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Notes: 03

(Entry-2016)

Code: ME-121

Tutor: Khalid Masood Khan

Pure Substance and Substance Phase

composition.

A pure substance can exist in more than one phase, but its chemical

composition must be the same in each phase.

composition and physical structure is called a phase.

Liquid, Vapor, and Gas

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

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).

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.

constant.

vaporization.

vaporization.

For any one pressure at which vaporization is complete, the specific

volume of vapor has a definite value.

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 .

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.

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.

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 ).

temperature of 311 has a specific volume, , of 0.01802 3 , specific

internal energy, , of 2545 and specific enthalpy, , of 2725 .

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

of 605 .

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

= 1 +

is negligibly small for most practical cases,

= 3.1

2. Specific Enthalpy

= 1 +

= + ( )

= + fg 3.2

= 1 + 3.3

= + 3.4

Example 3.1

Statement

energy of wet steam at 18 , dryness fraction 0.9.

Solution

= 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:

Example 3.2

Statement

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

temperature corresponding to 2 is 120.2.

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

this condition, find the temperature, the specific enthalpy and the specific

internal energy.

Solution

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

condition, find the temperature, the specific volume and the specific internal

energy.

Solution

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

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).

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

. . = 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.

The Perfect Gas

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)

= (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.

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.

= =

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

Example 3.5

Statement

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

8314.4

, = = = 296.9

28

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

2 2 = 2 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

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

Specific Heats

heat to raise unit mass through one degree temperature rise.

(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

= 2 1 3.12

= 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

= =

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

in process,

2 1 = m 2 1 3.16

Relationship between the specific heats

= 2 1 + 3. f

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

+ 2 1 = 2 1

+ =

= 3.17

Enthalpy of a Perfect Gas

gas) and = (Joules law), then gives

= + = ( + )

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

= 3.18

= 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

= 3.20

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

some gases.

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

= 0.846 = 0.657

Find the gas constant and the molar mass of the gas.

Solution

=

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

Calculate the heat rejected per kg of gas:

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

8314

= = = 319.8

26

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 .

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 .

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