FME2 – Thermodynamics 1

TOPIC 3: PROPERTIES OF PURE SUBSTANCE

Pure Substance

• Pure substance is a substance that is homogeneous in composition and homogeneous

and invariable in chemical aggregation (faires, 1978).
• A substance is said to be pure substance if its chemical compositions do not change
even in solid, liquid, or gaseous phase. Example of which is water that has two atoms
of hydrogen and one atom of oxygen as it is in solid, liquid or gaseous state.
• State of pure substance or system refers to its condition as quantified or identified
through the thermodynamic properties of the substance.
• Phase is a quantity of substance that is homogeneous throughout
• Relevant Reversible work modes refer only to the important work modes for the
system in question and irreversible work modes are not considered.
• Reversible work mode refers to the amount of energy added in a forward process that
can be removed by the reversed process.

Additional Thermodynamic Properties

1. Enthalpy is a thermodynamic property with the following definitions

For closed system, it means the sum of internal energy and the product of pressure
and specific volume, and given by the relation

h = u + pv

kj
Where: h = enthalpy, ⁄kg , Btu⁄lb
p = pressure, kPaa, psia
3 3
v = specific volume, m ⁄kg , ft ⁄lb

For an open system, enthalpy means the sum of internal energy and flow energy or
flow work, and given by the relation:

H = U + Ef
H = mh = m(u + pv)

Where: H = total enthalpy, kJ, kW, Btu, Btu⁄min

U = total internal energy, kJ, kW, Btu, Btu⁄min
Ef = flow energy or work, kJ, kW, Btu, Btu⁄min

2. Entropy is a thermodynamic property first introduced by Clausius in 1865 and could

be defined as follows:
• Entropy is the measure of the microscopic disorder of the molecules of a
substance
• It is a thermodynamic property that remains constant in an adiabatic
reversible process
• The change of entropy in an irreversible process is the measure of the
unavailable energy.
• Entropy is also defined as the measure of the irreversibility of the system or
substance.
• The change of entropy for a reversible process is given by the following
relation:
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dQ
∆s = s2 − s1 = ∫ ( )
T rev

kJ Btu
Where: ∆s = change of entropy, ,
kg∙°K lb∙°R
kJ Btu
s1 = initial entropy, kg∙°K, lb∙°R
kJ Btu
s2 = final entropy, kg∙°K, lb∙°R
Q = heat transfer during the process, kJ, Btu
T = absolute temperature, °K, °R

Three Phases of Matter or Pure Substance

1. Solid
2. Liquid
3. Vapor or gaseous phase

Manners of changing the Phases

o Melting of fusion is the change of phase from solid to liquid.

o Freezing or solidifying is the change of phase from liquid to solid.
o Vaporization is the change of phase from liquid to gaseous phase.
o Condensation is the change of phase from vapor to liquid; during the process it is
called as condensing.
o Sublimation is the change of phase from solid to vapor or vice versa.

Change of Phase at Constant Pressure

o Change of phase at constant pressure means that a pure substance changes its phase
from solid to gaseous without changing the applied or existing pressure.
o A typical example of which is water that changes its phases from solid to vapor at
existing pressure, say standard atmospheric pressure 101.325 kPa. As illustrated in
the figure 3.1, consider 1 kg water.

Figure 3.1. Change of Phases of 1-kg Water at 101.325 kPa

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Explanation for the Change of Phase in Figure 3.1

