PROPERTIES OF PURE SUBSTANCES

PART 1 : STEAM
1.0 Importance of steam
Pure substance is a substance that has fixed chemical composition throughout. Example of a pure
substances are water, helium and carbon dioxide.
A pure substance can be either single element / compound or a homogeneous mixture of various
chemical elements / compound. Air for example is a mixture of several gases, but it is often
considered to be pure substance because it has uniform chemical composition. owever, a mixture
of oil and gas is not a pure substance because oil is not soluble in water.
Figure 3.0
!team is the most common wor"ing fluid used in power generation plant. #his is because of its
desirable characteristic such as low cost, availabilit$ and high enthalp$ of vapori%ation. #he steam
power plant mainl$ consists of four ma&or parts. 'igure (.0 shows the steam power plant ma&or
components which are boiler, turbine, condenser and compressor.
'uel )coal, nuclear or natural gas * will be burned to suppl$ heat to produce steam in the
boiler. !team is produced in boiler which reached superheated phase will be used to rotates the
turbine blades. #he rotation of the turbine, will isentropicall$ expands the steam and then
generates an electrical power which is transferred to power distributor before can be supplied to
our resident. #he steam which has been used or does not reached the superheated phase will be
converted into water again b$ the condenser. In the condenser, the temperature of the steam
remains constant. 'rom the condenser, the wet steam is compressed isentropicall$ until it returns
to its initial state in boiler again. #hese processes will continuousl$ repeated.
Boiler
Turbine
Condenser
Pump W
12
Q
23
W
34
1
2 3
4
5
Q
451
1.1 Phase and phase changes processes
1.1.1 Phase
!ubstances can be exist in different phases. At room temperature and pressure, copper is
solid, mercur$ is li+uid and nitrogen is a gas. Although phase changes in thermod$namic does not
concerned with the molecular structure, but it is ver$ helpful to have some understanding on
molecular phenomena in each phases.
Solid
, -istances between molecules is small
, Attractive forces of molecules on each other is large
, .annot move relative to each other
Liquid
, -istances between molecules is not much different
from solid but no
longer at fixed position
, Attractive forces of molecules on each other are wea"er
than solid
Gas
, #he molecules are far apart from each other
, #he molecules move about at random
, .onsiderabl$ higher energ$ level than li+uid
1.1./ Phase,change processes
#here are man$ practical situation where two phases of a pure substance coexist in e+uilibrium. As
a familiar substance, water will be used to demonstrated the basic principle involved. .onsider a
piston,c$linder
State 1
- 0i+uid water at /01. and 1 atm
- .ompressed li+uid or subcooled li+uid
- eat is now transferred to water until temperature rises
- 0i+uid water at 201. and 1 atm
- 3ater expands, piston move up slightl$
State 2
- As more heat transferred, temperature "eep
rising until 1001. and 1 atm
- 3ater is still a li+uid but an$ heat addition will
cause water to vapori%ed
- !aturated li+uid state
State 3
- 4oiling starts
- #emperature stop rising ) constant *
- !aturated li+uid,vapor mixture state
State
- As we continue transferring heat, the
vapori%ation process will continue until last drop of li+uid is
vapori%ed
- !aturated vapor state
1.1.( Propert$ diagram for phase,changes process
!uperheated
steam
steam
steam
water
water
T
s
.ritical
point
Sauraed li!uid line
"r# sauraed seam line
P
2
$ %ons.
P
1
$ %ons.
C&'P()SS
*+Q,+"
()-+&.
W)T ST)/'
()-+&.
S,P)(0)/T)"
ST)/'
()-+&.
P
2
1 P
1
water
T!s dia"#a$ o% &u#e su'sta()e
P! dia"#a$ o% &u#e su'sta()e
(.1.2 'or most substances, the relationship among thermod$namic properties are too complex
to be expressed b$ simple e+uations. #herefore, properties are fre+uentl$ presented in
form of tables. !ome thermod$namic properties can be measured easil$ , but others
cannot and are calculated b$ using the relationship between them and measurable
properties.
E(t*al&+
Enthalp$ can be calculated using formula5
PV U H + ) 6 *
7r per unit mass
pv u h +
) 6/"g * where h enthalp$

u
specific internal
energ$

p
pressure

v
specific volume
a* Satu#ated Liquid a(d Satu#ated ,a&o# States
#he properties of saturated li+uid and saturated vapor for water are listed in !team
tables. 'igure (.10 shows parts from the steam table at /0 bar for saturated water
and steam.
P
v
Crii%al
poin
Sauraed li!uid line
"r# sauraed seam line
T
2
$ %ons.
T
1
$ %ons.
C&'P()SS
*+Q,+"
()-+&.
W)T ST)/'
()-+&.
S,P)(0)/T)"
ST)/'
()-+&.
T
2
1 T
1
[ ] bar
P
[ ] C
t

