Chapter 3

Properties of Simple
Compressible Substances
R D Yadav
Assistant Professor
INSTITUTE OF ENGINEERING
TRIBHUVAN UNIVERSITY
• A pure substance is called simple compressible substances when the
mechanical work of expansion or compression is the only quasi-static mode of
work, i.e. W = P. dv
• In simple compressible substance others effects such as electrical effects,
surface effects etc. are neglected and hence named as simple compressible
substance.
• A pure substance is of constant chemical composition throughout its mass and
is of one component system. It may have one or more phases, e.g. a mixture
of ice, water and steam is an example of pure substance or one component
system since chemical composition of all three phases is the same
• State postulate of simple compressible substance
• The equilibrium state of simple compressible substance is completely specified
by two property rule. In two property rule any equilibrium state can be
specified by two independent intensive properties.
• For example, for simple compressible substance in liquid phase
• P is specified if T and v are specified.
• v is specified if P and T are specified.
• T is specified if P and v are specified.
• The above conditions are true for solid as well as vapor phases also. But for
mixture of liquid and vapor phases in equilibrium the following conditions exist:
• P is specified if T and v are specified.
• v cannot be specified if P and T are specified.
• T is specified if P and v are specified.
• From above we see that for specific volume T and P are not independent
properties.
 Formation of steam
In engineering application the formation of steam includes
• Heating water to its boiling point
• Evaporation of water and conversion of it into dry saturated vapor.
• Heating the dry saturated steam into superheated steam.
• Formation of steam from ice is not economical and not applicable in
engineering as water is already available
• Even though, for the knowledge of the students the formation of
steam from ice at -100C to steam at 2500C at atmospheric pressure is
discussed and are depicted on T-Q, T-v and P-v diagrams as shown in
figures
 T

2500 𝐶 6 For substance other than

T
6 water
2500 𝐶 For water 6

4 5
Superheat 1000 𝐶
1000 𝐶 4 5 ing
4 5
Evaporat 0
3′
00 𝐶 2 3 ion 4 𝐶
Heating 00 𝐶 3 2 2 3
water
Heating 1 1
−100 𝐶 1 −100 𝐶
Ice v

Q
1-2 Solid state (heating ice from -100C to 00C)
2-3 Melting ice (melting ice from 00C to water 00C)
3-4 Liquid state (heating water at 00C to 1000C) p
4-5 Vaporization (heating water at 1000C to vapor at1000C)
5-6 Vapor state (heating vapor at 1000C to superheated vapor at 2500C) Atmospheric pressure

1 3 2 4 5 6

v
• Process 1-2: It is heating ice from -100C to ice at 00C. Since temperature rises during this heating, it is sensible
heating. The amount of heat during this heating process is as
• Q1−2 = mi × cpi × {0 − −10 }
• Process 2-3: It is heating ice at 00C to water at 00C. It is melting process. During this process of heating, ice is
converted into water at same temperature as there is two phase mixture i.e. ice and water. It is to be noted
that for water volume decreases during this process. However, for normal substance there is increase in
volume when changes from solid to liquid. The entire ice is melt at point 3. The heat required during the
process is called latent heat of fusion and is given by
• Q2−3 = mi × Lf
• Process 3-4: It is heating of water at 00C to water at 1000C. This is sensible heating as there is rise in
temperature. During this process of heating volume gets increased. It is to be noted that for water volume
further gets decreased from 00C to 40C and after then its volume gets increased as shown in T-v diagram. The
heat required during this process is given by
• Q3−4 = mw × cpw × (100 − 0)
• Process 4-5: It is heating water at 1000C to vapor at 1000C. During this heating process as there is mixture of
liquid and vapor i.e. two phase mixture, temperature remains constant. It is sensible heating and at point 4
entire liquid is converted into vapor. The heat required during this process of heating is called latent heat of
evaporation or vaporization and is given by
• Q4−5 = mw × Lv
• Process 5-6: It is heating vapor at 1000C to superheated vapor at 2500C. It is also sensible heating as there is
rise in temperature and called as superheating the vapor or steam. The heat required during this superheating
is given by
• Q5−6 = mv × cpv × (250 − 100)
 Pc = 221.2 bar
P t c = 374.150 C
C (critical point) vc = 0.00317 m3 /kg
(L) G mg mf
x = m +m y=
mf + mg
f g
(V)
Liquid region
Vapor region
E
Saturated liquid line F Saturated vapor line
(L+V) D
2 𝑡𝑓 A 3 𝑡𝑔 4𝑡
𝑠𝑢𝑝
1
Two phase region
X=0 X=1
X=0.1
A B
𝑣𝑓𝑔 X=0.9
v
𝑣𝑓 𝑣𝑔

