( ) ( )
( ) ( )
;
; ; ; ; ; ; ;
; ; ; ;
; gen,univ
. (
where,


i i e e ( u
i e (
(
T d
m m * + /
dt T
E T S p V E T S p V
- T s - T s
/ T S

_
+

,
+ +


& & &
& &
& &
Momentum 3)#. 4
-;
&ig. -.+5.. 'ystem
schematic to accompany
'ection -.<...
[ ]
, ,
1
.
(A
.;;;
(A (g.m
where, (A.s> s
.;;; A s
x
i x i e x e x
i i
x
x
dM
mV mV ,
dt
mV
M
_
+

,
1

1
]

& &
3.4.& C!se" S#s$e%s
Considerable simplification results as the mass transfer terms are
dropped from the balance e#uations for closed systems. 0oreover,
flow wor( being completely absent,
ext
+ +
& &
.
Mass 3)#. 4
[ ]
(g
; ; constant (g
s
dm
m
dt
1

1
]
Ene$% 3)#. 4
( ) [ ] ( ;
B )
dE
* + * + +
dt
+
& & & & &
Ent$op 3)#. 4
gen
(

B
B
dS *
S
dt T
1
+
1
]
&
&
Exe$% 3)#. 4
[ ]
;
. (
( u
(
(
T d
* + /
dt T
_


,

& & &


Momentum 3)#. 4
[ ] (A ; constant
x
x x
dM
, M
dt

3.4.3 C!se" P(!)ess


hen an unsteady closed system undergoes a change of state from a
begin-state to a finish-state, it is said to have executed a closed
process.
Mass 3)#. 4
-.
&ig. -.+5.1 'ystem
schematic to accompany
'ection -.<.1.

constant M(gN m
Ene$% 3)#. 4
( )
" b B )
E E E * + * + + +
Ent$op 3)#. 4 gen " b
B
*
S S S S
T
+
Exe$% 3)#. 4
;
.
" b ( u
(
(
T
* + /
T
_


,


3.4.* C!se" S$e'"#
hen the image of a closed system ta(en with a state camera does
not change with time, the time derivative of all global properties
becomes zero and the system is said to be a closed steady system.
3losed cycles, as will be shown in the next chapter, can be treated as
a special case of a closed steady system.
Mass 3)#. 4 constant m
Ene$% 3)#. 4 ; * +
& &
Ent$op 3)#. 4
gen
;
B
*
S
T
+
&
&
Exe$% 3)#. 4
;
; .
( u
(
(
T
* + /
T
_


,

& & &


3.4./ Open S$e'"#
hen the image of an open system ta(en with a state camera does
not change with time, the time derivative of all global properties
becomes zero and the system is said to be an open steady system.
Mass 3)#. 4

(g
;
s
i e
i e
m m
1

1
]

& &
Ene$% 3)#. 4
-1
&ig. -.+5.- 'ystem
schematic to accompany
'ection -.<.-.
&ig. -.+5.+ 'ystem
schematic to accompany
'ection -.<.+.
&ig. -.+5., 'ystem
schematic to accompany
'ection -.<.,.
ext
; M(N
i i e e
i e
m - m - * + +

& &
& &
Ent$op 3)#. 4
gen
(
;
B
i i e e
i e
B
*
ms m s S
T
1
+ +
1
]

&
&
& &
Exe$% 3)#. 4
[ ]
;
; . (
i i e e ( u
i e (
(
T
m m * + /
T

_
+

,

& & &
& &
Momentum 3)#. 4
[ ]
, ,
.
; (A
.;;;
i x i e x e x
i i
mV mV ,
_
+

,

& &
3.4.1 Open P(!)ess
hen an unsteady open system undergoes a change of state from a
begin-state to a finish-state, it is said to have executed an open
process. The inlet and exit states are carefully chosen so that their
properties can be assumed to remain unchanged over time and over
the cross-sectional areas. This is (nown as the uni"orm state uni"orm
"lo' assumption.
Mass 3)#. 4
;
" b i e
i e
m m m m m

Ene$% 3)#. 4
ext " b i i e e
i e
E E E m - m - * + +

Ent$op 3)#. 4
gen " b i i e e
i i
B
*
S S S ms m s S
T
+ +

Exe$% 3)#. 4
;
.
" b i i e e (
i i (
(
T
m m * /
T

_
+

,

--
&ig. -.+5.5 'ystem
schematic to accompany
'ection -.<.5.

