Properties of Pure

Substances
Suchit Kumar Gupta
 Introduction
• Simple System: A simple system is one in which the effects of motion, viscosity, fluid shear, capillarity, anisotropic
stress, and external force fields are absent

• Homogeneous Substance: A substance that has uniform thermodynamic properties throughout is said to be
homogeneous

• Pure Substance: A pure substance has a homogeneous and invariable chemical composition and may exist in more
than one phase
Examples:
1. Water (solid, liquid, and vapor phases)
2. Mixture of liquid water and water vapor
3. Carbon dioxide, CO2
4. Nitrogen, N2
5. Mixtures of gases, such as air, as long as there is no change of phase
DEFINITION OF THE PURE SUBSTANCE
A pure substance is a system which is
- homogeneous in composition
- homogeneous in chemical aggregation
- invariable in chemical aggregation
the chemical elements must be combined chemically in
the same way in all parts of the system

the state of chemical combination of the

system does not change withtime

Steam CO2 H2
+
O2

Pure Substance Pure Substance Not a Pure Substance

 Phase Change of a Pure Substance
• Let's consider the results of heating liquid water from 20oC, 1 atm. while keeping the pressure
constant

- We will follow the constant pressure process

- First place liquid water in a piston-cylinder device where a fixed weight is placed on the piston to
keep the pressure of the water constant at all times

- As liquid water is heated while the pressure is held constant, the following events occur

• Process 1-2:
- The temperature and specific volume will increase from the compressed liquid, or subcooled liquid,
state 1, to the saturated liquid state 2
State 1
- In the compressed liquid region, the properties of the liquid are approximately equal to the
properties of the saturated liquid state at the temperature
P = 1 atm. T
= 20oC
• Process 2-3:
- At state 2 the liquid has reached the temperature at which it begins to boil, called the saturation
temperature, and is said to exist as a saturated liquid
- Properties at the saturated liquid state are noted by the subscript f andv 2
v
=f

- During the phase change both the temperature and pressure remain constant (according to the
International Temperature Scale of 1990, ITS-90, water boils at 99.975oC & 100oC when the pressure is
1 atm or 101.325 kPa)
- At state 3 the liquid and vapor phase are in equilibrium and any point on the line between states 2
and 3 has the same temperature and pressure
State 2 State 3

P = 1 atm. T P = 1 atm. T
= 100oC = 100oC
• Process 3-4:
- At state 4, a saturated vapor exists and vaporization is complete
- The subscript g will always denote a saturated vapor state,v4
=
vg

- The saturation temperature is the independent property

- The saturation pressure is the independent property
- The saturation pressure is the pressure at which phase change will occur for a given temperature
- In the saturation region the temperature and pressure are dependent properties; if one is known, then
the other is automatically known
State 4

P = 1 atm. T
= 100oC
Process 4-5:
- If the constant pressure heating is continued, the temperature will begin to increase above the
saturation temperature, 100oC in this example, and the volume also increases
- State 5 is called a superheated state because T5
i
sg
r
ea
t
e
r
th
a
nt
h
es
a
t
ur
a
t
i
on
t
em
p
e
r
at
u
r
ef
o
rt
h
e

pressure and the vapor is not about to condense

- Thermodynamic properties for water in the superheated region are found in the superheated
steam tables

State 5

P = 1 atm. T
= 300oC
Constant Pressure Steam Generation Process

99.975

It should be noted that the points 2 and 3

are at the same boiling point temperature
and pressure and also that, at those
conditions, the liquid and the steam are in
equilibrium with each other
Types of steam
• Wet steam: A mixture of water plus steam (liquid plus vapor) at the boiling point temperature of water
at a given pressure
- Quality of steam refers to the fraction or percentage of gaseous steam in a wet steam mixture

• Dry steam: Steam, at the given pressure, that contains no water (also referred to as saturated steam)

- The steam quality = 100%.

