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PropertiesofFluids
To evaluate heat and work interactions of a
thermodynamic system, aknowledgeof properties is
essential.
Aswell astherelationshipbetweenproperties
(P, v, T, U andHetc.)
Pure substance:
A substancewhichhassinglechemical species
(Air isnot apuresubstance)
Phase:
Commonly physical states of aggregation of any
substance
(a) solid(b) liquid(c) gas
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Phase: Different states in which a pure substance can
exists
Generally, A system which is uniform in chemical
compositionandphysical state, iscalledaphase.
System consisting different phases, all phases are
separatedbyphaseboundaries.
Thermodynamic properties of substance change abruptly
at phase boundary even though the temperature and p y g p
pressuresaresame.
Mixturesalsoexist indifferent phases.
Example: liquid and vapour phases of alcohol-water
system
Phase Change of Water
Consider a piston cylinder device containing
liquid water at 20C and 1 atm pressure
water exists in the liquid phase, is called a
compressed liquid, or a subcooled liquid.
As temperature rises, liquid water expands
slightly, specific volume increases.
As more heat is transferred, the temperature
keeps rising until it reaches 100C. At this
point water is about to vaporize, called a
saturated liquid.
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Once boiling starts, the temperature
stops rising until the liquid is
completelyvaporized.
As heating continue mixture of As heating continue, mixture of
saturated liquid and saturated
vapour exist inequillibrium.
At end, theentirecylinder isfilledwith
vapor vapor.
A vapor that is about to condense is
calledasaturated vapor.
Further heating to saturated vapor,
rise of temperature and specific
volume, superheated vapour
Again, cooling results in same
reversible process (superheated
vapour tosubcooledliquid)
Saturation temperature and Saturation temperature and
Saturation pressure
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Thermodynamic diagrams
(Phase change of pure substance)
P-T Diagrams
Sublimation
Fusion or melting
Vapourization
Critical point
For H
2
O, T
C
=374C &
P
C
=218 atm
Triple point
T-V Diagram
Figure: T-V diagram for pure substance
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boilingat higher temperatureat higher pressure
Above the critical state, no line that separates the
compressedliquidandsuperheatedvapor.
Saturatedliquidlineandsaturatedvapour linemeet at
thecritical point
Compressed liquid region, superheated vapor region, p q g , p p g ,
saturated liquidvapor mixture region, or the wet
region
P-V Diagram
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Shapeof theP-V diagram, muchliketheT-V diagram, T=
constant linesaredownwards
P-V linefor compressedliquidregionisalmost vertical.
P-V linefor superheatedvapour regionislesssteep.
For amixtureof saturatedliquidandsaturatedvapour
Qualityor drynessfraction=
Massof sat vapour / Total massof mixture Massof sat. vapour / Total massof mixture
X =m
g
/m
Total volumeof mixtureisgivenby,
mv=(m m
g
)v
f
+m
g
v
g
. (1)
Where, v
g
=specificvolumeof saturatedvapour and
v
f
=specificvolumeof saturatedliquid
v =specificvolumeof themixture
Dividebytotal massm, Dividebytotal massm,
v = (1 X ) v
f
+ X v
g
Put m=m
f
+m
g
inequation(1),
(m
f
+m
g
)v =m
f
v
f
+m
g
v
g
Rearranging,
(v
g
v) / (v v
f
) =m
f
/m
g
(lever rule)
Similarly, specificenthalpyof aSat. liquid-vapour mixture,
h=(1 X)h
f
+Xh
g
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Specific entropy of a liquid-vapour mixture,
s =(1 X)s
f
+Xs
g
Above the critical temperature, no amount of pressure can
condensethevapor toaliquid. p q
abc
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Table2
Table3
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Table4
Table5
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Example (Use of Sat. Temp. table)
A vessel having a capacity of 0.05 m
3
contains a mixture of
saturated water and saturated steamat a temperature of 245C.
Themassof theliquidpresent is10kg. Findthefollowing:
(i) The pressure (ii) The mass (iii) The specific volume (iv) The
ifi h l ( ) Th ifi d( i) Th ifi specific enthalpy (v) The specific entropy and (vi) The specific
internal energy.
