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In this chapter, the concept of a pure substance and the physics of phase-change
processes were introduced. Various property diagrams and P-v-T surfaces of pure substances
were also illustrated. After demonstrating the use of the property tables, the hypothetical
substance ideal gas and the ideal-gas equation of state were discussed. The compressibility
factor, which accounts for the deviation of real gases from ideal-gas behavior, was introduced,
and some of the best known equations of state such as the van der Waals, Beattie-Bridgeman,
and Benedict-Webb-Rubin equations were presented.
Pure Substance
A substance that has a fixed chemical composition throughout is called
a pure substance such as water, air, and nitrogen.
A pure substance does not have to be of a single element or compound.
A mixture of two or more phases of a pure substance is still a pure
substance as long as the chemical composition of all phases is the same.
COMPRESSED
LIQUID
T2 = const. >T1
REGION
SATURATEDLIQUID
sat. liquid VAPOUREGION
line R T1 = const
Property Tables
For most substances, the relationships among thermodynamic
properties are too complex to be expressed by simple equations. Thus,
properties are frequently presented in the form of tables, see Table A4.
The subscript f is used to denote properties of a saturated liquid and
g for saturated vapour. Another subscript, fg, denotes the difference
between the saturated vapour and saturated liquid values of the same
property. For example: vf = specific volume of saturated liquid vg =
specific volume of saturated vapour vfg = difference between vg and vf
( vfg = vg vf)
Enthalpy: is a property defined as H = U + PV (kJ) or h = u + Pv
(kJ/kg) (per mass unit).
Enthalpy of vapourization (or latent heat): represents the amount of
energy needed to vapourize a unit mass of saturated liquid at a given
temperature or pressure. It decreases as the temperature or pressure
increase, and becomes zero at the critical point.
x=vave -v f
v fg
P or critical point
T
sat.
sat.
vapour
liquid
states
states
sat. vapour
sat. liquid
Fig. 4: The relative amounts of liquid and vapour phases (quality x) are
used to calculate the mixture properties.
Similarly,
uave =uf +xu fg
y f yave
yg
Note: pressure and temperature are dependent in the saturated mixture
region.
v1=v f 1 +x1(vg1 - v f1 )
From Table A -5 at P =1 bar =100 kPa
v1 =0.001043+0.5 (1.694 - 0.001043)
=0.8475 m3 /kg
At state 2, the pressure is known. Volume and mass remain constant
during the heating process within the container, so v2=v1. For P2= 0.15
MPa, Table A5 gives vf2= 0.001053 and vg2=1.1593 m3/kg. Since
vf2 < v2 < vg2
State 2 must be in the twophase region as well. Since state 1 and 2 are
in the twophase liquidvapour region, the temperatures correspond to
the saturation temperatures for the given. Table A5:
T1 = 99.63 C and T2 = 111.4 C
To find the mass of water vapour present, we first find the total mass, m.
V 0.5m3
m= v = 0.8475m3 / kg
=0.59kg mg1
=x1m=0.5(0.59kg)=0.295kg
3
P2 = 1.5 bar
2
P1 = 1 bar
1
The mass of vapour at state 2 is found similarly using quality x2. From
Table A5, for P2 = 1.5 bar, we have:
v-v f 2
x2 =
vg2 -
vf2
x2 = = 0.731
mg2 = 0.731(0.59kg)=0.431
kg
If heating continued, state 3 would be on the saturated vapour line, as
shown in on the Tv diagram above. Thus, the pressure would be the
corresponding saturation pressure.
Interpolating in Table A5 at vg = 0.8475 m3 /kg, we get P3 = 2.11 bar.
2 Superheated Vapour
Superheated region is a single phase region (vapour only), temperature
and pressure are no longer dependent. See Table A6 for superheated
vapour properties.
If T>> Tcritical or P<<Pcritical, then the vapour can be approximated as an
ideal gas.
T 323K
TR = = =0.863
Tcr 374.3K
From Fig. A28, Z= 0.84. Thus,
v = Z videal = 0.84 (0.02632 m3/kg) =0.02211 m3/kg
The error is less than 2%.