• Superheated steam: Dry steam, at the given pressure, that has been heated to a temperature higher
than the boiling point of water at that pressure
• Repeating this process for other constant pressure lines as shown below

oC

oC
T,

T,
374.14

0.003155 v, m3kg v, m3kg

• Heat of vaporization or Latent Heat: The amount of heat required to convert the liquid water
completely into vapor.
• Saturation temperature and saturation pressure: The temperature at which vaporization takes place

• Sub- cooled liquid: If the temperature of the liquid water on cooling becomes lower than the saturation
temperature for the given pressure
• Compressed liquid: When the pressure on the liquid water is greater than the saturation
pressure at a given temperature
• The term compressed liquid or sub-cooled liquid is used to distinguish it from saturated liquid. All
points in the liquid region indicate the states of the compressed liquid
• Superheated temperature: When all the liquid has been evaporated completely and heat is further
added, the temperature of the vapor increases
- When the temperature increases above the saturation temperature (in this case 100°C), the vapor is
known as the superheated vapor
- There israpid increase in volume and the piston moves upwards

• Degree of superheat: The difference between the superheated temperature and the saturation
temperature at the given pressure
• When the pressure is greater than the critical pressure, the liquid water is directly converted into
superheated steam.
 saturated liquid and saturated vapor line
intersect at the critical point and form what is
often called the “steam dome”
All of the saturated liquid
states are connected, All of the saturated

oC
P2= 1000 kPa vapor states are

T,
the saturated liquid line is
established connected, the
P1
=
10
0k
P
a
saturated vapor line is
established
179.88oC

99.61oC
The region to the right of
The region to the left of the the saturated vapor line
saturated liquid line and and above the critical
below the critical temperature is called the
temperature is called the superheated region
compressed liquid region
v, m3kg

The region between the saturated liquid line and the saturated vapor line
is called by these terms: saturated liquid-vapor mixture region, wet region
(i.e., a mixture of saturated liquid and saturated vapor), two-phase region,
and just the saturation region
• The critical-point properties of water are

oC
-Pc
2
2.
06
M
pa

T,
r

-Tc
3
7
r3
.9
5
°
C

-v c
0
.
r0
03
1
0
6
m3
/
k
g

At temperatures and pressures

above the critical point, the
phase transition from liquid to
vapor is no longer discrete

v, m3kg
P -T diagram, often called the phase diagram, for pure substances

Pressure
Pressure

The triple point is merely

the point of intersection of
sublimation and
vaporization curves

Temperature
Temperature

• It must be understood that only onp -T diagram is the Vaporisation : liquid to vapor transition
triple point represented by apoint Melting : solid to liquid transition
• Onp -V diagram it is aline Sublimation: solid to vapor transition

• The triple point of water is 0.01oC, 0.6117 kPa

• The critical point of water is 373.95oC, 22.064 MPa
 Quality and Saturated Liquid-Vapor Mixture

T,oC; P
Saturated Vapor vg
Saturated Liquid
= Vapor Mixture vf
g
Saturated Liquid vf

v, m3kg

• Since state 3 is a mixture of saturated liquid and saturated vapor, how do we locate it on the T-v
diagram?
- To establish the location of state 3, aparameter called the quality or dryness fractionx is defined
as mass
s
a
t
u
r
at
e
dm
v
a
po
r
xm m g

masst fg

otal
• Sensible heat of water (hf
)
It
is
d
e
fin
e
d
a
st
h
eq
u
an
t
i
t
yo
fh
e
a
t
ab
s
o
r
be
d
b
y1
k
g
o
fw
a
t
e
rw
h
en
i
t
i
s

heated from 0°C (freezing point) to boiling point.

- It is also called total heat (or enthalpy) of water or liquid heat invariably.
- It is reckoned from 0°C where sensible heat is taken as zero
- If 1 kg of water is heated from 0°C to 100°C the sensible heat added to it will be 4.18 × 100 = 418 kJ but if water
is at say 20°C initially then sensible heat added will be 4.18 × (100 – 20) = 334.4 kJ

This type of heat is denoted by letter hf

a
ndi
t
sv
a
lu
e
c
an
b
e
d
ir
e
c
tl
y
re
a
df
r
o
mt
h
es
t
e
am
t
ab
l
e
s

• Note: The value of specific heat of water may be taken as 4.18 kJ/kg K at low pressures but at high pressures it is
different from this value