o State 1, water is at solid phase at, say, -20 C under atmospheric pressure of 101.325
kPa. Heat is added to the solid water to undergo the process from state 1 to state 2
without melting. This process is heating of solid with temperature increases from -20
°C to 0 °C.
o State 2, water is still at solid phase at 0 °C. This is the time in which melting process
is about to start. With the heat addition continues, melting process is from state 2 to
state 3. During the melting process, temperature remains the same at 0 °C. The
temperature for process 2 to 3 is known as melting temperature or melting point.
o State 3 is the end of melting process but the temperature remains 0 °C. Water at this
point is at liquid phase. Then heat addition continues to perform heating process from
state 3 to state 4. During this process, temperature increases to, say, 20 °C.
o State 4, water is called subcooled liquid and the temperature is called subcooled
liquid temperature. Water heated but still no occurring of evaporation. With the heat
addition continues, process 4 to 5 is performed with the increase of temperature from
20 °C to 100 °C. This process is still heating process.
o State 5, water is called as saturated liquid and at this point evaporation or boiling
process is about to start at 100 °C. With the heat addition continues, process 5 to 6 is
performed without changing the temperature.
o State 6, water is a mixture liquid and vapor and is called as wet vapor or wet steam.
At his point the temperature remains the same at 100 °C. The proportion of the liquid
and vapor components depends on time being considered from state 5 to state 6. The
amount of vapor content may be determined if the quality of vapor or steam is given.
With the heat addition continues, evaporation process is performed from state 6 to
state 7 with the same temperature at 100 °C.
o State 7, boiling or evaporation process ended with the temperature still 100 °C. At
this point, all liquid is converted into vapor or steam and is called as saturated
vapor/steam or dry and saturated vapor/steam. With the heat addition continues,
process 7 to 8 is performed with an increase of temperature from 100 °C to, say, 150
°C.
▪ Temperature for processes 5 to 6 and 6 to 7 is called boiling temperature or
boiling point and technically termed in thermodynamics as saturation
temperature and the existing pressure is also called as saturation pressure.
o State 8, the condition of water is called superheated vapor/steam and the
temperature is superheated vapor temperature at, say, 150 °C. The temperature at
this point is higher than the saturation temperature. Any point above point 7 at a
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given temperature higher than the saturation temperature and following the same
existing pressure is called as superheated vapor or steam.
▪ The difference of superheated temperature and the saturation temperature or
boiling temperature is called degrees of superheat (°SH).
▪ The difference of saturation temperature and the subcooled liquid
temperature is called degrees subcooled (°SC).

Note:

o If the existing pressure is increased, melting and boiling temperatures are also
increased. With further increased of an existing pressure, a critical point is attained,
a point in which saturated liquid and saturated vapor conditions are coexisted in
equilibrium.
o If the existing pressure is decreased, melting and boiling temperature are also
decreased. With further decreased of an existing pressure, a triple point will be
attained, a point in which melting and boiling temperatures are the same. Existing
pressure lower than the triple point, sublimation will take place.

Other Definitions

• Existing pressure or applied pressure refers to the pressure of the system in which
change of phase at constant pressure is considered.
• Solid water is a condition of water in which the temperature is below the freezing
temperature corresponding to an existing pressure.
• Subcooled liquid is a liquid condition in which the given temperature is higher than
the melting temperature and lower than the saturation or boiling temperature
corresponding to an existing pressure.
• Compressed liquid is a liquid condition in which the pressure is higher than
saturation pressure corresponding to the given temperature.
• Saturated liquid is a liquid condition in which boiling or evaporation is about to
begin and with the temperature is equal to the saturation or boiling temperature
corresponding to an existing pressure.
• Wet vapor or wet steam is the mixture of saturated liquid and saturated vapor with
the temperature equal to the saturation temperature corresponding to an existing
pressure.
• Saturated vapor/steam or dry and saturated vapor/steam is vapor condition in
which evaporation is ended and condensation is about to begin with the temperature
equal to the saturation temperature equal to the saturation temperature
corresponding to an existing pressure.
• Superheated vapor or steam is a vapor in which the temperature is higher than the
saturation temperature corresponding to an existing pressure.
• Heat of fusion is the amount of heat required to change the phase from solid to liquid
or vice versa.
• Latent heat or enthalpy of evaporation is the amount of heat required to convert
saturated liquid to saturated vapor; it is the amount of heat required to change
saturated liquid to saturated vapor at constant temperature without changing the
pressure.
• Sensible heat is the amount of heat required change the temperature without
changing the pressure.
• Critical point is a point in which liquid and vapor are coexisted in equilibrium.
• Critical pressure is the existing pressure at the critical point. Critical temperature is
the temperature at the critical point corresponding to an existing critical pressure.
o For water, critical pressure, pc = 22.09 MPaa,, and critical temperature, tc =
374.14 °C
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• Triple point is a point in which the melting and boiling or saturation temperature
are the same corresponding to the existing pressure.
o For water, at triple point: p = 0.6113 kPaa and t = 0.01 °C
• Sublimation is the process in which solid will directly change from solid to vapor at
a temperature corresponding to an existing pressure.
o For water, sublimation process will occur at p = 0.260 kPaa and t = -10 °C.
• Super critical condition is a condition above the critical point (p > 22.09 kPaa for
water). This is a condition where there is no liquid or vapor phase of pure substance
existing in equilibrium.
• The thermodynamic properties considered in the study of pure substance are:
o Pressure, MPaa, psia
o Temperature, °C, °F
o Specific volume, m3/kg, ft/lb
o Internal energy, kJ/kg, Btu/lb
o Enthalpy, kJ/kg/ Btu/lb
o Entropy, kJ/kg-°K, Btu/lb-°R

Diagrams

• Diagrams hereto are graphical representation of the relation of thermodynamic

properties for the change of phase at constant pressure such as pV, TV, Ts, pT and ph
diagrams.