EXAMPLE 3-/ 0))) )#uations for a Closed 9rocess.
Cevelop the appropriate form of 0))) 3mass, energy, entropy and
exergy4 e#uations for the following problem.
Cetermine the amount of heat necessary to raise the temperature of .
(g of aluminum from -;
o
C to .;;
o
CH
SOLUTION The customized form of balance e#uations for various
classes of systems have been already identified in this chapter.
Therefore, the tas( at hand is to simplify the problem with suitable
assumptions and choose the appropriate bloc( of e#uations from
'ection -.<.
Simpli&ication The system, obviously closed, is uniform so that a
single state describes its state at a given time. The system is
obviously unsteady, its image ta(en with a state camera changing
with time. Fowever, the problem description clearly indicates the
system travels from a b-state to a f-state, the hallmar( of any
process. The bloc( of e#uation summarized in 'ection -.<.-,
therefore, describes the appropriate form of the balance e#uations.
The e#uations can be further simplified by noting that changes in
B) and 9) are most li(ely negligible ma(ing E $ .
Mass constant m
Ene$%
E $ %E +
;
&E +
;
* +
;
( )
6r,
" b
$ m u u *
Ent$op gen,univ
(
" b
(
(
*
S S S S
T
+

Exe$%
;
.
" b ( u
(
(
T
* +
T
_


,

;
; gen,univ
T S
Simpli&ication Usin% TEST 'tarting at the Caemons page,
progressively navigate through Closed, 9rocess, =eneric and
8niform pages. A system schematic and the set of e#uations that
describe that system are displayed at the bottom of the page. An
appropriate material model is selected as the last step before the
Closed 9rocess daemon is launched.
!iscussion The boundary temperature is un(nown in this problem.
'ince the body is being heated to a temperature of .;;
o
C, at least
one of the heat sources must be at a temperature of .;;
o
C or more.
Also note that the 0))) e#uations derived in this problem are
-+
&ig. -.+7 Feating the
bloc( from a b-state to a
f-state constitutes a
closed process.
applicable regardless of the model chosen. %ndividual terms of the
balance e#uations will be discussed in the next two chapters. Aotice
that the e#uations are derived here for the extended system. Also
observe that the balance e#uations in their current form are
independent of the material model.
EXAMPLE 3-3 0))) )#uations for a Closed 9rocess.
Cevelop the appropriate form of 0))) 3mass, energy, entropy and
exergy4 e#uations for the following problem.
A piston-cylinder device initially contains 1; g of saturated water
vapor at -;; (9a. A resistance heater is operated within the cylinder
with a current of ;.+ A from a 1+; O source until the volume
doubles. At the same time a heat loss of + (* occurs. Cetermine the
final temperature and the duration of the process.
SOLUTION To develop a customized set of 0))) e#uations.
Simpli&ication The simplification carried out in )x. --1 applies to
this problem as well. %n addition to heat transfer, there are two
modes of wor( transfer, electrical and boundary wor(. The closed
process e#uations of 'ection -.<- can be simplified as follows.
Mass constant m
Ene$% E $ %E +
;
&E +
;
B )
* + * + +
( )
6r,
" b B )
$ m u u * + +
Ent$op gen,univ
(
" b
(
(
*
S S S S
T
+