• Latent heat or hidden heat (hf

)
gI
ti
s
th
ea
m
o
u
nt
o
fh
e
at
r
e
qu
i
r
ed
t
oc
o
n
v
er
t
wa
t
e
ra
t
ag
i
v
en
temperature and pressure into steam at the same temperature and pressure
- It is expressed by the symbol hf
a
gn
di
t
sv
a
lu
e
i
sa
v
ai
l
a
bl
ef
r
o
ms
t
ea
m
t
ab
l
e
s

- The value of latent heat is not constant and varies according to pressure variation
• If in 1 kg of wet steam 0.9 kg is the dry steam and 0.1 kg water particles thenx = 0.9
- Note: No steam can be completely dry and saturated, so long as it is in contact with the water from which it is
being formed
• The quality is zero for the saturated liquid and one for the saturated vapor (0 ≤ x ≤ 1)

• Total heat or enthalpy of wet steam (h): defined as the quantity of heat required to convert 1 kg of
water at 0°C into wet steam at constant pressure
- It is the sum of total heat of water and the latent heat and this sum is also called enthalpy.
- In other words, h = hf
+x
hI
f
gf
st
e
a
mi
sd
r
ya
n
d
sa
t
u
r
at
e
d
,t
h
en
x
=1
a
n
d
h=
h
g
f+
h
f
g
• Volume of wet and dry steam: If the steam has dryness fraction of x, then 1 kg of this steam will
containx kg of dry steam and (1 –x ) kg of water. Ifv f
i
st
he
v
o
l
um
eo
f
1
kg
o
fw
a
t
e
r
an
dv
i
s
gt
h
e

volume of 1 kg of perfect dry steam (also known as specific volume),

volume of 1 kg of wet steam = volume of dry steam + volume of water

= xvg
+
(
1–
x)
v
f
• Note. The volume of vf
a
tl
ow
p
re
s
s
u
r
es
i
s
ve
r
ys
m
a
l
la
n
di
s
ge
ne
r
a
l
l
yn
e
gl
e
ct
e
d.
T
hu
si
s
ge
ne
r
a
l
,t
h
e

volume of 1 kg of wet steam is given by, xvg

a
nd
de
n
s
i
t
y1
/x
v
k
g
g/
m3

=xvg
+
v–
x
fv
f

=vf
+x
(
v–
v
g
f)

= vf
+x
vf
g

=vf
+
xv
f+
v
g–
f
gv
f
g

=(vf
+v
f
g)
–
(1
–x
)
v
f
g

= vg
–
(1
–x
)
v
f
g
• Volume of superheated steam. As superheated steam behaves like a perfect gas its volume can be
found out in the same way as the gases.
If,vg
=
Sp
e
ci
fi
cv
ol
u
meo
f
d
r
ys
t
ea
m
a
tp
r
e
s
sp
u
r
e

Ts
=
Sa
t
ur
a
t
i
on
t
em
p
e
r
at
u
r
ei
n
K

Ts
=
u
pT
e
mp
e
r
a
t
ur
e
of
s
u
pe
r
he
a
t
e
ds
t
e
am
i
nK
vs
=
u
pV
ol
u
meo
f
1
kg
o
fs
u
p
e
r
he
a
t
e
ds
t
e
am
a
tp
r
e
s
su
r
ep
T
h
en
,

p.vg
/
T=
p.
v/
T s
u
pgs
u
ps
v
=
vT
/T
ss
ups
u
p

If steam is superheated to a volume of vs

p
u
pe
r
kg
.
h
s=
u
ph
+
fh
f
g+
c
p(
T
s
s–
u
pT
)
s
 Temp., Sat. Press. Specific volume, Internal energy, Enthalpy, Entropy,
T oC , Ps
a
t kP a m3 /kg kJ/kg kJ/kg kJ/kg -K

Sat. liquid, Sat. vapor, Sat. liquid, Evap., Sat. Sat. liquid, Evap., Sat. Sat. Evap., sf
g Sat.
vf vg uf ufg vapor, ug
hf h vapor, hgliquid, sf vapor, sg
fg

0.01 0.6117 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556

TABLE: Saturated Steam-Pressure Table

5 0.8725 0.001000 147.03 21.02 2360.8 2381.8 21.02 2489.1 2510.1 0.0763 8.9487 9.0249

