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University of Engineering and Technology Taxila

Mechanical Engineering Department

Notes: 03
(Entry-2016)

Course Title: THERMODYNAMICS-I


Code: ME-121
Tutor: Khalid Masood Khan
Pure Substance and Substance Phase

A pure substance is one that is uniform and invariable in chemical


composition.

A pure substance can exist in more than one phase, but its chemical
composition must be the same in each phase.

A quantity of matter that is homogeneous throughout in both chemical


composition and physical structure is called a phase.
Liquid, Vapor, and Gas

Depending on the condition of pressure and temperature, a substance may


exist in any one of its phases, i.e. solid, liquid, or gas.

Solid phase is not important in engineering thermodynamics, being more


the concern of metallurgist and physicist.

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).

The points , , represent the boiling points of a liquid at


pressures , , respectively.
When a liquid at boiling point is heated further at constant
pressure, the additional heat supplied changes the phase of the
substance from liquid to vapor.

During this change of phase, pressure and temperature remain


constant.

The heat supplied is called the enthalpy (latent heat?) of


vaporization.

The higher the pressure, the smaller is the amount of enthalpy of


vaporization.
For any one pressure at which vaporization is complete, the specific
volume of vapor has a definite value.

Therefore, a series of points such as , , can be plotted and


joined to form a line (fig-3.2).
Extending the two curves (fig-3.1 and fig-3.2) to higher pressures leads
the curves to join at a point thus forming a loop (fig-3.3).

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 .

The condition or quality of wet vapor is defined by its dryness fraction.


Dryness fraction, = mass of dry vapor in 1 of mixture 3. a
hence, wetness fration = 1
Note: for a saturated liquid, = 0; and that for a dry saturated vapor, = 1.
The isothermal at 6 (fig-3.4) is almost a hyperbola, i.e. = .

Now, the properties of an ideal substance called a perfect gas are related by
= constant, called the equation of state.

Applying it to a highly superheated vapor, such as shown by the isothermal at 6 ,


i.e. = 6 = constant along the isothermal .

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.

Unlike a gas, properties of a substance in liquid or vapor phase are not


related by definite laws, and values of properties are found empirically and
tabulated.
Use of Vapor Tables
Saturation State Properties
A specimen row from the tables (Rogers, G. F. C. and Mayhew, Y. R.,
Thermodynamics and Transport Properties of Fluids, SI Units, Basil Blackwell,
1980) is shown in fig-3.5.

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 ).

At point B, dry saturated steam at a pressure of 100 and saturation


temperature of 311 has a specific volume, , of 0.01802 3 , specific
internal energy, , of 2545 and specific enthalpy, , of 2725 .

At point , saturated water at a pressure of 4 and saturation temperature of


143.6 has specific internal energy, , of 605 , and specific enthalpy, ,
of 605 .

The saturated liquid line on a -diagram is very nearly


coincident with the pressure axis in comparison with
the width of the saturation (or wet) loop (fig-3.6).
The change in specific enthalpy from to is given the symbol . When
saturated water is changed to dry saturated vapor, from equation 2.2,

= 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

Using dryness fraction, , as defined (equation 3.a) in equation 3.d,


= 1 +
is negligibly small for most practical cases,
= 3.1
2. Specific Enthalpy

= 1 +
= + ( )
= + fg 3.2

3. Specific Internal Energy

= 1 + 3.3
= + 3.4
Example 3.1

Statement

Find the specific volume, specific enthalpy, and specific internal


energy of wet steam at 18 , dryness fraction 0.9.
Solution

From equation 3.1, = , which on inserting the values gives:


= 0.1104 0.9 3 = 0.0994 3
Note: has to be looked up in steam tables against saturation pressure of
18 . Only one property is required in this case because dry saturated steam
properties exit at the point that is fixed, found, or located by the corresponding
saturation pressure on the -diagram. It is the point on the horizontal line (in
the wet region) for the saturation pressure of 18 , where it connects to the
dry saturated vapor line. One the other extreme is the point for the saturated
liquid that gives the value for should there arise the need to find it.

(next page)
From equation 3.2, = + fg , inserting the values gives:

= 885 + 0.9 1912 = 2605.8

From equation 3.3, = 1 + , inserting the values gives:

= 1 0.9 883 + 0.9 2598 = 2426.5


Example 3.2

Statement

Find the dryness fraction, specific volume and specific internal


energy of steam at 7 and enthalpy 2600 .
Solution
At 7 , = 2764 . Since the given (actual) enthalpy, = 2600 ,
therefore the steam in this condition is wet. From equation 3.2, = + fg ,
2600 = 697 + 2067
2600 697
= = 0.921
2067
From equation 3.1,
= = 0.921 0.2728 3 = 0.2515 3
From equation 3.3, = 1 + , inserting the values gives:
= 1 0.921 696 + 0.921 2573 = 2420
Properties of superheated Vapor

Steam at 2 and 200 is superheated since the saturation


temperature corresponding to 2 is 120.2.