Figure: pressure-specific volume diagram 𝑡𝑠𝑢𝑝 − 𝑡𝑔 = 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟 ℎ𝑒𝑎𝑡

𝑐𝑝 𝑡𝑠𝑢𝑝 − 𝑡𝑔 = ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟 ℎ𝑒𝑎𝑡

• Saturation State
• A saturation state is the state from which change of phase occurs without
change of pressure or temperature.
• A saturation solid state is that from which solid is changed into liquid state
at constant temperature and pressure.
• A saturation liquid state is that from which liquid is either changed into
solid or liquid is changed into vapor. If liquid is change into solid, then it is
called saturation with respect to solid. In case that liquid is changed into
vapor, then it is called saturation with vapor.
• A saturation vapor state is that from which vapor is condensed into liquid.
• quality or dryness fraction
• The vapor produced at saturation temperature in the transformation stage will contain liquid droplets in the
suspension as long as there is liquid present. The vapor so produced is called wet vapor. If dry vapor is made
wet by liquid droplets in the suspension, it is interesting and also very important to know the degree of
wetness.
• If in 1 kg of water-vapor mixture, x kg is dry vapor and (1-x) kg is liquid, then x is called dryness fraction or
quality of liquid-vapor mixture.
• Quality or dryness fraction is defined as the ratio of mass of dry saturated vapor to the mass of wet vapor
containing dry saturated vapor.
• That is,
mass of dry saturated vapor
• Quality or dryness fraction =
mass of wet vapor containing dry saturated vapor
mg
• Or, x =
mf +mg
• Where, mg = mass of dry vapor
• mf = mass of liquid
• The value of x lies between 0 to 1. For saturated water which just starts boiling, the value of x is zero and for
saturated vapor when vaporization is completed, the value of x is one. Between zero and one vapor is wet.
• If the value of x is 0.8, it means that in one kg of wet vapor there is 0.8 kg dry vapor and 0.2 kg is suspended
water droplets. It should be noted that the quality of vapor x is treated as intensive property of vapor.
• Liquid fraction or moisture fraction is defined by the ratio of mass of liquid to the mass of liquid and mass of
vapor, i.e.
mass of liquid mf
• Moisture fraction, y = =
mass of liquid+mass of vapor mf +mg
 T
C (critical point)

Saturated vapor line D

Liquid region
(V)

(L)
E Constant pressure line
F
Vapor region
Saturated liquid line
Two phase region

(L+V)
G
B
A Saturated liquid line
v

Figure: Temperature-specific volume diagram

 P P B
B C (critical point) C (critical point)
Fusion Liquid Fusion Liquid
curve Vaporization curve Vaporization
1
curve curve
2 Solid A
Solid A
Triple
Triple point point
Sublimation
curve Sublimation
Vapor curve Vapor

T O
O T

Figure: substance that expands on freezing Figure: substance that contracts upon freezing
 C (critical point)
P

s=C
Liquid P=C, t=C
v=C
region

P=C, t=C

Two phase region

t=C Vapor region

Saturated liquid line Saturated vapor line

A
Quality line
B
h

Figure : Pressure-enthalpy diagram

 T V =C
C (critical point)

Liquid
P=C
region

P=C, t=C
Vapor region

Saturated liquid line P=C, t=C h=C

Two phase region Saturated vapor line

A B

𝑠𝑓 𝑠𝑔 s

Figure : Temperature-entropy diagram

h
P=C t=C
Critical point
C
Liquid v=C
region
Vapor region

Saturated vapor line

Saturated
liquid line
B
Two phase region
X=0.9
A 𝑠𝑓𝑔 X=0.8
𝑠𝑓 𝑠𝑔 s

Figure : Enthalpy-entropy diagram

 Pc = 221.2 bar
P t c = 374.150 C
C (critical point) vc = 0.00317 m3 /kg
(L) G mg mf
x = m +m y=
mf + mg
f g
(V)
Liquid region
Vapor region
E
Saturated liquid line F Saturated vapor line
(L+V) D
2 𝑡𝑓 A 3 𝑡𝑔 4
1
Two phase region
X=0 X=1
X=0.1
A B
𝑣𝑓𝑔 X=0.9
v
𝑣𝑓 𝑣𝑔

Figure: pressure-specific volume diagram 𝑡𝑠𝑢𝑝 − 𝑡𝑔 = 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟 ℎ𝑒𝑎𝑡

𝑐𝑝 𝑡𝑠𝑢𝑝 − 𝑡𝑔 = ℎ𝑒𝑎𝑡 𝑜𝑓 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟 ℎ𝑒𝑎𝑡