10 1.228 0.001000 106.32 42.02 2346.6 2388.7 42.02 2477.2 2519.2 0.1511 8.7488 8.8999

15 1.706 0.001001 77.885 62.98 2332.5 2395.5 62.98 2465.4 2528.3 0.2245 8.5559 8.7803

20 2.339 0.001002 57.762 83.91 2318.4 2402.3 83.91 2453.5 2537.4 0.2965 8.3696 8.6661

25 3.170 0.001003 43.340 104.83 2304.3 2409.1 104.83 2441.7 2546.5 0.3672 8.1895 8.5567

30 4.247 0.001004 32.879 125.73 2290.2 2415.9 125.74 2429.8 2555.6 0.4368 8.0152 8.4520

35 5.629 0.001006 25.205 146.63 2276.0 2422.7 146.64 2417.9 2564.6 0.5051 7.8466 8.3517

40 7.385 0.001008 19.515 167.53 2261.9 2429.4 167.53 2406.0 2573.5 0.5724 7.6832 8.2556

45 9.595 0.001010 15.251 188.43 2247.7 2436.1 188.44 2394.0 2582.4 0.6386 7.5247 8.1633

50 12.35 0.001012 12.026 209.33 2233.4 2442.7 209.34 2382.0 2591.3 0.7038 7.3710 8.0748

55 15.76 0.001015 9.5639 230.24 2219.1 2449.3 230.26 2369.8 2600.1 0.7680 7.2218 7.9898

60 19.95 0.001017 7.6670 251.16 2204.7 2455.9 251.18 2357.7 2608.8 0.8313 7.0769 7.9082

65 25.04 0.001020 6.1935 272.09 2190.3 2462.4 272.12 2345.4 2617.5 0.8937 6.9360 7.8296

70 31.20 0.001023 5.0396 293.04 2175.8 2468.9 293.07 2333.0 2626.1 0.9551 6.7989 7.7540

75 38.60 0.001026 4.1291 313.99 2161.3 2475.3 314.03 2320.6 2634.6 1.0158 6.6655 7.6812

80 47.42 0.001029 3.4053 334.97 2146.6 2481.6 335.02 2308.0 2643.0 1.0756 6.5355 7.6111

85 57.87 0.001032 2.8261 355.96 2131.9 2487.8 356.02 2295.3 2651.4 1.1346 6.4089 7.5435

90 70.18 0.001036 2.3593 376.97 2117.0 2494.0 377.04 2282.5 2659.6 1.1929 6.2853 7.4782

95 84.61 0.001040 1.9808 398.00 2102.0 2500.1 398.09 2269.6 2667.6 1.2504 6.1647 7.4151

100 101.42 0.001043 1.6720 419.06 2087.0 2506.0 419.17 2256.4 2675.6 1.3072 6.0470 7.3542

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360 18666 0.001895 0.006950 1726.16 625.7 2351.9 1761.53 720.1 2481.6 3.9165 1.1373 5.0537

365 19822 0.002015 0.006009 1777.22 526.4 2303.6 1817.16 605.5 2422.7 4.0004 0.9489 4.9493

370 21044 0.002217 0.004953 1844.53 385.6 2230.1 1891.19 443.1 2334.3 4.1119 0.6890 4.8009

373.95 22064 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070
 TABLE: Saturated Water-Pressure Table
Press. Sat. Temp., Specific volume, Internal energy, Enthalpy, Entropy,
P kPa Tsat o C m3 /kg kJ/kg kJ/kg kJ/kg - K
Sat. liquid, Sat. vapor, Sat. liquid, Evap., Sat. vapor, Sat. liquid, Evap., Sat. vapor, Sat. liquid, Evap., Sat. vapor,
vf vg uf ufg ug hf hfg hg sf sfg sg
• The last entry is the critical
0.6117 0.01 0.001000 206.00 0.00 2374.9 2374.9 0.00 2500.9 2500.9 0.0000 9.1556 9.1556 point at 22.064MPa
1.0 6.97 0.001000 129.19 29.30 2355.2 2384.5 29.30 2484.4 2513.7 0.1059 8.8690 8.9749