Therefore, in the absence of exact tabulated data, the generalized
compressibility chart can be used with confidence.
THEORY
Figure 1. H2 example
Part B: Phases of Pure Substance
Substances can be divided into three different phases (figure 2) such as:
- State A: Fixed position
- State B: Group together and move about each other
- State C: Random movement
where
The properties of saturated liquid remain the same either it exists alone or in a mixture
with saturated vapour. The mixture also dependent on pressure and temperature. For
convenience, this two phases system can be treated as a homogenous mixture. Therefore, the
average volume of saturated liquid-vapour mixture is the sum of saturated vapour and
saturated liquid. Below figure show the derivation of formula using the condition of
homogenous mixture.
y = v, u, or h.
where
v= specific volume
u= internal energy
h= enthalpy
With the condition
Several equations have been proposed to represent the P-v-T behavior of substances
accurately over a larger region with no limitations.
This model includes two effects not considered in the ideal-gas model
- the intermolecular attraction forces
-the volume occupied by the molecules themselves
Beattie-Bridgeman Equation of State
Benedict-Webb-Rubin Equation of State
CASE STUDY
Example 1
Determine the internal energy of refrigerant 134a at a temperature of 0C and a quality of
60%.
From table A-5:
Uf = 51.63 kJ/kg
Ug = 230.16 kJ/kg
The internal energy of R 134a at a given condition:
U = Uf + x(Ug Uf)
= 51.63 + (0.6)(230.16 51.63)
= 158.75 kJ/kg
Example 2
A rigid tank contains 50kg of saturated liquid water at 90C. Determine the pressure in tank
and the volume of the tank.
m = 50kg T = 90C
From table A-4,
P = 70.183 kPa
v= 0.001036 m^3/kg
V = mv
= (50)(0.001036)
= 0.0518 m^3
Example 3
A piston cylinder device contains 0.06m^3 of saturated water vapor at 350kPa pressure.
Determine the temperature and mass of vapor inside the cylinder.
P = 350kPa V = 0.06m^3
From table A-5,
T = 138.86C
V = 0.22422 m^3/kg
V = mv
m = 0.06 / 0.52422
= 0.114 kg
Example 4
A closed, rigid container of volume 0.5 m3 is placed on a hot plate. Initially the container holds
a two-phase mixture of saturated liquid water and saturated water vapor at P1= 1 bar with a
quality of 0.5. After heating, the pressure in the container is P2=1.5 bar. Indicate the initial and
final states on a T-v diagram, and determine:
a) the temperature, in C, at each state.
b) the mass of vapor present at each state, in kg.
c) if heating continues, determine the pressure, in bar, when the container holds only
saturated vapor.
Solution:
Assumptions:
1. Water in the container is a closed system.
2. States 1, 2, and 3 are equilibrium states.
3. The volume of container remains constant.
Two independent properties are required to fix state 1 and 2. At the initial state, the pressure
and quality are known. Thus state 1 is known, as mentioned in the problem. The specific
volume at state 1 is found using the given quality:
v1 v f 1 x1 v g1 v f 1
From Table A - 5 at P 1 bar 100 kPa
v1 0.001043 0.5 (1.694 0.001043) 0.8475 m 3 / kg
At state 2, the pressure is known. Volume and mass remain constant during the heating
process within the container, so v2=v1. For P2= 0.15 MPa, Table A-5 gives vf2= 0.001053 and
vg2=1.1593 m3/kg. Since
vf2 < v2 < vg2
State 2 must be in the two-phase region as well. Since state 1 and 2 are in the two-phase
liquid-vapor region, the temperatures correspond to the saturation temperatures for the
given. Table A-5:
T1 = 99.63 C and T2 = 111.4 C
To find the mass of water vapor present, we first find the total mass, m.