The degree of superheat is 200 120.2 = 79.8 .

Superheated steam tables range in pressure from 0.006112 to


the critical pressure of 221.2 , and there is an additional table of
supercritical pressures up to 1000 .
Fig-3.7 shows a specimen row of values in a superheat table corresponding
to saturation pressure 20 [temperature (212.4)] and a range of
temperatures up to high degrees of superheat.
For example, at 20 and 400 the specific volume is 0.1511 3
and the enthalpy is 3248 .

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

Steam at 110 has a specific volume of 0.0196 3 . For steam in


this condition, find the temperature, the specific enthalpy and the specific
internal energy.
Solution

At 110 , = 0.01598 3 , which is less than the given (actual) specific


volume of 0.0196 3 . Therefore, steam is superheated. The state of steam
is shown as point of fig-3.8. From superheat tables, = 2889 . Using
equation 2.7, = , and inserting the values:
110 105
= = 2889 3
0.0196
10
= 2889 215.6 = 2673.4
Example 3.4

Statement

Steam at 150 has a specific enthalpy of 3309 . For steam in this


condition, find the temperature, the specific volume and the specific internal
energy.
Solution

At 150 , = 2611 , which is less than the actual (given) enthalpy


of 3309 , and hence the steam is superheated. From superheat tables
at 150 , = 3309 at a temperature of 500. The specific volume
is = 0.02078 3 . Using equation 2.7,
150 105
= = 3309 3
0.02078 = 2997.3
10
For properties which are not tabulated exactly in the tables, it is necessary
to interpolate between the values tabulated.

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

Similarly, other properties can be obtained at 9.8 .


Sometimes, it is necessary to perform a double interpolation.
For example, to find the enthalpy of superheated steam at 18.5
and 432, an interpolation between 15 20 as well as
between 400 and 450 is necessary.
A tabular presentation is usually better in such cases (fig-3.10).

p t 400 432 450


15 h 3256 ? 3364
18.5 h ?
20 h 3248 ? 3357
Fig-3.10: Double interpolation
First, find the enthalpy at 15 432,
32
= 3256 + 3364 3256 = 3256 + 0.64 108
50
. . = 3325.1

Then, find the enthalpy at 20 , 432,

. . = 3248 + 0.64 3357 3248 = 3248 + 0.64 109


. . = 3317.8

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.

. . at 18.5 , 432 = 3325.1 0.7 7.3 = 3320


The Perfect Gas

At temperatures that are considerably in excess of the critical temperature of a


fluid, and also at very low pressures, the vapor of the fluid tends to obey the
equation

= =

No gases in practice obey this law rigidly, but many gases tend towards it. An
imaginary gas which obeys the law is called a perfect gas, and the equation,
/ = , is called the characteristic equation of state for a perfect gas.

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)

Or, for a mass occupying a volume ,

= (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.

When mole is used, the elementary entities must be specified


and may be atoms, molecules, ions, electrons, or other particles,
or specified groups of such particles. The unit symbol used for
mole is . For convenience, kilomole is used.
Mass per kilomole of any substance is known as the molar mass, , i.e.

= (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.

Substituting for from equation 3.7 in equation 3.6 gives



= =

Avogadros hypothesis states that the volume of 1 mole of any gas is the same as
the volume of 1 mole of any other gas, when the gases are at the same
temperature and pressure.
Therefore, , is the same for all gases at the same value of and . That is, the

quantity = is a constant for all gases. This constant is called the

molar gas constant, or universal gas constant, and is given the symbol, ,
. . = =
or, = 3.8
or, since = ,

= 3.9

has been shown to be 8314.4 .


Example 3.5

Statement

A vessel of volume 0.2 3 contains nitrogen at 1.013 and 15.