1.5 13.02 0.001001 87.964 54.69 2338.1 2392.8 54.69 2470.1 2524.7 0.1956 8.6314 8.8270

2.0 17.50 0.001001 66.990 73.43 2325.5 2398.9 73.43 2459.5 2532.9 0.2606 8.4621 8.7227

2.5 21.08 0.001002 54.242 88.42 2315.4 2403.8 88.42 2451.0 2539.4 0.3118 8.3302 8.6421

3.0 24.08 0.001003 45.654 100.98 2306.9 2407.9 100.98 2443.9 2544.8 0.3543 8.2222 8.5765

4.0 28.96 0.001004 34.791 121.39 2293.1 2414.5 121.39 2432.3 2553.7 0.4224 8.0510 8.4734

5.0 32.87 0.001005 28.185 137.75 2282.1 2419.8 137.75 2423.0 2560.7 0.4762 7.9176 8.3938

7.5 40.29 0.001008 19.233 168.74 2261.1 2429.8 168.75 2405.3 2574.0 0.5763 7.6738 8.2501

10 45.81 0.001010 14.670 191.79 2245.4 2437.2 191.81 2392.1 2583.9 0.6492 7.4996 8.1488

15 53.97 0.001014 10.020 225.93 2222.1 2448.0 225.94 2372.3 2598.3 0.7549 7.2522 8.0071

20 60.06 0.001017 7.6481 251.40 2204.6 2456.0 251.42 2357.5 2608.9 0.8320 7.0752 7.9073

25 64.96 0.001020 6.2034 271.93 2190.4 2462.4 271.96 2345.5 2617.5 0.8932 6.9370 7.8302

30 69.09 0.001022 5.2287 289.24 2178.5 2467.7 289.27 2335.3 2624.6 0.9441 6.8234 7.7675

40 75.86 0.001026 3.9933 317.58 2158.8 2476.3 317.62 2318.4 2636.1 1.0261 6.6430 7.6691

50 81.32 0.001030 3.2403 340.49 2142.7 2483.2 340.54 2304.7 2645.2 1.0912 6.5019 7.5931

75 91.76 0.001037 2.2172 384.36 2111.8 2496.1 384.44 2278.0 2662.4 1.2132 6.2426 7.4558

100 99.61 0.001043 1.6941 417.40 2088.2 2505.6 417.51 2257.5 2675.0 1.3028 6.0562 7.3589

125 105.97 0.001048 1.3750 444.23 2068.8 2513.0 444.36 2240.6 2684.9 1.3741 5.9100 7.2841

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٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠ ٠

20,000 365.75 0.002038 0.005862 1785.84 509.0 2294.8 1826.59 585.5 2412.1 4.0146 0.9164 4.9310

21,000 369.83 0.002207 0.004994 1841.62 391.9 2233.5 1887.97 450.4 2338.4 4.1071 0.7005 4.8076

22,000 373.71 0.002703 0.003644 1951.65 140.8 2092.4 2011.12 161.5 2172.6 4.2942 0.2496 4.5439

22,064 373.95 0.003106 0.003106 2015.8 0 2015.8 2084.3 0 2084.3 4.4070 0 4.4070
Superheated Water Table
- A substance is said to be superheated if the given temperature is greater than the saturation
temperature for the given pressure
• In the superheated water Table, T and P are the independent properties
• The value of temperature to the right of the pressure is the saturation temperature for the
pressure

- The first entry in the table is the saturated vapor state at the pressure
Compressed Liquid Water Table
• A substance is said to be a compressed liquid when the pressure is greater than the saturation
pressure for the temperature.
• It is now noted that state 1 is called a compressed liquid state because the saturation pressure for
the temperature T 1
i
sl
e
ss
t
hP
a
n
1
 ENTHALPY-ENTROPY (h-s) CHART OR MOLLIER DIAGRAM
• The plot of total heat against entropy, is more widely used than any other entropy diagram, since the work done on
vapor cycles can be scaled from this diagram directly as a length; whereas on T-s diagram it is represented by an
area

• Lines of constant pressure are indicated by p1

,
pe
2t
c
.
,
li
n
es
of
c
o
ns
t
an
t
t
e
mp
er
a
t
ur
e
by
T
,
1T
,
2e
t
c

• Any two independent properties which appear on the chart are sufficient to define the state (e.g., p1
a
nd
xd
e
1fi
n
e
state 1 and h can be read off the vertical axis)