V 0.5m 3
m 0.59kg
v 0.8475m 3 / kg
m g1 x1 m 0.50.59kg 0.295kg
3
P2 = 1.5 bar
2
P1 = 1 bar
1
The mass of vapor at state 2 is found similarly using quality x2. From Table A-5, for P2 = 1.5 bar,
we have:
v vf2
x2
vg 2 v f 2
0.8475 0.001053
x2 0.731
1.159 0.001053
mg 2 0.731 0.59kg 0.431 kg
Example 5
Determine the enthalpy of 1.5 kg of water contained in a volume of 1.2 m3 at 200 kPa.
Recall we need two independent, intensive properties to specify the state of a simple substance.
Pressure P is one intensive property and specific volume is another. Therefore, we calculate
the specific volume.
Volume 12. m3 m3
v 0.8
mass 15
. kg kg
Using Table A-5 at P = 200 kPa,
vf = 0.001061 m3/kg, vg = 0.8858 m3/kg
Is v v f ? No
Is v f v v g ? Yes
Is v g v ? No
We see that the state is in the two-phase or saturation region. So we must find the quality x
first.
v v f x (v g v f )
=
0.8 .0001061
0.8858 0.001061
=0.903
Then,
h h f x h fg
504.7 (0.903)(2201.6)
kJ
2492.7
kg
Example 6
Calculate the specific volume of nitrogen at 300 K and 8.0 MPa and compare the result with the
value given in a nitrogen table as v = 0.011133 m3/kg.
From Table A.1 for nitrogen
Tcr = 126.2 K, Pcr = 3.39 MPa R = 0.2968 kJ/kg-K
T 300 K
TR 2.38
Tcr 126.2 K
P 8.0 MPa
PR 2.36
Pcr 3.39 MPa
Since T > 2Tcr and P < 10Pcr, we use the ideal gas equation of state
Pv RT
kJ
0.2968 (300 K ) 3
RT kg K m MPa
v
P 8.0 MPa 103 kJ
m3
0.01113
kg
Example 7
An ideal gas is contained in a closed assembly with an initial pressure and temperature of 220
kPa and 70C respectively. If the volume of the system is increased 1.5 times and the
temperature drops to 15C, determine the final pressure of the gas.
State 1:
P1 = 220kPa
T1 = 70 + 273K = 343K
State 2:
T2 = 15 +273 = 288K
V2 = 1.5V1
From ideal gas law:
11 22
=
1 2
1 288
P2 =
1.51
(343) (220103 )
= 123.15 kPa
Example 8
A closed assembly contains 2 kg of air at an initial pressure and temperature of 140 kPa and
210C respectively. If the volume of the system is doubled and temperature drops to 37C,
determine the final pressure of the air. Air can be modelled as an ideal gas.
State 1:
P1 = 140 kPa
T1 = 210 + 273K = 483K
State 2:
T2 = 37 + 273 = 310K
V2 = 2V1
From ideal gas law:
11 22
=
1 2
1 310
P2 =
21
(483) (140103 )
= 44.93 kPa
Example 9
An automobile tire with a volume of 0.6 m^3 is inflated to a gage pressure of 200kPa calculate
the mass of air in the tire if the temperature is 20C.
State 1:
P = 200 + 100 kPa
T = 20 + 273K = 293K
From ideal gas law:
=
300103 (0.62 )
3
=
287 (293)
.
= 2.14 kg
Example 10
Determine the specific volume of R-134a at 1 MPa and 50C, using (a) ideal gas equation (b)
the generalized compressibility chart. Compare the values obtained with the actual value of
0.02171 m3/kg.
Solution:
From Table A-1, for R-134a, R = 0.0815 kPa.m3/(kg.K), Pcr = 4.067 MPa, and Tcr = 374.3 K
(a) Ideal gas equation of state
v
RT
0.0815 kPa.m 3 / kg.K 323 K
0.02632 m 3 / kg
P 1000 kPa
Comparing with the tabulated value, using ideal gas equation one would get an error of
(0.02632-0.02171)/0.02171=0.212 or 21.2%.