[ ] kg m
v
g
2
3

uf ug
8 "6/"g9
hf hfg hg
8"6/"g9
sf sfg sg
8"6/"g:9
/0 /1/.( 0.0;;<= ;0= />00 ;0; 1?;0 /=;; /.22= (.?;( >.(20
'igure (.10
P refers to pressure in bar,
s
t
refers to saturated temperature for the state pressure,
g
v
refers to volume in saturated vapor,
f
u
refers to internal energ$ in saturated li+uid,
fg
u
is f g
u u
g
u
refers to internal energ$ in saturated vapor,
f
h
refers to enthalp$ in saturated li+uid,
fg
h
is f g
h h
g
h
refers to enthalp$ in saturated vapor
f
s
refers to entrop$ in saturated li+uid
fg
s
is f g
s s
g
s
refers to entrop$ in saturated vapor
b* Satu#ated Liquid!,a&o# Mi-tu#e
#he value of dr$ness fraction or +ualit$ of steam is between 0 to 1
3hen x @ 0 the steam is on the saturated li+uid line
3hen x @ 0 to 1 the steam is in the li+uid,vapor mixture region
3hen x @ 1 the steam is on the saturated vapor line
c* Su&e#*eated ,a&o#
P
(ts)
t 2.. 2/. 3.. 3/. .. /. /.. 0..
10
)1=;.;*
vg 0.1;22 v 0./0>1 0./(/? 0./<?0 0./?/< 0.(0>< 0.((0( 0.(<20 0.2010
ug /<?2 u />/( /=11 /=;2 /?=< /;<= (020 (1/2 (/;=
hg /==? h /?/; /;22 (0</ (1<? (/>2 ((=0 (2=? (>;?
sg >.<?> s >.>;< >.;/> =.1/2 =.(01 =.2>2 =.>1= =.=>1 ?.0/?
'igure (.11
'igure (.11 shows superheated steam table at 10 bar.
d* Co$&#essed Liquid
1./ Interpolation
1./.1 !ingle interpolation
!ingle interpolation method is used to determine the value of properties that is not available in
steam table. 'or example, to determine the value of sf at 21 bar.
[ ] bar
P
[ ] C
t

[ ] kg m
v
g
2
3

uf ug
8 "6/"g9
hf hfg hg
8"6/"g9
sf sfg sg
8"6/"g:9
20 /<0.( 0.02;==
2/ /<(./ 0.02=(/
10?/ />0/
10;/ />01
10?= 1=12 /?01
110/ 1>;? /?00
/.=;= (./=( >.0=0
/.?/( (.//> >.02;
3e have to refer to the steam table at 20 bar and 2/ bar. #he value for 21 bar is situated in
between these two values.
'irst, we have to build the table
#hen, we arrange it to form this e+uation
P ) bar * !f )"6/"g:*
20 /.=;=
21
2/ /.?/(
40 42
40 41
343 . 2 523 . 2
343 . 2

f
s
2
1
026 . 0
343 . 2

f
s
343 . 2 7 026 . 0 8
2
1
+
f
s
kgK kJ s
f
2 510 . 2
1././ -ouble interpolation

-ouble interpolation method is used to determine the value of properties that is not available in
steam table at two different condition. . 'or example, to determine the value of h at ;.< bar and
(/01.
P
(ts)
t 2.. 2/. 3.. 3/. .. /. /.. 0..
;
)1=<.2*
vg 0./12;
ug /<?1
hg /==2
sg >.>/(
v 0./(0< 0./<;= 0./?=2 0.(122 0.(210 0.(>=2 0.(;(= 0.22<?
u />/? /=12 /=;> /?== /;<; (021 (1/> (/;?
h /?(< /;2? (0<< (1>0 (/>> ((=/ (2?0 (>;;
s >.=<( >.;?0 =.1=> =.(</ =.<1< =.>>= =.?11 ?.0==
10
)1=;.;*
vg 0.1;22 v 0./0>1 0./(/? 0./<?0 0./?/< 0.(0>< 0.((0( 0.(<20 0.2010
ug /<?2 u />/( /=11 /=;2 /?=< /;<= (020 (1/2 (/;=
hg /==? h /?/; /;22 (0</ (1<? (/>2 ((=0 (2=? (>;?
sg >.<?> s >.>;< >.;/> =.1/2 =.(01 =.2>2 =.>1= =.=>1 ?.0/?
'or double interpolation, / method can be used.
MET1O2 1
'irst we must build the table
4 10
4 5 . 4
3055 3052
3055
1

h
1
5 . 0
3
3055
1

h
3055 7 3 8
1
5 . 0
1
+ h
kg kJ h 2 5 . 3053
1

4 10
4 5 . 4
3160 3155
3160
2

h
1
5 . 0
2
3160
2

h
3160 7 2 8
1
5 . 0
2
+ h
kg kJ h 2 3154
2

P ) bar * (00 (/0 (<0
; (0<< (1>0
;.< h1 h( h/
10 (0</ (1<?
300 350
300 320
5 . 3053 3154
5 . 3053
3

h
50
20
5 . 105
5 . 3053
3

h
5 . 3053 7 5 . 105 8
50
20
3
+ h
kg kJ h 2 3 . 3045
3

MET1O2 2
'irst we must build the table
300 350
300 320
3055 3160
3055
1

h
50
20
105
3055
1

h
3055 7 105 8
50
20
1
+ h
kg kJ h 2 3043
1

300 350
300 320
3052 3155
3052
2

h
50
20
106
3052
2

h
P ) bar * (00 (/0 (<0
; (0<< h1 (1>0
;.< h(
10 (0</ h/ (1<?
3052 7 106 8
50
20
2
+ h
kg kJ h 2 4 . 3044
2

