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Chapter 3 Cont'
Chapter 3 Cont'
Thermodynamics
CHAPTER 3
Volumetric Properties of Pure Fluids
3. Phase-
Change of PURE 7. Compressibility
Pure SUBSTANCE Factor- A
Substances Measure of
Deviation from
Ideal-Gas
2. Phases of a Behavior
Pure Substance
1. Pure 8. Other Equations
Substance of State
1. Pure Substance
A substance that has a fixed
chemical composition throughout is
called a Pure Substance.
Pure Substance:
- N2, O2, gaseous Air
-A mixture of liquid and gaseous
water is a pure substance, but a
mixture of liquid and gaseous air is
not.
2. Phases of a Pure Substance
The molecules
in a SOLID are
kept at their
positions by
the large
spring like
inter-molecular
forces. In a solid, the
attractive and
repulsive forces
between the
molecules tend to
maintain them at
relatively constant
distances from each
other.
The state of the saturated liquid water is shown on a T-v diagram. Since
saturation conditions exist in the tank, the pressure must be the saturation
pressure at 90 oC.
P = Psat@90oC = 70.14 kPa (Table A-4)
The specific volume of the saturated liquid at 90 oC is
v = vf@90oC = 0.001036 m3/kg (Table A-4)
Then the total volume of the tank is
V = mv = (50 kg)(0.001036 m3/kg) = 0.0518 m3
Example 3.2 (Temperature of saturated vapor)
A piston-cylinder device contains 2 ft3 of saturated water vapor at 50-psia
pressure. Determine the temperature and the mass of the vapor inside the
cylinder.
Solution
The state of the saturated water vapor is shown on a P-v diagram. Since the
cylinder contains saturated vapor at 50 psia, the temperature inside must be
the saturation temperature at this pressure.
T = Tsat@90oC = 281.03 oF (Table A-5E)
The specific volume of the saturated vapor at 50 psia is;
v = vf@50 psia = 8.518 ft3/lbm (Table A-5E)
Then the mass of water vapor inside the cylinder becomes;
V 2 ft 3
m 3
0.235 lbm
v 8.518 ft /lbm
Example 3.3 (Volume and Energy Change during Evaporation)
m m f mg
V mv, V f m f v f , Vg mg v g
4(b). Saturated Liquid-Vapor Mixture-cont’
Therefore,
mv m f v f mg v g
mf vf mg v g
v
m m
mg mg
since x
m m f mg
mf m mg
1 x
m m
v (1 x )v f xvg
or v v f x (v g v f )
with v fg v g v f
v vf
x
v fg
This analysis can be repeated for internal energy and enthalpy;
u u f xu fg
h h f xhfg
Example 3.4 (Pressure and Volume of a Saturated Mixture)
A rigid tank contains 10 kg of water at 90 oC. If 8 kg of the water is in the
liquid form and the rest is in the vapor form, determine (a) the pressure in the
tank and (b) the volume of the tank.
Solution
(a) Since the two phases coexist in equilibrium, we have a saturated mixture
and the pressure must be the saturation pressure at the given temperature;
(b) At 90 oC, we have vf = 0.001036 m3/kg and vg = 2.361 m3/kg (Table A-4)
One way of finding the volume tank is to determine the volume occupied by
each phase and then add them:
V V f Vg m f v f m g v g
(8 kg)(0.0010 36 m 3 /kg) (2kg)(2.36 1m 3 /kg)
4.73m 3
Example 3.4 (Pressure and Volume of a Saturated Mixture) cont’
(b) Another way is to first determine the quality x, then the average specific
volume v, and finally the total volume:
mg 2 kg
x 0.2
mf 10 kg
v v f xv fg
0.001036 m 3 /kg [( 2.361 0.001036)m 3 /kg]
0.473 m 3 /kg
and
V mv (10 kg)(0.473 m 3 /kg) 4.73 m 3
Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)
A 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.
Determine (a) the temperature of the refrigerant, (b) the quality, the enthalpy
of the refrigerant, and (d) the volume occupied by the vapor phase.
Solution
(a) Basically, we do not know whether the refrigerant is in the compressed
liquid, superheated vapor, or saturated mixture region.
This can be determined by comparing a suitable property to the saturated
liquid and saturated vapor values. From the given information, we can
determine the specific volume;
V 0.080 m3
v 0.02 m3 /kg
m 4 kg
At 160 kPa, we read
v f 0.0007435 m3 /kg
vg 0.1229 m3 /kg Table A -12
Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)-cont’
v vf 0.02 - 0.007435
x 0.158
v fg 0.1229 - 0.0007435
(c) At 160 kPa, we also read from Table A-12 that hf = 29.78 kJ/kg and
hfg = 208.18 kJ/kg. Then;
h h f xhfg
29.78 kJ/kg (0.158)(20 8.18 kJ/kg)
62.7 kJ/kg
Example 3.5 (Properties of Saturated Liquid-Vapor Mixture)-cont’
Obviously, the temperature is between 200 and 250 oC. By linear interpolation
it is determined to be:
T = 216.4 oC.