(b) To determine the correction factor Z,
P 1MPa
PR 0.246
Pcr 4.067 MPa
T 323K
TR 0.863
Tcr 374.3K
From Fig. A-28, Z= 0.84. Thus,
v = Z videal = 0.84 (0.02632 m3/kg) =0.02211 m3/kg
DISCUSSION
T-v diagram shows the state of saturated liquid water of the phases change process of
water at 1 atm pressure. The saturation line continues to shrink when the pressure increase
further and comes to a point call critical point. This point is which the saturated liquid and
saturated vapor states are identical. The temperature at that point is critical temperature. The
pressure at critical point is critical pressure and the volume at that point is critical volume. P-
v diagram is also similar to T-V diagram. The difference of P-V diagram is just that the
constant lines are having downward trend. P-T diagram is related to pure substance and its
called phase diagram. Saturated liquid water is vaporized at constant pressure. The amount of
energy needed to vaporize a unit of mass substance at a given pressure is the enthalpy of
vaporization of that pressure. At the saturation temperature, the temperature of water is
higher than the saturation temperature because the water is in superheated vapor region. The
temperature and pressure are not dependent properties and used as two independent
properties. Water vapor does not consider as ideal gas or not depends on the pressure that
acting on it. When the pressure is below 10kPa, water vapor is treated as ideal gas. This was
applied in applications such as air conditioning applications as the pressure of water vapor is
relatively small. Meanwhile, for steam power plant, which has a high pressure of water vapor
does not able to apply the ideal gas relations as the pressure exceed the critical point and the
saturated vapor line. The pressure in gas container is due to the individual molecules striking
the wall of container and exerting a force on it. This force is proportional to the average
velocity and the number of molecules per unit volume of the container. Therefore, the
pressure exerted by gas is a function of density and temperature of gas. Relatively humidity is
the ratio of the actual amount of moisture in the air at a given temperature to the maximum
amount air can hold at that temperature. For imbalance of a commodity in a medium, nature
ends to redistribute it until balance is establish. This tendency is often called driving force
which occurs behind many naturally occurring transport phenomena. The amount of
commodity per unit volume is concentration, which occurs from high concentration to the
direction of lower concentration, which is also known as diffusion process. The natural
tendency of water to evaporate in order to achieve phase equilibrium with the water vapor in
surrounding air forms the basis for the operation of the evaporative coolers. Boiling and
evaporation are often used interchangeably to indicate phase change from liquid to vapor.
Evaporation occurs at the liquid vapor interface when the vapor pressure is less than the
saturation pressure of the liquid at a given temperature. Boiling on the other hand occurs at
the solid liquid interface when a liquid is brought into contact with a surface maintained at a
temperature, T which is sufficiently above the saturation temperature of a liquid.
CONCLUSION
A substance that has a fixed chemical composition throughout is called a pure substance. A
pure substance exists in different phases depending on its energy level. In the liquid phase, a
substance that is not about to vapourize is called a compressed or sub cooled liquid. In the
gas phase, a substance that is not about to condense is called a superheated vapour. During a
phase-change process, the temperature and pressure of a pure substance are dependent
properties. At a given pressure, a substance changes phase at a fixed temperature, called the
saturation temperature. Likewise, at a given temperature, the pressure at which a substance
changes phase is called the saturation pressure. During a boiling process, both the liquid and
the vapour phases coexist in equilibrium, and under this condition the liquid is called
saturated liquid and the vapour saturated vapour. In a saturated liquid-vapour mixture, the
mass fraction of vapour is called the quality and is expressed as
Quality may have values between 0 (saturated liquid) and 1 (saturated vapour). It has no
meaning in the compressed liquid or superheated vapour regions. In the saturated mixture
region, the average value of any intensive property y is determined from
where/stands for saturated liquid and g for saturated vapour. In the absence of compressed
liquid data, a general approximation is to treat a compressed liquid as a saturated liquid at the
given temperature,
where Pcr and Ta are the critical pressure and temperature, respectively. This is known as the
principle of corresponding states. When either P or T is unknown, it can be determined from
the compressibility chart with the help of the pseudo reduced specific volume, defined as
The P-w-T behaviour of substances can be represented more accurately by more complex
equations of state. Three of the best known are
Beattie-Bridgeman:
Where,
Benedict- Webb-Rubin:
where Ru is the universal gas constant and v is the molar specific volume.