4 10
4 5 . 4
3043 4 . 3044
3043
3

h
1
5 . 0
6 . 2
3043
3

h
3043 7 6 . 2 8
1
5 . 0
3
+ h
kg kJ h 2 3 . 3045
3

PART 2 : GAS
232 PERFECT GAS
23231 2EFINATION
-id $ou "now, one important t$pe of fluid that has man$ applications in thermod$namics is the t$pe in which
the wor"ing temperature of the fluid remains well above the critical temperature of the fluidA In this case,
the fluid cannot be li+uefied b$ an isothermal compression, i.e. if it is re+uired to condense the fluid, then
cooling of the fluid must first be carried out. In the simple treatment of such fluids, their behavior is li"ened
to that a perfect gas. Although, strictl$ spea"ing, a perfect gas is an ideal which can never be reali%ed in
practice. #he behavior of man$ BpermanentC gases, e.g. h$drogen, ox$gen, air etc is ver$ similar to the
behavior of a perfect gas to a first approximation.
A perfect gas is a collection of particles that5
are in constant, random motion,
have no intermolecular attractions )which leads to elastic collisions in which no energ$ is
exchanged or lost*,
are considered to be volume,less points.
Dou are more familiar with the term BidealC gas. #here is actuall$ a distinction between these two terms but
for our purposes, $ou ma$ consider them interchangeable. #he principle properties used to define the state
of a gaseous s$stem are pressure )P*, volume )V* and temperature )T*. !I units )!$stems International* for
these properties are Pascal )Pa* for pressure, m
(
for volume )although liters and cm
(
are often substituted*,
and the absolute scale of temperature or :elvin ):*.
#wo of the laws describing the behavior of a perfect gas are 4o$leCs 0aw and .harlesC 0aw.
23232 LA4 OF I2EAL GAS
a5 Bo+le6s La7
#he 4o$leCs 0aw ma$ be stated as follows5
Provided the temperature T of a perfect gas remains constant, then volume, V of a given mass of gas is
inversel$ proportional to the pressure P of the gas, i.e. P 1/V )as shown in 'ig. (.1,1*, or P x V @ constant
if temperature remains constant.
Fi"u#e 331!1 Eraph P 1/V
If a gas changes from state 1 to state / during an isot*e#$al &#o)ess, then
P1 V1 @ P/ V/ @ constant )(.1*
P
12V
P 12V
If the process is represented on a graph having axes of pressure P and volume V, the results will be as
shown in 'ig. (.1,/. #he curve is "nown as a rectangular h$perbola, having the mathematical e+uation xy @
constant.
P
P1 1
P/ /
(
P(
V1 V/ V( V
Fi"u#e 331!2 P-V graph for constant temperature
'5 C*a#les6 La7
#he .harlesCs 0aw ma$ be stated as follows5
Provided the pressure P of a given mass of gas remains constant, then the volume V of the gas will be
directl$ proportional to the absolute temperature T of the gas, i.e.
V T, or V @ constant x T. #herefore V/T @ constant, for constant pressure P.
If gas changes from state 1 to state / during a )o(sta(t &#essu#e &#o)ess, then
If the process is represented on a P V diagram as before, the result will be as shown in 'ig. (./.
PV $ %onsan
%onsan
2
2
1
1

T
V
T
V
83.27
1 2
P
V
0
V
1
V
2
Fi"u#e 332 P-V graph for constant pressure process
)5 U(i8e#sal Gases La7
.harlesC 0aw gives us the change in volume of a gas with temperature when the pressure remains constant.
4o$leCs 0aw gives us the change in volume of a gas with pressure if the temperature remains constant.
#he relation which gives the volume of a gas when both temperature and the pressure are changed is
stated as e+uation (.( below.
i.e. )(.2*
Fo gases in practice obe$ this law rigidl$, but man$ gases tend towards it. An imaginar$ ideal that obe$s
the law is called a perfect gas, and the e+uation
is called the characteristic equation of state of a perfect gas.
#he constant, R, is called the gas constant. #he unit of R is Fm/"g : or 6/"g :. Each perfect gas has a
different gas constant.
#he characteristic e+uation is usuall$ written
PV = RT )(.<*
or for m "g, occup$ing V m
(
,
PV = mRT )(.>*
( )
9 366
m 0.54
m 0.32
9 615
:
3
3
1
2
1 2
2
2
1
1