Solution:
Given, V =0.05 m
3
, Sat. liq. vap. mixture, T =245C, m
f
=10 kg
From steam tables, corresponding to 245C :
P
sat
=36.523 bar, v
f
=0.001240 m
3
/kg, v
g
=0.0546 m
3
/kg, h
f
=
1061.6 kJ /kg, h
g
=2801.6 kJ /kg, s
f
=2.748 kJ /kg K, s
g
=6.106
kJ /kgK
(i) Pressure =Sat. pressure =36.5 bar (3.65 MPa)
(ii) Mass (m):
We have, Volume of liquid =V
f
=m
f
v
f
=10 0.00124 =0.0124 m
3
So, Volume of vapour, V
g
=0.05 0.0124 =0.0376 m3
and mass of vapour =m
g
=V/v
g
=0.0376/0.0546 =0.689 kg
So, total mass of mixture =m
f
+m
g
=10 +0.688 =10.689 kg
(iii) The specific volume (v) :
Here, Quality of the mixture x =m
g
/ (m
g
+m
f
) =0.064
Now, v =x.v
g
+(1 - x)v
f
=0.00356 m
3
/kg
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(iv) Specific enthalpy, h :
h =x.h
g
+(1 x).h
f
=1172.96 kJ/kg
(v) Specific entropy, s :
s =x.s
g
+(1 x).s
f
=2.9629 kJ/kg K
g
( )
f
g
(vi) Specific internal energy, u :
u =h pv=1172.96 3650 0.00356 =1159.97 kJ/kg
Example (Use of superheated tables)
Steam at 120 bar has a specific volume of 0.01721 m
3
/kg, find the
temperature, enthalpy and the internal energy.
Solution:
Given: Pressure of steam(p) =120 bar and specific volume (v) =
0.01721m
3
/kg
(i) Temperature:
With use of Sat. pressure steam table,
At 120 bar, v
f
=0.001527 and v
g
=0.014285 m
3
/kg
H (001721
3
/k ) > (0014285
3
/k ) Here, v
actual
(0.01721 m
3
/kg) >v
g
(0.014285 m
3
/kg)
So, steam is superheated.
From the superheat steam volume tables at 120 bar, the specific volume
is 0.01721 m
3
/kg at a temperature of 350C.
So, steam temperature =350C
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(ii) Enthalpy:
From superheated steam enthalpy table,
Specific enthalpy at 120 bar and 350C, h =2849.7 kJ/kg
(iii) Internal energy: ( ) gy
u =h pv
=2849.7 (12000)(0.01721)
=2643.18 kJ/kg
Vander waals Equations of State
(Real Gases)
Manyattemptsmadetorepresent P-V-T dataaccurately.
V WEquation:
Takesintoaccount theeffect of volumeof molecules
Aswell asattractionforcebetweenmolecules Aswell asattractionforcebetweenmolecules
V WEq. cubicinmolar volume,
For T <T
C
,Threereal rootsat somePandT.
For T >T
C
,onereal andtwoimaginaryroots
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Criticalisothermmustshowapointofinflectionat
criticalpoint.
a=27R
2
T
C
2
/64P
C
andb=RT
C
/8P
C
Compressibility Factor
Gases deviate from idealgas behavior significantly
(e.g. near the saturation region and critical point)
Accounting of deviation from idealgas behavior by
use of compressibility factor (Z)
Defined as:
= Ideal Volume/ Actual Volume
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Z=1foridealgas
Fornonidealgasbehaviour,Z=f(P
r
,T
r
)
Where,T
r
=Reducedtemperature=T/T
c
andP
r
=Reducedpressure=P/P
c
T
c
=Criticaltemperatureofgas
P
c
=Criticalpressureofthegas
Critical properties can be obtained from tables Criticalpropertiescanbeobtainedfromtables
Compressibility Charts
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At very low pressures (P
r
<< 1), all gas behaviour as
ideal gas regardless of temperature.
At high temperatures (T
r
> 2), idealgas behavior can
be assumed with good accuracy regardless of
pressure (except when P
r
>> 1).
Th d i ti f f id l b h i i The deviation of a gas from idealgas behavior is
greatest in the vicinity of the critical point.
Example: Onekmol of ammoniais filledina0.1m3vessel at a
temperature of 200C. Using the generalized compressibility
chart determinethepressurewhichammoniaexerts.
(Given: T
C
=405.5 K, P
C
=112.77 bar)
Solution:
Here, T
r
=473/405.5 =1.17
P
r
=P / P
C
=P
ideal
(assume) / P
C
=(RT/v) / P
C
=(8.314*473.15/0.1) / 11277 =3.5
Use, generalized compressibility charts,
Z =0.57 (for P
r
=3.5 and T
r
=1.17)
So, New P =ZRT/v =(0.57* 8.314*473.15/0.1) =22423 kPa
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New P
r
=P/P
C
=22423 / 11277 =2
Again, use of generalized compressibility charts,
Z =0.52 (for P
r
=2 and T
r
=1.17)
So, New P =ZRT/v =(0.52* 8.314*473.15/0.1) =20455 kPa
And New P
r
=P/P
C
=20455 / 11277 =1.81
Again, use of generalized compressibility charts,
Z 053(for P 181andT 117) Z =0.53 (for P
r
=1.81 and T
r
=1.17)
So, New P =ZRT/v =(0.53* 8.314*473.15/0.1) =20.8 MPa