Exe$%
;
.
" b ( u
(
(
T
* +
T
_


,

;
; gen,univ
T S
Simpli&ication Usin% TEST The procedure remains unchanged to
the one described in the last problem.
!iscussion 'team trapped in a piston-cylinder device apparently has
no similarity with the bloc( of aluminum of the last example.
Fowever, as far as the governing 0))) e#uations are concerned,
the only difference between the two systems is the presence of wor(
transfer in this problem. As in the previous problem, the balance
e#uations in their current form are independent of the material
model.
EXAMPLE 3-0 0))) )#uations for a Aon-0ixing Closed 9rocess.
-,
&ig. -.+: 'team
undergoes a closed
process $ust li(e the
bloc( in &ig. -.+7.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
A +; (g aluminum bloc( at .;;
o
C is dropped into an insulated tan(
that contains ;., m
-
of li#uid water at 1;
o
C. Cetermine the entropy
generated in this process.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication ater and the bloc( constitute a non-uni&o$m close#
sstem going through a process in this problem. Two states, one for
the bloc( and one for water, can be used to describe the composite
begin state. At the end of the process, even though the temperature is
uniform, the finish-state still re#uires a composite description as the
density is different for the two sub-systems. Cesignating the two
subsystems as A and /, and neglecting any changes in B) and 9),
the closed process e#uations can be simplified as follows.
Mass constant; constant;
A B
m m
Ene$% E $ %E +
;
&E +
;
*
;
+
;
( ) ( )
, , , ,
6r, ;
" b A " A B " B A b A B b B
$ $ $ m u m u m u m u + +
Ent$op
(
" b
(
*
S S S
T

;
gen,univ
(
S +

( ) ( )
, , , , gen
6r,
" b A " A B " B A b A B b B
S S S m s m s m s m s S + +
Exe$%
" b (
*
;
;
.
u
(
(
T
+
T
_


,

;
; gen
T S
( ) ( )
, , , , ; gen,univ
6r,
" b A " A B " B A b A B b B
m m m m T S + +
Simpli&ication Usin% TEST Aavigate through the 'ystems, Closed,
9rocess, =eneric, Aon-8niform, Aon-0ixing, pages to display the
progressively simplified system schematic and balance e#uations.
!iscussion The subsystems are closed themselves since there is no
mass transfer between them. %n T)'T such systems are called non-
mixin% non-uni&o$m systems. %n the following example, on the
other hand, the subsystems of a non-uniform system can be seen to
be mixin%. As in the previous problem, the balance e#uations in their
current form are independent of the material model.
EXAMPLE 3-1 0))) )#uations for a 0ixing Closed 9rocess.
-5
&ig. -.+< The composite
system goes through a
non-mixing closed
process.
&ig. -.,; The
composite closed system
goes through a mixing
process.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
A ;., m
-
rigid tan( containing hydrogen at +;
o
C, 1;; (9a is
connected to another . m
-
rigid tan( containing hydrogen at 1;
o
C,
5;; (9a. The valve is opened and the system is allowed to reach
thermal e#uilibrium with the surroundings at .,
o
C. Cetermine the
irreversibility in this process. Assume variable
p
c
.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication /y drawing the system boundary as shown in the
accompanying figure, gases in the two tan(s, each of which acts as
an open system during the process, behave li(e a closed system. %n
the resulting non-uniform system, two states, one for tan( A and one
for tan( /, must be used to describe the composite begin state. At the
end of the mixing process, the finish state is uniform and can be
represented by a single state. Aeglecting any changes in %E and
&E , the closed process e#uations can be simplified as follows.
Mass constant;
A B
m m +
Ene$%
E $ %E +
;
&E +
;
* +
;
( ) ( )
, ,
6r,
" b A B " A b A B b B
$ $ $ m m u m u m u * + +
Ent$op gen
(
" b
( (
*
S S S S
T
+


( ) ( )
, , gen,univ
;

" b A B " A b A B b B
*
S S S m m s m s m s S
T
+ + +
Exe$%
;
.
" b (
(
T
*
T
_


,
;
u
(
+

;
; gen,univ
T S
( ) ( )
, , ; gen,univ

" b A B " A b A B b B
m m m m T S + +
Simpli&ication Usin% TEST Aavigate through the 'ystems, Closed,
9rocess, =eneric, Aon-8niform, 0ixing, pages to display the
progressively simplified system schematic and balance e#uations.
!iscussion An interpretation of different terms of the balance
e#uation is postponed until the next chapter. %f the valve is closed
before mixing is complete, the finish state must be expressed through
a composite state $ust li(e the begin state. The balance e#uations, it
should be noted, are independent of the material model.
-7
EXAMPLE 3-2 0))) )#uations for a Closed 'teady 'ystem.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
A.; m
1
bric( wall separates two chambers at ,;; B and -;; B
respectively. %f the rate of heat transfer is ;., (?m
1
, determine the
entropy generation rate and the rate of exergy destruction in the wall.
Assume the wall surface temperatures to be the same as the ad$acent
chamber temperatures. Also assume steady state.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication The bric( wall in this problem, obviously, constitutes
a closed system at steady state. /ecause the area of the wall at the
edges are negligible compared to the two main faces, heat transfer
through the end faces can be neglected. Also the time derivatives of
B) and9) can be assumed zero.
Mass
constant; m
Ene$%
;
2 3
* * + +
& & &
;
;
2 3
* *
& &
Ent$op
gen,univ
;
(
(
(
*
S
T
+

&
&

gen,univ
. .

