lncompresslble SubsLance

An !"#$%&'())!*+( )-*)./"#( ls one whose

speclc volume (or denslLy) remalns consLanL
regardless of changes ln oLher properues
Sollds and mosL llqulds may be assumed
lncompresslble wlLhouL much loss ln accuracy
Are Lhey really lncompresslble?
1he dlerence beLween consLanL pressure and
consLanL volume speclc heaLs ls zero,
1
( ) ( ) ( )
v p
C T C T C T = =
lncompresslble SubsLance
Changes ln lnLernal energy and enLhalpy


1he LemperaLure dependence of C may be handled ln a
manner ldenucal Lo ldeal gases
2
u
2
!u
1
= C T
( )
dT
1
2
"
h
2
!h
1
= du+ P dv
=0
+ v
=const
dP
1
2
"
= du+vdP
1
2
"
= u
2
!u
1
( )
+v P
2
! P
1
( )
= C T
( )
dT
1
2
"
+v P
2
! P
1
( )
Compressed Llqulds
Compressed llquld daLa are frequenLly noL
LabulaLed or only brlef Lables are avallable
1he lnLernal energy ls, as before, a fn of
LemperaLure only

lf sLaLe 2 ls a compressed llquld sLaLe aL Lhe same
LemperaLure as a saLuraLed llquld aL sLaLe 1, Lhen

1he speclc volumes are also approxlmaLely equal,
Lherefore
3
u
2
!u
1
= C T
2
!T
1
( )
u
CL
T
1
( )
! u
f
T
1
( )
h
CL
!h
f
= u
CL
!u
f
( )
+v
f
P
2
! P
1
( )
= v
f
P
2
! P
1
( )
or
h
CL
= h
f
+v
f
P
CL
! P
sat
( )
all evaluated at T
1
Lqulllbrlum ulagrams
All known subsLances can exlsL ln solld, llquld, or
gaseous (vapor) phase
MlxLures of more Lhan one phase are posslble
no slngle equauon expresslng Lhe -v-1 behavlor
of such mlxLures exlsL
Conslder a plsLon-cyllnder lled wlLh llquld waLer
aL room LemperaLure and pressure. 1he plsLon
has mass and ls allowed Lo move.
now, leL Lhere be heaL Lransfer Lo Lhe waLer.
WhaL happens Lo , v, 1?
4
PeaL SubsLance aL ConsLanL p

1 - 2 SCLlu
2 - 3 SCLlu + LlCulu
3 - 4 LlCulu
4 - 3 LlCulu + CAS
3 + CAS
T
v
P
hi
1
2
4
5
Solid+
Liquid
Liquid
Liquid+Gas
Gas
P
lo
3
3
Lqulllbrlum ulagrams
lrom 1-2 Lhe Lemp. of Lhe
llquld waLer lncreases aL
consLanL
(compressed or sub-cooled
llquld)
AL 2, saLuraLed llquld
AL 3, llquld/vapor equlllbrlum
AL 4, saLuraLed vapor
lrom 4-3, Lhe Lemp. of Lhe
vapor lncreases aL consLanL
(superheaLed vapor)
WhaL happens lf we repeaL
Lhe experlmenL aL hlgher
pressure?
6
! lrom 2-4 - vaporlzauon
! lrom 4-2 - condensauon
Lqulllbrlum ulagrams
SLarung aL sLaLe 1, lncreaslng Lhe
pressure lowers v, so Lhe sysLem
moves Lo 1'
PeaL Lransfer Lo Lhe sysLem
resulLs ln a slmllar progresslon of
sLaLes as before
noLe: Lhe hlgher 1 of saLurauon
sLaLes aL hlgher pressure
Also, noLe LhaL Lhe dlsLance from
2'-4' ls shorLer Lhan from 2-4
Conunued lncreaslng of Lhe
pressure conunues Lo shorLen
Lhe dlsLance beLween saLuraLed
sLaLes unul Lhey colnclde
7
! 1he polnL where Lhe saL.
sLaLes colnclde ls Lhe
crlucal polnL
Lqulllbrlum ulagrams
CompleLe equlllbrlum
dlagram ln -v-1 space
Complex, so noL llkely Lo
develop a slmple expresslon
wlll be developed
lnLerpolauon requlred when
uslng Lhe Lable - llnear
lnLerpolauon
WanL Lo nd, for example,
Lhe lnLernal energy u aL
properLy 1 LhaL ls noL on Lhe
Lable
8
( )
upper lower
lower lower
upper lower
u u
u u T T
T T
!
= + !
!
Lqulllbrlum ulagrams
ro[ecuon of 3d surface on
1-v plane
SubsLance LhaL conLracLs on
freezlng - nC1 waLer
9
Lqulllbrlum ulagrams
ro[ecuon of Lhe 3d surface
on Lhe -v plane
noLe lsoLherms - slope
changes as phase
boundarles are crossed
10
Typical T-v Diagram
Solid + gas/
vapor
Liquid+Gas
(Saturated)
Vapor Dome
Solid
Gas/
Superheated Vapor
C
r
itic
a
l P
o
in
t
T
v
P
crit
P
hi
P
low
S
u
p
e
r
c
r
i
t
i
c
a
l
S
t
a
t
e
s

Triple Line
Saturation States
= Phase Transitions
S
o
l
i
d
+
L
i
q
u
i
d

(
S
u
b
c
o
o
l
e
d
)