,
_

V
V
T T
T
V
T
V
R
T
PV
%onsan 83.37
R
T
PV

2
2 2
1
1 1
T
V P
T
V P

Another form of the characteristic e+uation can be derived using the "ilogram,mole as a unit. #he kiogram-
moe is defined as a +uantit$ of a gas e+uivalent to m "g of the gas, where ! is the molecular weight of the
gas )e.g. since the molecular weight of ox$gen is (/, then 1 "g mole of ox$gen is e+uivalent to (/ "g of
ox$gen*.
'rom the definition of the "ilogram,mole, for m "g of a gas we have,
m = n! )(.=*
)where n is the number of moles*.
Fote5 !ince the standard of mass is the "g, "ilogram,mole will be written simpl$ as mole.
!ubstituting for m from e+uation (.= in e+uation (.>,
PV = n!RT or )(.?*
Fow "voga#ro$s hypothesis states that the volume of 1 mole of an$ gas is the same as the volume of 1
mole of an$ other gas, when the gases are at the same temperature and pressure. #herefore V/n is the
same for all gases at the same value of P and T. #hat is the +uantit$ PV/nT is constant for all gases. #his
constant is called the universa gas constant, and is given the s$mbol Ro.
i.e. )(.;*
or since !R = Ro then,
R
R
M
o
)(.10*
Experiment has shown that the volume of 1 mole of an$ perfect gas at 1 bar and 1
o
. is approximatel$
//.=1 m
(
. #herefore from e+uation (.?
'rom e+uation (.10 the gas constant for an$ gas can be found when the molecular weight is "nown, e.g. for
ox$gen of molecular weight (/, the gas constant is
9 ;2<g 5 . 254
32
4 . 5314

M
R
R
o
nT
PV
MR
T nR PV
nT
PV
R MR
o o
or
9 ;2mole 5314.4
233.15 : 1
22.31 : 10 : 1
5
0

nT
PV
R
23233 SPECIFIC 1EAT
a5 S&e)i%i) 1eat Ca&a)it+ at Co(sta(t ,olu$e 9Cv5
#he specific heat capacities of an$ substance is defined as the amount of heat energ$ re+uired to
raise the unit mass through one degree temperature raise. In thermod$namics, two specified
conditions are used, those of constant volume and constant pressure. #he two specific heat
capacities do not have the same value and it is essential to distinguish them.
If 1 "g of a gas is supplied with an amount of heat energ$ sufficient to raise the temperature of the
gas b$ 1 degree whilst the volume of the gas remains constant, then the amount of heat energ$
supplied is "nown as the specific heat capacity at constant voume, and is denoted b$ %v. #he unit
of %v is 6/"g : or "6/"g :.
'or a reversible non,flow process at constant volume, we have
d& @ m%vdT
)(.11*
'or a perfect gas the values of %v are constant for an$ one gas at all pressures and temperatures.
E+uations )(.11* can then be expanded as follows 5
eat flow in a constant volume process, &1/ @ m%v)T/ G T1* )(.1/*
Also, from the non,flow energ$ e+uation
& ' = (() (*)
mcv)T/ G T1* G 0 @ (() (*)
(() (*) = m%v)T/ G T1* )(.1(*
i.e. #( = &
Fote5
In a reversible constant volume process, no wor" energ$ transfer can ta"e place since the
piston will be unable to move i.e. ' @ 0.
#he reversible constant volume process is shown on a P-V diagram in 'ig. (.2.
Fi"u#e 33 P-V diagram for reversible constant volume process
'5 S&e)i%i) 1eat Ca&a)it+ at Co(sta(t P#essu#e 9Cp5
If 1 "g of a gas is supplied with an amount of heat energ$ sufficient to raise the temperature of the gas b$ 1
degree whilst the pressure of the gas remains constant, then the amount of heat energ$ supplied is "nown
as the specific heat capacity at constant pressure, and is denoted b$ %p. #he unit of %p is 6/"g : or "6/"g :.
'or a reversible non,flow process at constant pressure, we have
d& @ m%pdT )(.12*
'or a perfect gas the values of %p are constant for an$ one gas at all pressures and temperatures. E+uation
)(.12* can then be expanded as follows5
eat flow in a reversible constant pressure process & @ m%p)T/ G T1* )(.1<*
Relatio(s*i& Bet7ee( T*e S&e)i%i) 1eats
0et a perfect gas be heated at constant pressure from T
1
to T
/
. 3ith reference to the non,flow e+uation & @
(/ G (1 H ', and the e+uation for a perfect gas
(/ G (1 = m%v(T/ T1), hence,
& @ m%v(T/ T1) H '
In a constant pressure process, the wor" done b$ the fluid is given b$ the pressure times the change in
volume, i.e. ' = P(V/ V1)3 #hen using e+uation PV = mRT+ we have
' = mR(T/ T1)
#herefore substituting,
& @ m%v(T/ T1) H mR(T/ T1) = m(%v , R)(T/ T1)
-ut for a constant pressure process from equation ./*0+
P
2
P
1
1
2
P
V
V
1
= V
2
& @ m%p)T/ G T1*
ence, b$ e+uating the two expressions for the heat flow I, we have
m%p)T/ G T1* @ m(%v , R)(T/ T1)
%p = %v , R
Alternativel$, it is usuall$ written as
R = %p - %v (.1>