2
3 2
S *
T T
_


,
& &
Exe$%
;
; .
( u
(
(
T
* +
T
_


,

& &
;
; gen,univ
T S
&

; ;
; gen,univ
; . .
2 3
2 3
T T
* * T S
T T
_ _


, ,
& & &
Simpli&ication Usin% TEST Aavigate through the 'ystems, Closed,
'teady pages to display the progressively simplified system
schematic and balance e#uations .
!iscussion 6nce again we will defer interpretation of various terms
until the next chapter. ith
2 3
* *
& &
, the exergy e#uation can be
shown to reduce to entropy e#uation for this particular system.
Aotice that the e#uations are derived here for the extended system.
EXAMPLE 3-3 0))) )#uations for an 6pen 'teady 'ystem.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
Carbon dioxide enters steadily a nozzle at -, psia, .+;;
o
&
, and 1,;
ft?s and exits at .1 psia and .1;;
o
&
. Assuming the nozzle to be
adiabatic and the surroundings to be at .+.7 psia, 5,
o
&
, determine
-:
&ig. -.,. A closed
system at steady state.
&ig. -.,1 A nozzle
operating at steady state.
3a4 the exit velocity, and 3b4 the entropy generation rate by the device
and the surroundings.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication The image of the nozzle ta(en with a state camera
remains frozen even though the state of the fluid flowing through the
nozzle changes. Fence, a nozzle is an open steady device. Although
change in 9) can be neglected, the purpose of a nozzle is to
accelerate a flow and, therefore, the change in B) must be
considered significant. /ecause there is a sin%le &lo( through the
nozzle, the summation over inlets and exits of the open, steady
e#uations of section -.<., reduce to
Mass
i i
m m m & & &
Ene$%
( ) ;
i e
m - - * +
&
&
;
ext
+
&
;
;
i e
- -
Ent$op ( ) ;
(
i e
(
*
m s s
T
+
&
&
( )
;
gen,univ gen,univ i e
(
S m s s S + +

& &
&

gen,univ

e i
S
s s
m
+
&
&
Exe$% ( ) ;
i e (
m * +
&
&
;
;
.
u
(
(
T
+
T
_


,

&
;
; gen,univ
T S
&

; gen,univ

e i
T S
m

&
&
Simpli&ication Usin% TEST Aavigate through the 'ystems, 6pen,
'teady, =eneric, and 'ingle-&low pages to display the progressively
simplified system schematic and balance e#uations.
!iscussion %ndividual terms of the balance e#uations will be
discussed in the next two chapters. Aotice that the e#uations are
derived here for the extended system. Also observe that the balance
e#uations in their current form are independent of the material
model.
EXAMPLE 3-4 0))) )#uations for a 0ixing, 6pen 'teady
'ystem.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
"i#uid water at .;; (9a and .;
o
C is heated by mixing it with an
un(nown amount of steam at .;; (9a and 1;;
o
C, and by heating
-<
&ig. -.,- A steady state
mixing chamber.
the mixing chamber with a resistance heater with a power rating of ,
(. "i#uid water enters the chamber at . (g?s, and the chamber
looses heat at a rate of ,;; (*?min with the ambient at 1,
o
C. %f the
mixture leaves at .;; (9a and ,;
o
C, determine 3a4 the mass flow
rate of steam, and 3b4 the entropy generation rate during mixing.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication The mixing chamber can be assumed to operate at
steady state. Although heat is transferred from the electrical heating
elements to the wor(ing fluid, it is electrical power
el
+
&
that crosses
the boundary and, therefore, must appear in the energy and exergy
e#uations as
ext
+
&
and
ext,u
+
&
respectively. Two inlet states, i.-'tate
and i1-'tate, and one exit state, e-state, are re#uired in this multi
&lo( mixin% configuration. The open, steady e#uations of section
-.<., reduce to
Mass
. 1 i i e
m m m + & & &
Ene$%
. . 1 1 el
; ;
i i i i e e
m - m - m - * + + +
& &
& & &
Ent$op
. . 1 1 gen,univ
;
;
i i i i e e
*
m s m s m s S
T
+ + +
&
&
& & &
Exe$%
. . 1 1
;
i i i i e e (
m m m * + +
&
& & &
;
;
; gen,univ
.
u
(
(
T
+ T S
T
_