L
i
q
u
i
d

11
Lqulllbrlum ulagrams
ro[ecuon on Lhe -1 plane
noLe Lrlple llne appears Lo be a
polnL - noL really a slngle sLaLe,
raLher, loLs of sLaLes
Llquld-solld - called freezlng or
fuslon
Solld-vapor - subllmauon - mosL
common examples CC2,
paradlchlorobenzene (moLhballs)
noLe Lhe varlous Lransluons
across phase boundarles
noLe LhaL lce can be melLed by
lncreaslng Lhe pressure - lce
skaung
12
SuperheaLed vapor
A subsLance ls a super-
heaLed vapor lf
1>1
saL
aL Lhe pressure of
lnLeresL
<
saL
aL Lhe LemperaLure of
lnLeresL 1
v>v
saL
for elLher
saL
(aL 1) or
1
saL
(aL )
lnLernal energy and enLhalpy
are also hlgher Lhan Lhose
correspondlng Lo Lhe
saLurauon sLaLe
Any Lwo properues are
sumclenL Lo x Lhe sLaLe
13
Compressed Llquld
14
! A subsLance ls a compressed
llquld lf
! 1<1
saL
aL Lhe pressure of lnLeresL
buL greaLer Lhan solldlcauon
Lemp
! >
saL
aL Lhe LemperaLure of
lnLeresL
! v<v
saL
for elLher
saL
(aL 1) or
1
saL
(aL )
! lnLernal energy and enLhalpy
are also lower Lhan Lhose
correspondlng Lo Lhe saLurauon
sLaLe
! Any Lwo properues are
sumclenL Lo x Lhe sLaLe
Lqulllbrlum ulagrams
noL drawn Lo scale:
compressed llquld reglon ls
shown much larger Lhan
reallLy
Cnly llquld-vapor reglon
shown
uoes noL lnclude all posslble
equlllbrlum sLaLes - no solld
or solld/llquld, solld/vapor
sLaLes shown
roperLy called 0-/+!.1
expresses fracuon of mass
of vapor Lo Lhe LoLal mass

13
vapor g
vapor liquid f g
m m
x
m m m m
= =
+ +
1.u. roperues ln Mlxed hase
V
mix
= m
g
v
g
+m
f
v
f
= m
mix
[
m
g
v
g
m
mix
+
m
f
v
f
m
mix
]
V
mix
= m
mix
[Xv
g
+(1! X)v
f
]
Therefore : v
mix
= Xv
g
+(1! X)v
f
= v
f
+ X(v
g
!v
f
)
for any variable y :
y
mix
= Xy
g
+(1! X)y
f
= y
f
+ X(y
g
! y
f
) = y
f
+ Xy
fg
where y
fg
= y
g
! y
f
16
Lqulllbrlum ulagrams
and 1 are noL lndependenL ln Lhe saLurauon dome
Average properues for mlxed equlllbrlum sLaLes
17
mu =U = m
g
u
g
+m
f
u
f
u =
U
m
f
+m
g
=
m
g
u
g
+m
f
u
f
m
f
+m
g
u =
m
g
m
f
+m
g
u
g
+
m!m
g
m
f
+m
g
u
f
u = xu
g
+ 1! x
( )
u
f
u = u
f
+ x(u
g
!u
f
)
u = u
f
+ xu
fg
Lxamples from ChapLer 2
roblems glven as examples ln Lhe book
should be carefully revlewed and undersLood
Many varlanLs of Lhe same examples are
posslble as problems buL Lhe procedures are
mosLly Lhe same
1able famlllarlLy ls essenual
1ables A-u and AL-uL essenual for now
ldenufy Lables for dlerenL unlLs carefully
18
Lxamples
A conLalner wlLh a volume of 4
3
ls lled wlLh waLer aL a pressure
of 200 psla and a LemperaLure of 800 l. ueLermlne Lhe mass of Lhe
waLer ln Lhe conLalner.
CalculaLe Lhe mass ln kllograms of waLer conLalned ln a 3 m
3
Lank
under
SaLuraLed vapor aL 1 = 160 C
SaLuraLed llquld aL 1 = 160 C
1 = 600 C, = 2 Mpa
1 = 30 C, = 101 ka
x = 0.3, = 300 ka
A plsLon-cyllnder arrangemenL conLalnlng refrlgeranL-12 aL 400 ka
and 80 C ls compressed. 1he properues of Lhe refrlgeranL-12 are
assumed Lo obey Lhe relauon v
1.2
= consLanL. 1he compresslon
process sLops when Lhe pressure reaches 1 Ma. ueLermlne Lhe
amounL of work requlred Lo compress 3 kg of refrlgeranL.
19
Lxamples
A rlgld conLalner used Lo lnaLe a spare ure ls Lyplcally ln some cars
and ls pressurlzed Lo 80 psla aL 80 l. lL ls supposed Lo have deslgn
margln of 3. lf Lhe LemperaLure of Lhe Lrunk ln Lhe car becomes 130l
can Lhe conLalner explode
WaLer exlsLs aL a pressure of 430 psla and 600 l. ueLermlne Lhe
speclc volume of Lhe waLer (a) by assumlng Lhe waLer ls an ldeal
gas, (b) by uslng Lhe LabulaLed daLa. Whlch one ls more accuraLe?
A closed sysLem conLalns a subsLance whose volume ls reduced Lo
one-half of lnlual volume durlng an lsoLhermal process.
SubsLance ls waLer lnlually ln saLuraLe vapor sLaLe aL 200 C
SubsLance ls alr aL 30 C and 400 ka
SkeLch Lhe -v dlgram
ls Lhe work for Lhls process (greaLer Lhan, equal Lo, less Lhan) zero?
ls Lhe lnLernal energy change (greaLer Lhan, equal Lo, less Lhan) zero?
20