If 0.2 of nitrogen is now pumped into the vessel, calculate the
new pressure when the vessel has returned to its initial temperature.
The molar mass of nitrogen is 28 , and it may be assumed
to be a perfect gas.
Solution

Using equation 3.9,


8314.4
, = = = 296.9
28

Applying equation 3.6 to the system (nitrogen) initial condition,


1 1 = 1 1
1 1 1.013 105 0.2
1 = = = 0.237
1 296.9 288
where 1 = 15 + 273 = 288
0.2 kg of nitrogen is pumped into the vessel, therefore

final mass, 2 = 0.2 + 1 = 0.2 + 0.237 = 0.437

Applying equation 3.6 to the system (nitrogen) final condition,

2 2 = 2 2

However, system (or vessel) volume (2 ) and system (nitrogen) temperature 2


remain the same during the pumping (process),

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

From equation 3.6, 1 1 = 1


1 1 7 105 0.003
= = = 520
1 0.01 404
Note: Both pressure and temperature 131 + 273 = 404 used in the
above equation are in absolute units.
Then from equation 3.9,

= =

Inserting the values,
8314
= = = 16
520
For final temperature, using equation 3.6

2 2 = 2

2 2 1 105 0.02
2 = = = 384.5
0.01 520

i. e. final temperature = 384.5 273 = 111.5


Specific Heats

The specific heat of a solid or liquid is energy transferred by means of


heat to raise unit mass through one degree temperature rise.

For energy transfer as heat while the temperature of a substance


(system) of mass is raised through , the relation is

= 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

Energy transfer as heat in a reversible constant pressure process,


= 2 1 3.12

Energy transfer as heat in a reversible constant volume process,


= 2 1 3.13
Let 1 kg of a perfect gas is heated at constant volume. Using equation 2.3,
= + , and noting that in a constant volume process, = 0, gives

Using equation 3.11, for 1 kg, gives

= =

and integrating, = +
where is a constant
For a perfect gas it can be assumed that = 0 when = 0, which
gives = 0, i.e.

specific internal energy, = 3.14

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

internal energy, = 3.15

Gain in internal energy, between states 1 and 2, of a prefect gas


in process,

2 1 = m 2 1 3.16
Relationship between the specific heats

Using equation 3.16 in non-flow energy equation 2.2, = 2 1 + , gives

= 2 1 + 3. f

In a constant pressure process, = (2 1 ). Using equation 3.6, 1 =


1 and 2 = 2 , then gives,

= 2 1 3. g
Using equation (3. f) in equation (3. g) gives

= 2 1 + 2 1 = ( + ) 2 1

Using equation 3.12 for gives

+ 2 1 = 2 1

+ =

= 3.17
Enthalpy of a Perfect Gas

Equation 2.7 gives, = + . Using = (characteristic equation for a perfect


gas) and = (Joules law), then gives
= + = ( + )

Using equation (3.h) reduces the above expression for specific enthalpy to
= 3.18

For mass, m, of a perfect gas


= 3.19
Like , it is assumed = 0 at = 0; is the thermodynamic temperature, i.e. its
unit is the kelvin (K) in the SI standard of units.
Ratio of Specific Heats

It is the ratio of the two specific heats, i.e.



= 3.20

is always greater than unity. Following table shows typical values for
some gases.

monoatomic diatomic triatomic hydro-carbons


carbon carbon sulphur ethane iso-
Gases argon helium hydrogen nitrogen oxygen
monoxide dioxide dioxide (2 6 ) butane
(A) (He) (2 ) (2 ) (2 )
(CO) (2 ) (2 ) (4 10 )
Gamma
1.6 1.4 1.3 1.11
()
Some Useful Relationships Between , , ,

Dividing, = , by gives

1=


1=


= 3.21
1


Substituting = in equation 3.21 gives


= 3.22
1
Example 3.7

Statement

A certain perfect gas has specific heats as follows


= 0.846 = 0.657
Find the gas constant and the molar mass of the gas.
Solution

Equation 3.17 gives


=
i. e. = 0.846 0.657 = 0.189
or = 189
Now, equation 3.9, gives

=

Inserting the values
8314
= = 44
189
Example 3.8

Statement

A perfect gas has a molar mass of 26 and a value of = 1.26.


Calculate the heat rejected per kg of gas:

a) When the gas is contained in a rigid vessel at 3 and 315, and is


then cooled until the pressure falls to 1.5 .

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

Using equation 3.9


8314
= = = 319.8
26

Equation 3.21 gives


319.8
= = 3
= 1.229
1 10 1.26 1


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 .

From equation 3.13


heat rejected per kg of gas = 2 1
= 1.229 588 294 = 361
b) From the SFEE (equation 2.8)
1 + 12 2 + = 2 + 22 2 +
Changes in velocity are negligible and no work is involved, therefore
= 2 1
For a perfect gas, from equation 3.18,
=
= 2 1
= 1 2 = 1.548 280 20
. . = 1.548 260 = 403
Note that it is not necessary to convert 1 = 280 and 2 = 20 into
kelvin (K) as 1 2 is numerically the same as
the difference 1 2 .