 Tabular Data

• We have already discussed the various thermodynamics diagrams

• In engineering calculation however the thermodynamics tables for
compressible substances are common in use
• The following tabular data are tabulated in thermodynamics tables
I. Table for saturated liquid
• For saturated liquid for one pressure there is corresponding saturation
temperature. Similarly, for one temperature there is corresponding saturation
pressure. So for each value of pressure or temperature, the value for specific
enthalpy, hf; specific entropy, sf; specific internal energy, uf and specific volume,
vf are tabulated, as shown below in both pressure table and temperature table.
These values are obtained experimentally. The value for specific internal energy
are generally not tabulated in the most of the tables, so it can be found by using
the relation
• hf = uf + p vf
II. Table for saturated vapor
• Like saturated liquid, the values for saturated vapor such as specific
enthalpy, specific entropy, and specific volume are tabulated for each value
of pressure or temperature
• The value for specific internal energy, which is generally not tabulated in
most of the tables is found by using the relation
hg = ug + p vg
• In thermodynamics table generally table for saturated liquid and table for
saturated vapor are combined together and given the name saturation
table
• In saturation table difference of specific enthalpy, specific entropy and
specific volume of saturated liquid and saturated vapor are also tabulated
and denoted by hfg, sfg and vfg respectively
 Table : properties of water-temperature table

T P vf vfg vg uf ufg ug hf hfg hg sf sfg sg

0C kPa m3/kg m3/kg m3/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg.K kJ/kg.K kJ/kg.K
5 0.8726 0.001 147.02 147.02 21.02 2360.4 2381.4 21.021 2488.7 2509.7 0.07626 8.9473 9.0236
10 1.2281 0.001 106.32 106.32 41.986 2346.3 2388.3 41.988 2476.9 2518.9 0.151 8.7476 8.8986
15 1.7056 0.001001 77.896 77.897 62.915 2332.3 2395.2 62.917 2465.1 2528 0.2242 8.555 8.7792

Table : properties of water-pressure table

P T vf vfg vg uf ufg ug hf hfg hg sf sfg sg

kPa 0C m3/kg m3/kg m3/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg.K kJ/kg.K kJ/kg.K

1 6.9696 0.001 129.19 129.19 29.287 2354.8 2384.1 29.288 2484 2513.3 0.1059 8.8678 8.9737
0.00100
1.5 13.021 87.97 87.971 54.634 2337.9 2392.5 54.635 2469.8 2524.4 0.1954 8.6304 8.8258
1
0.00100
2 17.497 66.997 66.998 73.364 2325.2 2398.6 73.366 2459.2 2532.6 0.2603 8.4613 8.7216
1
0.00100
2.5 21.08 54.248 54.249 88.353 2315.1 2403.5 88.356 2450.7 2539.1 0.3116 8.3295 8.6411
2
III. Table for compressed liquid
• For compressed or sub-cooled liquid, the change in properties with pressure is
very little. So the properties like specific enthalpy, specific entropy, specific
internal energy and specific volume are taken same as the value for saturated
liquid, i.e. also for compressed liquid
• Specific enthalpy = hf Specific entropy = sf
• Specific volume = vf Specific internal energy = uf
Table : Properties of WATER in Compressed Liquid State

P T v u h s P T v u h s
kPa 0C m3/kg kJ/kg kJ/kg kJ/kg.K kPa 0C m3/kg kJ/kg kJ/kg kJ/kg.K
5,000 10 0.000998 41.860 46.850 0.1505 10,000 10 0.000996 41.729 51.685 0.1500
30 0.001002 125.21 130.22 0.4350
30 0.001000 124.75 134.75 0.4334
50 0.001010 208.58 213.63 0.7014
50 0.001008 207.85 217.93 0.6991
70 0.001020 291.97 297.07 0.9520 70 0.001018 290.98 301.16 0.9491
IV. Table for superheated vapor
• The properties are very sensitive to pressure for superheated vapor. Therefore,
values for specific enthalpy, specific entropy, specific volume and specific
internal energy are tabulated for each value of pressure and temperature
independently.