S&e)i%i) 1eat Ratio 9 5
#he ratio of the specific heat at constant pressure to the specific heat at constant volume is given the
s$mbol )gamma*,

i.e. @
v
p
C
C
)(.1=*
2323 NON FLO4 PROCESS
7nce a fluid has entered a s$stem, it ma$ be possible for it to undergo a series of processes in
which the fluid does not flow. An example of this is the c$linder of an internal combustion engine. In the
suction stro"e, the wor"ing fluid flows into the c$linder in which it is then temporaril$ sealed. 3hilst the
c$linder is sealed, the fluid is compressed b$ the piston moving into the c$linder, after which heat energ$ is
supplied so that the fluid possesses sufficient energ$ to force the piston bac" down the c$linder, causing the
engine to do external wor". #he exhaust valve is then opened and the fluid is made to flow out of the
c$linder into the surroundings. Processes which are undergone b$ a s$stem when the wor"ing fluid cannot
cross the boundar$ are called (o(!%lo7 &#o)ess.
2i%%e#e()es Bet7ee( T*e Flo7 a(d No(!%lo7 &#o)esses
Flo7 P#o)ess
In an open s$stem, not onl$ the energ$ transfers ta"e place across the boundar$, the fluid ma$ also cross
the boundar$. An$ process undergone b$ an open s$stem is called a flow process. #his process ma$ be
sub,divided into an unstead$ flow process and stead$ flow process. #he general e+uation is shown below,
W
C
v P u gZ
C
v P u gZ + + + + + + + +
2 2
2
2
2 2 2 2
2
1
1 1 1 1
No(!%lo7 &#o)ess
In a close s$stem, although energ$ ma$ be transferred across the boundar$ in the form of wor" energ$ and
heat energ$, the wor"ing fluid itself never crosses the boundar$. An$ process undergone b$ a close s$stem
is referred to as the non,flow process.
If the fluid is undergoing a non,flow process from state )1* to state )/* then the terms from the general
e+uation for p*V* and p)V) )which represent the amount of wor" energ$ re+uired to introduce and expel the
fluid from the s$stem* will be %ero, since the fluid is alread$ in the s$stem, and will still be in the s$stem at
the end of the process. 'or the same reason, the changes in "inetic and potential energies of the fluid will
also be %ero. #hus the e+uation becomes
(* , & = () , '
or, () (* = & ' )2.1*
In words, this e+uation states that in a non,flow process, the change in the internal energ$ of the fluid is
e+ual to the nett amount of heat energ$ supplied to the fluid minus the nett amount of wor" energ$ flowing
from the fluid.
#his e+uation is "nown as the (o( %lo7 e(e#"+ equatio(, and it will now be shown how this ma$ appl$ to
the various non,flow processes.
#here is < process that can be classified as non flow process5
a* .onstant temperature process
b* .onstant pressure process
c* .onstant volume process
d* Adiabatic process
e* Pol$trophic process
a5 CONSTANT TEMPERATURE 9ISOT1ERMAL5 PROCESS
If the change in temperature during a process is ver$ small then that process ma$ be approximated
as an isothermal process. 'or example, the slow expansion or compression of fluid in a c$linder,
which is perfectl$ cooled b$ water ma$ be anal$sed, assuming that the temperature remains
constant
Fi"u#e 32 .onstant temperature )Isothermal* process
W
Q
P
=
=
1
=
2
W
1
2
#he general relation properties between the initial and final states of a perfect gas are applied as follows5
2
2 2
1
1 1
T
V p
T
V p

If the temperature remains constant during the process, T* = T) and the above relation becomes
2 2 1 1
V p V p
'rom the e+uation we can "now that an increase in the volume results in a decrease in the pressure. In
other words, in an isothermal process, the pressure is inversel$ proportional to the volume.
4o#: t#a(s%e#:
Jeferring to the process represented on the p V diagram in 'ig.2./ it is noted that the volume increases
during the process. In other words the fluid is expanding. #he expansion wor" is given b$

