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Properties of Fluids
• 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 20°C 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 100°C. 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
=374˚C &
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 liquid–vapor 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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• Table 2
• Table 3
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• Table 4
• Table 5
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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 245°C.
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 =245˚C, m
f
=10 kg
From steam tables, corresponding to 245°C :
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 350°C.
So, steam temperature =350˚C
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(ii) Enthalpy:
From superheated steam enthalpy table,
Specific enthalpy at 120 bar and 350°C, h =2849.7 kJ/kg
(iii) Internal energy: ( ) gy
u =h – pv
=2849.7 – (12000)(0.01721)
=2643.18 kJ/kg
Vander waal’s 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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• Critical isotherm must show a point of inflection at 
critical point.
• a = 27R
2
T
C

/ 64P
C
and    b = RT
C
/8P
C
Compressibility Factor
• Gases deviate from ideal‐gas behavior significantly
(e.g. near the saturation region and critical point)
• Accounting of deviation from ideal‐gas behavior by
use of compressibility factor (Z)
• Defined as:
= Ideal Volume/ Actual Volume
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• Z = 1 for ideal gas
• For non ideal gas behaviour, Z = f(P

, T
r
)
Where, T
r
= Reduced temperature =  T/T
c
and P
r
= Reduced pressure = P/P
c
T
c
= Critical temperature of gas
P
c
= Critical pressure of the gas
• Critical properties can be obtained from tables • Critical properties can be obtained from tables
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), ideal‐gas 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 ideal‐gas behavior is
greatest in the vicinity of the critical point.
Example: Onekmol of ammoniais filledina0.1m3vessel at a
temperature of 200˚C. 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