Table : Properties of Superheated Steam

P T v u h s P T v u h s
kPa 0C m3/kg kJ/kg kJ/kg kJ/kg.K kPa 0C m3/kg kJ/kg kJ/kg kJ/kg.K
10 (45.82) (14.674) (2437.0) (2583.8) (8.1482) 50 (81.33) (3.2408) (2483.3) (2645.3) (7.5928)
50 14.869 2443.1 2591.8 8.1731 100 3.4188 2511.2 2682.1 7.6941
100 17.196 2515.0 2687.0 8.4471 150 3.8895 2585.2 2779.7 7.9394
150 19.513 2587.4 2782.5 8.6873 200 4.3560 2659.4 2877.2 8.1572
V. Table for super critical vapor
• For long time engineers were constrained to work below the critical pressure
due to practical reason
• But, now the vapor above the critical level is generated. This is achieved by
generating vapor without boiling
• The values such as specific enthalpy, specific entropy and specific volume are
tabulated for each value of pressure or temperature independently.
 Thermodynamics properties
• We have already discussed the thermodynamics properties like pressure and temperature. The other remaining properties
such as internal energy, entropy, specific volume, enthalpy etc. are discussed as below.
I. Internal Energy
• Specific internal energy of simple compressible substance is given by
• u = h − pv ,Where, u = specific internal energy, h = specific enthalpy, p = pressure, v = specific volume
• The internal energy of saturated liquid is
uf
• The internal energy of wet vapor is
𝑢 = 𝑢𝑓 + 𝑥 × 𝑢𝑓𝑔
The internal energy of dry saturated vapor is
ug
• The internal energy of superheated vapor is
usup
The change in internal energy from liquid to vapor is
ug – uf = (hg – hf ) – (Pg . vg – Pf . vf ) = hfg – P (vg − vf )
• It is to be noted that in some cases, the value of P (vg − vf ) is negligible and this is neglected.
• Thus, neglecting P (vg − vf ), we get
• ug – uf = hfg = L = Latent heat of vaporization
II. Entropy
• The change of entropy is given by
𝜕q
• ds =
T
• Where, 𝜕q = cp dT = Heat added or removed.
• T=Temperature at the boundary.
𝜕q
• ∴ds =
T T2
cp dT T2
Or, s2 − s1 = = cp loge
T T1
T1
• If T1 is taken as 00C for entropy as datum, then
T
s = cp log e
273
• Entropy for saturated liquid is
Tf
sf = cpf log e
273
• Entropy for wet vapor is
Tf L
s = x sg = sf + x sfg = cpf loge +x
273 Tf
• Entropy of dry saturated vapor is
s = sg = sf + sfg
• Entropy of superheated vapor is
Tsup
s = sg + csup loge
Tf
Tsup
Or, s = sf + sg + csup loge
Tf
III. Enthalpy, h = u + Pv
• The enthalpy of saturated liquid is
hf = m ⨯ cp ⨯ (t f − 0) = m ⨯ cp ⨯ t f
For liquid heated from zero degree Celsius
• The enthalpy of wet vapor is
h = xhg = hf + xhfg = hf + xL
• Enthalpy of dry vapor is
hg = hf + hfg
• Enthalpy of superheated vapor is
hsup = hg + cp ⨯ (t sup − t f )
Here value of cp depends upon the degree of super heat and pressure of super-
heated vapor.
IV. Specific volume
Consider 1 kg of wet vapor. If x is the dryness fraction, then mass of dry vapor is x kg and
mass of liquid is (1-x) kg.
• The volume of saturated liquid is
vf
• The volume of dry saturated vapor is
vg
• The volume of wet vapor is
v = volume of water + volume of vapor
Or, v = (1 − x) vf + xvg
Or, v = vf − xvf + xvg = vf + x vg − vf = vf +
xvfg
The volume due water is very small except for very high pressure and hence it is
neglected. Thus, the volume of wet vapor becomes
• v = xvg
• Interpolation for tabulated data
• The values such as specific enthalpy, specific entropy, specific volume and specific
internal energy are not tabulated for each value of pressure and or temperature. For
example, the value for 10 bar and 10.5 bar are given, then the value for 10.25 bar can
be found by interpolation as follows:
P−P1 𝑦−𝑦1 𝑃−𝑃1
• y = y1 + (y2 − y1 ) Or, =
P2 −P1 𝑦2 −𝑦1 𝑃2 −𝑃1 ℎ − ℎ1 𝑃 − 𝑃1
=
Where, y = value at 10.25 to be found ℎ2 − ℎ1 𝑃2 − 𝑃1

y1 = the value at 10 bar

y2 = the value at 10.5 bar
ℎ − ℎ1 𝑡 − 𝑡1
P = 10.25 bar =
ℎ2 − ℎ1 𝑡2 − 𝑡1
p1 = 10 bar
p2 = 10.5 bar
• The above equation can be written in term of temperature also as
T−T1
• y = y1 + (y2 − y1 )
T2 −T1
• The above equation gives the values satisfactory for small increments of temperature
or pressure as we see for saturation liquid and saturation vapor
• But in case of superheated vapor there is not small increment in the variable like
pressure and temperature. So, the values if calculated by using above linear
interpolation relation does not give accurate values especially for specific entropy and
specific volume.
• As entropy is proportional to logarithm of temperature ratio for given pressure, the
above expression for specific entropy can be written as
S
T
ln
T1
= s1 + s2 − s1
T2
ln
T1
• For given temperature since specific volume is proportional to reciprocal of pressure
1 1
v−v1 −
P P1
• = 1 1
v2 −v1 −
P2 P1
1 1
−
P P1
• Or, v = v1 + ( 1 1 )(v2 − v1 )
−
P2 P1