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Notes: 03
(Entry-2016)
A pure substance can exist in more than one phase, but its chemical
composition must be the same in each phase.
When a liquid is heated at any one constant pressure, there is one fixed
temperature at which bubbles of vapor form in the liquid. This
phenomenon is called boiling.
A series of boiling points plotted on a -diagram will appear as a
sloping line (fig-3.1).
Pressure at which the turning point occurs is called the critical pressure
( ), and temperature is called critical temperature ( ). The point itself
is called the critical point (point on fig-3.3). Substance at this condition
undergoes change of phase directly from liquid to gas (highly
superheated vapor) and vice versa, i.e. its never a wet vapor.
Substance existing at a state point inside the loop is called a wet vapor. It is a mixture
of liquid and dry vapor.
Saturation state is defined as a state at which a change of phase may occur without
change of pressure or temperature. Saturation refers here to energy saturation.
Line in fig-3.1 is made up of boiling points (P, , , and numerous others). It is called
the saturated liquid line. Similarly, line in fig-3.2 is made up of saturated vapor points
( , , , and numerous others). It is called the saturated vapor line.
Saturated vapor is usually called dry saturated to distinguish it from liquid or wet
vapor.
Isothermals are lines of constant temperature (fig-3.4). There is
corresponding saturation temperature for each saturation pressure.
The critical temperature line just touches the top of the saturation
loop at the critical point .
Dry saturated vapor when heated at constant pressure becomes superheated.
Difference between the actual temperature of the superheated vapor and the
saturation temperature at the pressure of the vapor is called the degree of
superheat. The vapor at point (fig-3.4) is superheated at and 3 and the
degree of superheat is 3 2 .
Now, the properties of an ideal substance called a perfect gas are related by
= constant, called the equation of state.
All substances tend towards a perfect gas at very high degrees of superheat.
Oxygen ( = 119), nitrogen ( = 147), hydrogen ( = 240), etc.
are highly superheated at normal atmospheric conditions (say, 25 and 1 atm).
Substances normally existing as vapor must be raised to high temperature
before they begin to act as a perfect gas.
For example, at 0.34 the saturation temperature is 72, the specific volume
of dry saturated steam, , at the same pressure is 4.649 3 , the specific
internal energy of dry saturated steam, , is 2472 .
Steam in this state is represented by point A on fig-3.6 (0.34 , 4.649 3 ).
= 2 1 + = +
.
As far in this case, it is the area under the horizontal line on the -diagram,
. . =
which gives = +
= + + 3.
From equation 2.7
= +
. . = + and = +
Inserting hf and hg into equation 3. b,
= = fg = enthalpy latent heat of vaporization 3.
Triple point is the condition at which all the three phases of a substance coexist.
Water at 0.01 and 0.006112 is at the triple point.
In steam tables, the specific internal energy ( ) is taken as zero at the triple point of
water and from, = + , obtained is negligibly small and therefore may be
taken as zero. At the other end of pressure range, at = 221.2 =
374.15, corresponding to critical point of water, fg = 0 (no boiling!).
Properties of Wet Vapor
1. Specific Volume
specific volume of wet vapor =
volume of liquid in wet vapor + volume of dry vapor
= 3.
total mass of wet vapor
= 1 +
= + ( )
= + fg 3.2
= 1 + 3.3
= + 3.4
Example 3.1
Statement
(next page)
From equation 3.2, = + fg , inserting the values gives:
Statement
For pressures above 70 , there is no entry for internal energy and the
values can be found by using equation 2.7. For example, steam at
80 , 400 has an enthalpy, , of 3139 , and a specific
volume, , of 3.428 102 3 , therefore,
80105
3139 = + 3.428 102
103
. .
80 105 2
= 3139 3
3.428 10
10
= 3139 274.2 = 2864.8
Example 3.3
Statement
Statement
It is assumed that the variation between the given values is linear (fig-3.9).
For example, to find saturation temperature corresponding to the
saturation pressure of 9.8 , it is necessary to interpolate
between the values given in the steam tables, i.e.
9.8 9
= 175.4 + 179.9 175.4 = 179
10 9
Now, interpolate between at 15 , 432, and at 20 , 432 in order to find at 18.5 , 432,
3.5
. . = 3325.1 3325.1 3317.8
5
There is a negative sign, in this case, since at 15 , 432 is larger than at 20 , 432.
The constant is called the specific gas constant. The units of are
. Each perfect gas has a different specific gas constant.
The characteristic equation is usually written as
= (3.5)
= (3.6)
Another form of the characteristic equation can be derived using the mole as a
unit. The mole was defined by the 1971 General Conference of Weights and
Measures (CGPM) as follows:
Mole is the amount of substance of a system which contains as
many elementary entities as there are atoms in . of
carbon-12.
= (3.7)
where is in ; is the number of kilomoles; and is in .
Relative molecular mass is numerically equal to the molar mass, , but
is dimensionless.
Statement
2 2 = 2 2
2 2 0.437296.9288
2 = = = 1.87
2 105 0.2
Example 3.6
Statement
0.01 of a certain perfect gas occupies a volume of 0.003 3 at a
pressure of 7 and a temperature of 131. Calculate the molar mass
of the gas. When the gas is allowed to expand until the pressure is 1 ,
the final volume is 0.02 3 . Calculate the final temperature.
Solution
2 2 = 2
2 2 1 105 0.02
2 = = = 384.5
0.01 520
= 3.
where is the energy transferred as heat in a non-flow
process and c is the specific heat.
For a gas (system) there are an infinite number of ways in which energy may be
added between any two temperatures by means of heat, and hence a gas could have
an infinite number of specific heats.
However, only two specific heats for gases are defined; the specific heat at constant
volume, , and the specific heat at constant pressure, , i.e.
= 3.10
or, =
and, = , where = (, )
hence, =
Similarly,
= 3.11
or, =
and, = , where = (, )
hence, =
For a perfect gas the values of and are constant for any one gas at all
pressures and temperatures. Integrating equations 3.10 and 3.11, gives
= =
and integrating, = +
where is a constant
For a perfect gas it can be assumed that = 0 when = 0, which
gives = 0, i.e.
For constant , equation 3.14 establishes the fact that = (). This
is called Joules law, i.e. the internal energy of a perfect gas is a
function of the absolute temperature only.
Equation 3.14, for a mass , of a perfect gas, is
2 1 = m 2 1 3.16
Relationship between the specific heats
= 2 1 + 3. f
= 2 1 3. g
Using equation (3. f) in equation (3. g) gives
= 2 1 + 2 1 = ( + ) 2 1
+ 2 1 = 2 1
+ =
= 3.17
Enthalpy of a Perfect Gas
Using equation (3.h) reduces the above expression for specific enthalpy to
= 3.18
Dividing, = , by gives
1=
1=
= 3.21
1
Substituting = in equation 3.21 gives
= 3.22
1
Example 3.7
Statement
Statement
b) When the gas enters a pipeline at 280, and flows steadily to the end
of the pipe where the temperature is 20. Neglect changes in velocity
of the gas in the pipeline.
Solution
Also from equation 3.20, = , on rearranging it gives
= = 1.26 1.229 = 1.548
a) The volume remains constant for the mass of gas present, and hence the
specific volume remains constant.
1 1 = 1 2 2 = 2
Therefore, since 1 = 2 we have
2 1.5
2 = 1 = 588 = 294
1 3
where 1 = 315 + 273 = 588 .