2
1
p!V W
@

2
1
!V
V
"
)since pV = %, a constant*
@

2
1
V
!V
"
@

2
1
1 1
V
!V
V p
@
1
2
1 1
ln
V
V
V p

1
]
1

lume smaller =o
ume larger =ol

@
1
2
1
ln
V
V
mRT
)since p*V* = mRT**
@
2
1
1
ln
p
p
mRT
)since
2
1
1
2
p
p
V
V

* )2./*
Fote that during expansion, the volume increases and the pressure decreases. 7n the p V diagram, the
shaded area under the process line represents the amount of wor" transfer.
!ince this is an expansion process )i.e. increasing volume*, the wor" is done b$ the s$stem. In other words
the s$stem produces wor" output and this is shown b$ the direction of the arrow representing '/
1eat t#a(s%e#:
Energ$ balance to this case is applied5
(* , & = () , '
'or a perfect gas
In an industrial process, 0.2 "g of ox$gen is compressed isothermall$ from 1.01 bar and //
o
.
to <.< bar. -etermine the wor" done and the heat transfer during the process. Assume that
ox$gen is a perfect gas and ta"e the molecular weight of ox$gen to be K @ (/ "g/"mole.
(* = mcvT* an# () = mcvT)
As the temperature is constant
(* = ()
!ubstituting in the energ$ balance e+uation,
& = ' )2.(*
#hus, for a perfect gas, all the heat added during a constant temperature process is converted into wor" and
the internal energ$ of the s$stem remains constant.
E-a$&le
Solutio(
-ata5 m @ 0.2 "gL p*@ 1.01 barL t1@ //
o
.
p) @ <.< barL ' @ A & @ A
'rom the e+uation
R @
M
R
0
@
32
5314
@ />0 6/"g:
@ 0./>0 "6/"g:
'or an isothermal process
3or" input,
' = mRTln
1
2
p
p
@
01 . 1
5 . 5
ln 7 233 22 8 : 260 . 0 : 4 . 0 +
@ </ "6
In an isothermal process all the wor" input is re&ected as heat.
#herefore, heat re&ected, & = ' @ </ "6
'5 CONSTANT PRESSURE PROCESS
If the change in pressure during a process is ver$ small then that process ma$ be approximated as a
constant pressure process. 'or example, heating or cooling a li+uid at atmospheric pressure ma$ be
anal$sed b$ assuming that the pressure remains constant.
Fi"u#e /33 .onstant pressure process
.onsider the fluid in the piston c$linder as shown in 'igure <./. If the load on the piston is "ept constant the
pressure will also remain constant.
#he general propert$ relation between the initial and final states of a perfect gas is applied as5
2
2 2
1
1 1
T
V p
T
V p

If the pressure remain constant during the process, p) = p* and then the above relation becomes
2
2
1
1
T
V
T
V

or
1
2
1
2
V
V
T
T

)<.?*
'rom this e+uation it can be seen that an increase in volume results from an increase in temperature. In
other words, in constant pressure process, the temperature is proportional to the volume.
4o#: t#a(s%e#:
Jeferring to the process representation on the p-V diagram it is noted that the volume increases during the
process. In other words, the fluid expands. #his expansion wor" is given b$

2
1
p!V W

2
1
!V p )since p is constant*
@ p (V) V*) )larger volume G smaller volume* )<.;*
W
Q
P
v
v
1
v
2
W
1 2
v
2
> v
1
p
#he specific internal energ$ of a fluid is increased from 1/0 "6/"g to 1?0 "6/"g during a
constant volume process. -etermine the amount of heat energ$ re+uired to bring about this
increase for / "g of fluid.
Fote that on a p,M diagram, the area under the process line represents the amount of wor" transfer. 'rom
'igure <.(
' @ area of the shaded rectangle
@ height x width
@ p (V) V*) )larger volume G smaller volume*
#his expression is identical to e+uation <.;
1eat t#a(s%e#:
Appl$ing the non flow energ$ e+uation
& ' = () (*
or & = (() (*) , ' )<.10*
#hus part of the heat supplied is converted into wor" and the remainder is utili%ed in increasing the internal
energ$ of the s$stem.
!ubstituting for 3 in e+uation <.10
& = (() (*) , p(V) V*)
= () (* , p) V) p* V* )since p) = p* *
= (() , p) V)) ((* , p* V*)
Fow, we "now that h = u , pv or 1 = ( , pV
ence
& = 1) 1* )larger 1 G smaller 1* )<.11*
Jeferring to the process representation on the p,v diagram shown in 'igure <.(, it is noted that heating
increases the volume. In other words, the fluid expands. 'or a perfect gas, e+uation <.? tells us that an
increase in volume will result in corresponding increase in temperature.
E-a$&le
Solutio(
#he non flow energ$ e+uation is
& ' = () (*
'or a constant volume process
' @ 0
and the e+uation becomes
& = () (*
& @ 1?0 G 1/0
@ >0 "6/"g
#herefore for / "g of fluid
& @ >0 x / @ 1/0 "6
i.e. 1/0 "6 of heat energ$ would be re+uired.
)5 CONSTANT ,OLUME PROCESS
If the change in volume during a process is ver$ small then that process ma$ be approximated as a constant
volume process. 'or example, heating or cooling a fluid in a rigid walled vessel can be anal$sed b$
assuming that the volume remains constant.
a* eating b* .ooling
Fi"u#e /32 .onstant volume process )V)=V**
#he general propert$ relation between the initial and final states of a perfect gas is applied as5
2
2 2
1
1 1
T
V p
T
V p