,

& &
. . 1 1 el ; gen,univ
;
i i i i e e
m m m + T S +
& &
& & &
Simpli&ication Usin% TEST Aavigate through the 'ystems, 6pen,
'teady, =eneric, 0ulti-&low-0ixed pages to display the
progressively simplified system schematic and balance e#uations .
!iscussion %ndividual terms of the balance e#uations will be
discussed in the next two chapters. Aotice that the e#uations are
derived here for the extended system. Also observe that the balance
e#uations in their current form are independent of the material
model.
EXAMPLE 3-5 0))) )#uations for a Aon-0ixing, 6pen, 'teady
'ystem.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
'team enters a closed feedwater heater at ... 09a and 1;;
o
C and
leaves as saturated li#uid at the same pressure. &eedwater enters the
+;
&ig. -.,+ A closed feed
water heater used in a
steam power plant.
heater at 1., 09a and ,;
o
Cand leaves .1
o
C below the exit
temperature of steam. Aeglecting any heat losses, determine 3a4 the
mass flow rate ratio and 3b4 the entropy generation rate of the device
and its surroundings. Assume surroundings to be at 1;
o
C.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication The closed feed water heater shown in the
accompanying figure is a heat exchanger, where the flow of water is
heated by the flow of steam. &or this non-mixin% multi-&lo(
configuration, two inlet states, i.- and i1-states, and two exit states,
e.- and e1-states, describe the two flows, flow-A from i. to e. and
flow / from i1 to e1. Clearly there is no external wor( transfer for
this passive device. The open, steady e#uations of section -.<.,
simplify into
Mass
. . 1 1
; ;
i e A i e B
m m m m m m & & & & & &
Ene$%
. . 1 1 . . 1 1
;
i i i i e e e e
m - m - m - m - * + +
&
& & & &
;
ext
+
&
;
;

( ) ( )
. . 1 1 A i e B e i
m - - m - - & &
Ent$op
. . 1 1 . . 1 1
;
i i i i e e e e
*
m s m s m s m s + +
&
& & & &
;
gen,univ
B
S
T
+
&
( ) ( )
. . 1 1 gen,univ
;
A i e B i e
m s s m s s S + +
&
& &
Exe$%
. . 1 1 . . 1 1
;
i i i i e e e e
m m m m + & & & &

(
* +
&
;
;
.
u
(
(
T
+
T
_


,

&
;
; gen,univ
T S
&
( ) ( )
. . 1 1 ; gen,univ
;
A i e B i e
m m T S +
&
& &
Simpli&ication Usin% TEST Aavigate through the 'ystems, 6pen,
'teady, =eneric, 0ulti-&low Aon-0ixing pages to display the
progressively simplified system schematic and balance e#uations .
!iscussion %ndividual terms of the balance e#uations will be
discussed in the next two chapters.
EXAMPLE 3-16 0))) )#uations for an 6pen 9rocess.
Cevelop the appropriate form of 0))) e#uations for the following
problem.
An insulated rigid tan( is initially evacuated. A valve is opened, and
air at .;; (9a 1;
o
C enters the tan( until the pressure in the tan(
+.
&ig. -.,, The selection
of the inlet state on the
outer side of the valve
ensures that 'tate-i
remains unchanged
during the open process.
reaches .;; (9a when the valve is closed. Cetermine the final
temperature of the air in the tan(. Assume variable specific heats.
SOLUTION To simplify the problem so that the balance e#uations
can be reduced to one of the customized forms discussed in this
chapter.
Simpli&ication The tan(, an open system, goes from a vacuum b-
state to a filled f-state as air from the supply line rushes in. %f the i-
state is located above the position of the valve, its thermodynamic
state at all times can be considered identical to that in the supply
line. %n this open-p$ocess , there is no external wor( or heat
transfer. The open, process e#uations of section 1.<., simplify into
Mass
" b
m m m
;
; 6r,
i " i
m m m
Ene$%
" b
E E
;
i i
m - * +
;
ext
+
;
;
(e
" "
m u +
;
pe +
( )
;
(e
i i
m h +
;
pe +
( )
;