• In the superheat region, pressure and temperature can define the state (e.g., p3
a
nd
Td
e
4fi
n
et
h
es
t
a
te
2
,
an
dh
2
can be read off)

• A line of constant entropy between two state points 2 and 3 defines the properties at all points during an
isentropic process between the two states
• For any state, at least two properties should be
known to determine the other unknown properties
of steam at that state
• The Mollier diagram is used only when quality is
greater than 50% and for superheated steam
Example: Find the specific volume, enthalpy and internal energy of wet steam at 18 bar with dryness
fraction (x) = 0.85, by using Steam Tables and Mollier chart.

Solution: Given: Pressure of steam, p= 18 bar; Dryness fraction, x= 0.85

(a) By using steam tables (for dry saturated steam): at 18 bar pressure, we have:

ts
=
20
7
.1
1
°
C
,h
=8
84
.
5
kJ
/
kg
,
h=2
7
9
4.
8
kJ
/
kg
,
h=19
1
0
.
3
kJ
/
kg
,
v=0
.
1
10
m3
/
k
g
f g f
g g

(i) Specific volume of wet steam, v : = vf

x
+.
(
v–
v
g)
f

Answer: v =
Specific enthalpy of wet steam, h = hf
+x
hf
g

Answer: h = hf
+x
h=
f
g8
84
.
6
+0
.8
5
x
19
1
0
.
3
=2
50
8
.
3
5k
J/
k
g
.
(iii) Specific internal energy of wet steam, u = h – pv
Answer: u = h – pv= 2508.35 – 18 x 102 (0.0935) = 2340.75 kJ/kg
Locate point ‘1’ at an intersection of 18 bar pressure line and 0.85 dryness fraction line.
Read the value of enthalpy (h) and specific volume (v) from Mollier diagram corresponding to
point ‘1’.
(i) Specific enthalpy of wet steam, h = 2508 KJ/kg
(ii) Specific volume of wet steam,v = 0.0935 m3/kg
(iii) Specific Internal energy of wet steam, u = h – pv = 2508 – 18 x 102 (0.0935) = 2340 kJ/kg
 Property Tables
• Property tables give data for
- Temperature
- Pressure
- Volume
- Specific internal energy u
- Specific enthalpy h
- the specific entropy s

• The enthalpy is a convenient grouping of the internal energy, pressure, and volume and is given
- H = U + PV
- enthalpy per unit mass is h = u + Pv

• The enthalpyh is quite useful in calculating the energy of mass streams flowing into and out of control
volumes
• The enthalpy is also useful in the energy balance during a constant pressure process for a
substance contained in a closed piston-cylinder device
• Saturation pressure is the pressure at which the liquid and vapor phases are in equilibrium at a given
temperature
• Saturation temperature is the temperature at which the liquid and vapor phases are in equilibrium at a
given pressure
• The subscript fg
u
se
di
n
ta
bl
e
s,
r
ef
er
s
t
ot
h
ed
i
f
f
er
e
nc
e
b
et
w
ee
n
th
e
s
a
t
ur
a
t
ed
v
ap
o
r
v
a
lu
e
an
d
t
h
e

saturated liquid value region

- That is, uf
guu
gf

hf
ghh
gf

sf
gss
gf

• The quantityh f
i
s
gca
l
l
e
dt
he
e
n
t
ha
l
p
yo
fv
a
p
o
ri
z
at
i
on
(
or
l
a
te
n
th
e
a
t
of
v
a
po
r
i
za
t
i
on
)

• It represents the amount of energy needed to vaporize a unit of mass of saturated liquid at a given
temperature or pressure
• It decreases as the temperature or pressure increases, and becomes zero at the critical point
 The Lever Rule is illustrated in the following figures

Superheated Water Table

- A substance is said to be superheated if the given temperature is greater than the saturation
temperature for the given pressure
• In the superheated water Table, T and P are the independent properties
• The value of temperature to the right of the pressure is the saturation temperature for the
pressure

- The first entry in the table is the saturated vapor state at the pressure