4(d). Compressed Liquid
Answer:
R : gas constant
M : molar mass (kg/kmol)
Ru : universal gas constant
Different substances have
U = U(T) (Ideal gas) (3.15) different gas constants.
7. Compressibility Factor - A Measure of
Deviation from Ideal-Gas Behavior
The ideal-gas equation is very simple and thus very convenient to
use. But, gases deviate from ideal-gas behavior significantly at
states near the saturation region and the critical point.
This deviation from ideal-gas behavior at a given temperature and
pressure can accurately accounted by correction factor called as
compressibility factor, Z.
Pv
Z
RT
or
Pv ZRT
It can also be expressed as;
v actual
Z
v ideal
7. Compressibility Factor - A Measure of
Deviation from Ideal-Gas Behavior
Gases behave differently at a given temperature and pressure, but they
behave very much the same at temperatures and pressures normalized with
respect to their critical temperatures and pressures.
The normalization is done as; P T
PR and TR
Pcr Tcr
v
RT
0.0815 kPa. m3 /kg. K 323 K
0.02632m3 /kg
P 1000 kPa
Therefore, treating the R-134a vapor as an ideal gas would result in an error of
(0.02632-0.02171)/0.02171=0.212, or 21.2 percent in this case.
Example 3.8 (The use of Generalized Charts)-cont’
(b) To determine the correction factor Z from the compressibility chart, we can
first need to calculate the reduced pressure and temperature:
P 1 MPa
PR 0.246
Pcr 4.067 MPa
Z 0.84
T 323 K
TR 0.863
Tcr 374.3 K
Thus,
v Zvideal (0.84)(0.02632 m 3 /kg )
The error in this result is less than 2 percent. Therefore, in the absence of
tabulated data, the generalized compressibility chart can be used with
confidence.
Example 3.9 (Using Generalized Charts to Determine Pressure)
Determine the pressure of water vapor at 600 oF and 0.514 ft3/lbm, using (a)
the steam tables (b) the ideal equation, and (c) the generalized
compressibility chart.
Solution
The gas constant, the critical pressure, and the critical temperature of
refrigerant-134a are determine from Table A-1E to be;
R 0.05956 psia. ft 3 /lbm. R
Pcr 3204 psia
Tcr 1165.3 R
(a) The pressure at the specified state is determined from Table A-6E to be;
v 0.0514 ft 3 /lbm
P 1000 psia
T 600 F
o
This is the experimentally determined value, and thus it is the most accurate.
Example 3.9 (Using Generalized Charts to Determine Pressure)-cont’
(b) The pressure of steam under the ideal-gas assumption is determined from the
ideal-gas relation to be;
P
RT
0.5956 psia. ft 3 /lbm. R 1060 R
1228 psia
3
v 0.514 ft /lbm
Therefore, treating the steam as an ideal gas would result in an error of (1228-
1000)/1000 = 0.228, or 22.8 percent in this case.
(c) To determine the correction factor Z from the compressibility chart
(Fig A-30), we first need to calculate the pseudo-reduced specific volume
and the reduced temperature.
vactual (0.514 ft 3 /lbm)(3204 psia)
vR 2.373
3
RTcr / Pcr (0.5956 psia.ft /lbm. R)(1165.3 R)
PR 0.33
TR
T
1060 R
0.91
Tcr 1165.3 R
RT a
P 2 a,b constant
V b V 2bV b
8. Other Equations of State –cont’
Viral Equation:
PV
Z (3.10)
RT
B C D
Z 1 2 3 ... (3.12)
V V V
B
B' (3.13a )
RT
C B2 D 3BC 2 B 3
C' (3.13b) D' (3.13c)
( RT ) 2 ( RT )3
Equations of State Application
Equation Application
Ideal-gas Pr < 0.05, Tr >1.5
or, P < 2 atm, T > 25 oC
Van der Waals Only for vapor.
Lower pressure.
Viral Equation Only for vapor.
(C = D =…0) Tr > 0.436 Pr +0.6
Redlich/Kwong Only for vapor.
Lower pressure.
Soave/Redlich/Kwong Saturated vapor and saturated liquid.
Higher pressure.
Peng Robingson Saturated vapor and saturated liquid.
Higher pressure.
Standard to hydrocarbon industry.
Thank you
Prepared by,
MISS RAHIMAH OTHMAN