" i
u h
Ent$op
" b
S S
;
i i
*
ms +
;
gen,univ
gen,univ
gen,univ


B
" " i i
" i
"
S
T
m s ms S
S
s s
m
+
+
+
Exe$%
" b

;
i i (
m * +
;
;
.
u
(
(
T
+
T
_


,

;
; gen,univ
; gen,univ
; gen,univ


" " i i
" i
"
T S
m m T S
T S
m



Simpli&ication Usin% TEST Aavigate through the 'ystems, 6pen,
9rocess pages to display the progressively simplified system
schematic and balance e#uations.
!iscussion %ndividual terms of the balance e#uations will be
discussed in the next two chapters.
+1
3.1( Summary
The fundamental governing e#uations for the interactions between a
system and its surroundings are derived in a common format called
the balance e#uation in this chapter. The goal is to express the
governing e#uations in a customized format for a given system. The
2eynolds transport e#uation or the 2T) relates the rate of change of
any total extensive property of an open system at a given instant with
that of a closed system passing through, which happens to occupy
the entire open system at that time. ith the help of 2T) the
fundamental laws of thermodynamics, postulated for a closed
system, are converted into balance e#uation for a very general
system.
%n 'ection -.- systems are classified into a tree structure with
different branches representing groups of systems that show some
similar patterns. 0ass balance e#uation is derived and expressed in
different formats in 'ection -.+. 'imilarly, energy, entropy, exergy,
and momentum e#uations are derived in 'ections -., through -.:.
&inally, in 'ection -.< the complete set of e#uations, called the
0))) e#uations are summarized for important classes of systems
that are often encountered in the practice of thermodynamics.
The next two chapters are devoted to understanding the
various e#uations derived in this chapter through comprehensive
analysis of various closed and open systems.
3.11 )nde%
anchor states..........................<
atmospheric wor(................11
axioms.....................................
balance e#uation....................+
/alance )#uation...................-
/alance )#uations...................
Closed 9rocess &orm
'ummary......................-.
Closed 'teady &orm
'ummary......................-1
6pen 9rocess &orm
'ummary......................--
6pen 'teady &orm
'ummary......................-1
/alance )#uations, Closed
'ystems 'ummary...........-.
/alance )#uations, =eneral
&orm 'ummary................-;
begin-state..............................:
Classification of 'ystems......5
conservative form.................1
dead state.............................1-
)nergy /alance........................
Cifferent &orms.........+, .<
)ntropy /alance )#uation....,
exergy............................1;, 1+
)xergy /alance........................
Cifferent &orms..............15
)xergy /alance )#uation....1;
exergy destruction...............1,
extended system....................7
final-state...............................:
&irst "aw................................
flow diagram.........................;
general balance e#uation.......5
general balance e#uation,
energy...............................-
general balance e#uation,
entropy..............................:
+-
general balance e#uation,
exergy..............................1+
general balance e#uation,
momentum.......................1<
generalized friction...............5
heat reservoir.......................1.
irreversibility..................7, 1,
irreversible............................7
0ass /alance...........................
Cifferent &orms................
mass balance e#uation..........;
0ass /alance )#uation. .;, ..
0))) e#uations..................-;
mixing systems....................-5
0omentum /alance )#uation
.........................................1:
multi flow............................+;
multi flow, non-mixing........+.
AewtonEs 'econd "aw.........1<
non-mixing systems.............-5
non-uniform systems...........-5
open process....................<, +1
6pen 'ystems........................7
process...................................:
reversible..............................7
2eynolds Transport Theorem,
2T)........................................,
'econd "aw..........................,
single flow...........................-<
specific flow energy.............-
steady flow energy e#uation.,
steady state.............................7
'teady 'ystems......................7
'ystem classification............;
T)2......................................1.
thermal energy reservoir......1.
uniform and steady flow........<
unsteady.................................7
8nsteady %nstantaneous.........:
++

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