If the volume remain constant during the process, V) = V* and then the above relation becomes
2
2
1
1
T
p
T
p

or
1
2
1
2
p
p
T
T

)<.>*
'rom this e+uation it can be seen that an increase in pressure results from an increase in temperature. In
other words, in constant volume process, the temperature is proportional to the pressure.
4o#: t#a(s%e#:
3or" transfer )p#V* must be %ero because the change in volume, #V, during the process is %ero. owever,
wor" in the form of paddle,wheel wor" ma$ be transferred.
1eat t#a(s%e#:
Appl$ing the non flow energ$ e+uation
p
v
2
1
Q
p
v
2
1
Q
& ' = () (*
gives & 2 = () (*
i.e. & = () (* )<.=*
#his result, which is important and should be remembered, shows that the nett amount of heat energ$
supplied to or ta"en from a fluid during a constant volume process is e+ual to the change in the internal
energ$ of the fluid.
d5 A2IABATIC PROCESS 9 Q ; .5
If a s$stem is thermall$ well insulated then there will be negligible heat transfer into or out of the s$stem.
!uch a s$stem is thermall$ isolated and a process within that s$stem ma$ be idealised as an adiabatic
process. 'or example, the outer casing of steam engine, steam turbines and gas turbines are well insulated
to minimise heat loss. #he fluid expansion process in such machines ma$ be assumed to be adiabatic.
Fi"u#e 33 Adiabatic )%ero heat transfer* process
'or a perfect gas the e+uation for an adiabatic process is
pV

= %
where @ ratio of specific heat @
v
p
C
C
#he above e+uation is applied to states 1 and / as5

2 2 1 1
V p V p

1
]
1

2
1
1
2
V
V
p
p
)2.2*
W
P
=
=
1
=
2
W
1
2
T?ermal insulaion
Also, for a perfect gas, the general propert$ relation between the two states is given b$ the e+uation below
2
2 2
1
1 1
T
V p
T
V p

)2.<*
4$ manipulating e+uations 2.2 and 2.< the following relationship can be determined5
1
2
1
1
1
2
1
2

1
]
1

1
]
1

V
V
p
p
T
T
)2.>*
4$ examining e+uations 2.2 and 2.> the following conclusion for an adiabatic process on a perfect gas can
be drawn5
An increase in volume results in a decrease in pressure.
An increase in volume results in a decrease in temperature.
An increase in pressure results in an increase in temperature.
4o#: t#a(s%e#:
Jeferring to the process represented on the p,M diagram )'ig.2.(* it is noted that the volume increases
during the process.
In other words, the fluid expanding and the expansion wor" is given b$ the formula5

2
1
p!V W
@

2
1
!V
V
"

)since pV

= %, a constant*
@

2
1

V
!V
"
@
1
2 2 1 1

V p V p
8larger pV, small pV9 )2.=*
Fote that after expansion, p) is smaller than p*. In the p V diagram, the shaded area under the process
represents the amount of wor" transfer.
As this is an expansion process )i.e. increase in volume* the wor" is done b$ the s$stem. In other words, the
s$stem produces wor" output and this is shown b$ the direction of the arrow representing ' )as shown in
'ig 2.(*.
1eat t#a(s%e#:
In an adiabatic process, I @ 0.
Appl$ing an energ$ balance to this case )'ig.2.(*
(* - ' = ()
' = (* ()
In a thermall$ insulated reciprocating air compressor, air at 0.;? bar and /0
o
. is compressed
into one sixth of its original volume. -etermine the pressure and temperature of the air after
compression. If the compressor c$linder contains 0.0< "g of air, calculate the re+uired wor"
input. 'or air, ta"e @ 1.2 and cv @ 0.=1? "6/"g:.
#hus, in an adiabatic expansion the wor" output is e+ual to the decrease in internal energ$. In other words,
because of the wor" output the internal energ$ of the s$stem decreases b$ a corresponding amount.
'or a perfect gas, (* = mcvT* and (* = mcvT*
7n substitution
' = mcv(T*-T)) 8larger #, smaller #9 )2.?*
3e "now
cp- cv = R
or
cv =
1
R
!ubstituting in e+uation 2.?
1
8
7 2 1

T T mR
W )2.;*
4ut, mRT) = p)V) and mRT* = p*V*
#hen the expression for the expansion becomes

1
2 2 1 1

V p V p
W
)2.10*
Jeferring to the process represented on the p,M diagram it is noted that during this process the volume
increases and the pressure decreases. 'or a perfect gas, e+uation 2.> tells that a decrease in pressure will
result in a temperature drop.
E-a$&le
Solutio(
-ata 5 p* @ 0.;? barL T*@ /0 H /=( @ /;( :
@
6
1
1
2

V
V
m @ 0.0< "gL ' @ A
As the c$linder is well insulated the heat transfer is negligible and the process ma$ be treated as
adiabatic.
.onsidering air as a perfect gas
'rom e+uation 2.2,

1
]
1

2
1
1
2
V
V
p
p
p) @ 0.;? x >
1.2

@ 1/ bar
'rom e+uation 2.>,
1
2
1
1
2

1
]
1

V
V
T
T
T) @ /;( x >
0.2
@ >00 :
@ (/=
o
.
Je,writing e+uation 2.? for an adiabatic compression process
' = mcv(T)-T*) 8larger T, smaller T9
@ 0.0< x 0.=1? )>00,/;(*
@ 11 :&
e5 POL<TROPIC PROCESS 9pV
n
= C5
#his is the most general t$pe of process, in which both heat energ$ and wor" energ$ cross the boundar$ of
the s$stem. It is represented b$ an e+uation in the form
pV
n
@ constant )<.1*
If a compression or expansion is performed slowl$, and if the piston c$linder assembl$ is cooled perfectl$,
then the process will be isothermal. In this case the index n @ 1.
If a compression or expansion is performed rapidl$, and if the piston c$linder assembl$ is perfectl$ insulated,
then the process will be adiabatic. In this case the index n @ .
If a compression or expansion is performed at moderate speed, and if the piston c$linder assembl$ is cooled
to some degree, then the process is somewhere between those discussed above. Eenerall$, this is the
situation in man$ engineering applications. In this case the index n should ta"e some value, which is
between 1 and depending on the degree of cooling.
!ome practical examples include5
compression in a stationar$ air compressor )n @ 1.(*
compression in an air compressor cooled b$ a fan )n @ 1./*
compression in a water cooled air compressor )n @ 1.1*
W
P
1
P
1
pV
n
=C
Fi"u#e /31 Pol$tropic process
E+uation <.1 is applied at states 1 and / as5
n n
V p V p
2 2 1 1

or
n
V
V
p
p
1
]
1

2
1
1
2
)<./*
Also, for a perfect gas, the general propert$ relation between the two states is given b$
2
2 2
1
1 1
T
V p
T
V p

)<.(*
4$ the manipulation of e+uations <./ and <.( the following relationship can be determined5
1
2
1
1
1
2
1
2

1
]
1

1
]
1

n
n
n
V
V
p
p
T
T
)<.2*
4$ examining e+uations <./ and <.2 the following conclusions for a pol$tropic process on a perfect gas can
be drawn as5
An increase in volume results in a decrease in pressure.
An increase in volume results in a decrease in temperature.
An increase in pressure results in an increase in temperature.
4o#: t#a(s%e#:
Jeferring to the process represented on the p-V diagram )'ig.<.1* it is noted that the volume increases
during the process.
In other words the fluid is expands and the expansion wor" is given b$

2
1
p!V W
@

2
1
!V
V
"
n
)since pV
n
= %, a constant*
Q
loss
=
=
1 =
2
W
2
P
2
#he combustion gases in a petrol engine c$linder are at (0 bar and ?00
o
. before expansion.
#he gases expand through a volume ratio )
1
2
V
V
* of )
1
5 . 5
* and occup$ <10 cm
(
after
expansion. 3hen the engine is air cooled the pol$tropic expansion index n @ 1.1<. 3hat is the
temperature and pressure of the gas after expansion, and what is the wor" outputA
@

2
1
n
V
!V
"
@
1
2 2 1 1

n
V p V p
8larger pV, small pV9 )<.<*
Fote that after expansion p) is smaller than p*. In the p V diagram, the shaded area under the process
represents the amount of wor" transfer.
!ince this is an expansion process )i.e. increase in volume*, the wor" is done b$ the s$stem. In other words,
the s$stem produces wor" output and this is shown b$ the direction of the arrow representing ' as shown
in 'ig. <.1.
1eat t#a(s%e#:
Energ$ balance is applied to this case )'ig.<.1* as5
(* &oss - ' = ()
&oss = ((* ()) '
or
' = ((* ()) - &oss
#hus, in a pol$tropic expansion the wor" output is reduced because of the heat loses.
Jeferring to the process represented on the pV diagram )'ig.<.1* it is noted that during this process the
volume increases and the pressure decreases. 'or a perfect gas, e+uation <.2 tells us that a decrease in
pressure will result in a temperature drop.
E-a$&le
Solutio(
P
1
$ 30 bar
t
1
$ 500
o
C
Q
loss
W
V
2
$ 510 %m
3
p
2
$ A
t
2
$ A
!tate 1 !tate /
-ata5 p* @ (0 barL T* @ ?00 H /=( @ 10=( :L n @ 1.1<
1
2
V
V
@ ?.<L V) @ <10 cm
(
L
t) @ A p) @ A ' @ A
.onsidering air as a perfect gas, for the pol$tropic process, the propert$ relation is given b$ e+uation <.2 as5
1
2
1
1 2

1
]
1

n
V
V
T T
@
1 15 . 1
5 . 5
1
1033

1
]
1

#

@ ==?.2 :
@ <0<.2
o
.
'rom e+uation <./
n
V
V
p p
1
]
1

2
1
1 2
@
15 . 1
5 . 5
1
: 30
1
]
1

@ /.<> bar
Fow,
V) @ <10 cm
(
@ <10 x 10
,>
m
(
and,
1
2
V
V
@ ?.<
#hen,
5 . 5
10 510
6
1

#
V
@ >0 x 10
,>
m
(
3or" output during pol$tropic expansion is given b$ e+uation <.< as5
' @
1
2 2 1 1

n
V p V p
8larger pV, small pV9
@
1 15 . 1
7 10 510 8 7 10 56 . 2 8 7 10 60 78 10 30 8
6 5 6 5

# # # #
@ ((0 6
@ 0.(( "6