Figure 3.2. Tv Diagram

o From figure above

▪ Point sc is subcooled liquid condition
▪ Point f is saturated liquid condition
▪ Point x is wet vapor condition
▪ Point g is saturated vapor condition
▪ Point sh is superheated vapor condition
▪ Point cp is critical point condition
▪ °SH = tsh − tsat
▪ °SC = tsat − tsc
▪ f – stands for saturated liquid
▪ g – stands for saturated vapor
▪ fg – stands for evaporation or process from f to g
▪ Evaporation (fg) – the process of boiling, liquid to vapor phase
▪ Condensation (gf) – the process of opposite direction, from vapor to liquid
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Figure 3.3. pv Diagram

Figure 3.4. Ts Diagram

o From figure 3.4 above

▪ tmp = melting point temperature
▪ ttp = triple point temperature
▪ tsb = sublimation temperature
▪ ptp = triple point pressure
▪ psb = sublimation pressure
▪ pc = critical point pressure
▪ tc = critical point temperature
▪ p = existing or applied pressure
▪ Saturated liquid curve – is the locus of all states of saturated liquid
▪ Saturated vapor curve – is the locus of all states of saturated vapor
▪ Triple point is the state in which three phases may all be present in
equilibrium
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Quality of Vapor/Steam
• Quality of vapor/steam or dryness factor is the ratio of the mass of vapor content in
the mixture to that of the mass of the mixture of vapor and liquid.

mg
x= 100%
mf + mg
Moisture Content
• Moisture content is amount of saturated liquid in the mixture of saturated vapor and
saturated liquid; it is the ratio of the mass of saturated liquid to that of the mass of
mixture of saturated liquid and saturated vapor

mf
y= 100%
mf + mg

x + y = 100%

Figure 3.5. Quality of Vapor

Where: mf = mass of saturated liquid content, kg, lb

mg = mass of saturated vapor content, kg, lb
x = quality of vapor or steam, or dryness factor, %
y = moisture content, %

Thermodynamic Properties of Each State

• For Subcooled or Compressed Liquid

o To obtain the properties v, u, h & s, p and t must be given
o Properties obtained from steam tables if the given substance is water
o Values of properties for subcooled liquid must be lower than the properties of
saturated liquid as indicated in the following relations:

v vf
u uf
[ ] < [h ]
h f
s sf

o Subcooled temperature, t, is the lower than the saturation temperature

corresponding to the existing pressure, p. tsc < tsat .
o Quality, x, if computed is negative.
o Subcooled liquid condition is indicated by point sc in the Ts diagram.
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• For Saturated Liquid

o To obtain the properties, the given property is either pressure or temperature
o Properties to be obtain are indicated as follows, vf , uf, hf and sf
o Temperature is equal to the saturation temperature corresponding to an
existing pressure.
o The quality of vapor, x = 0 and Moisture content, y = 100%
o Values of properties of saturated liquid are lower than the properties of wet
vapor, and higher than the properties of subcooled liquid.

v vf v
u uf u
[ ] < [h ] < [ ]
h f h
s sc sf s wet

o Properties for water are obtained from steam tables.

o Saturated liquid condition is indicated by f in the figure below

• For Wet Vapor or Wet Steam

o To obtain the properties, there may have given properties of either pressure
& quality of vapor, or temperature & quality of vapor.
o Properties to be obtained are v, u, h, and s.
o Temperature of wet vapor must be equal to the saturation temperature
corresponding to an existing pressure.
o The quality is within the range: 0 % < x < 100%.
o Moisture content is within the range: 100% > y >0%.
o Values of properties are in accordance with the following relations:

vf v vg
uf u ug
[h ] < [ ] < [h ]
f h g
sf s wet sg

o Properties of wet vapor may be computed using the following equations:

v = vf + x(vfg )
u = uf + x(ufg )
h = hf + x(hfg )
s = sf + x(sfg )

Where: fg = refers to the properties of evaporation

vfg = vg − vf
ufg = ug − uf
hfg = hg − hf
sfg = sg − sf

o Values of fg properties for water are to be obtained directly from steam

tables except vfg .
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o Quality of vapor may also be obtained in terms of properties as indicated in

the following relations:

v − vf
x= [ ] 100%
vfg

u − uf
x= [ ] 100%
ufg

h − hf
x= [ ] 100%
hfg

s − sf
x= [ ] 100%
sfg

Where, the properties v, u, h and s are of wet vapor.

o Wet vapor condition is indicated by point x in the Ts diagram as in the figure.

• For the Saturated Vapor

o To obtain the properties of saturated vapor, there may have given properties
of either pressure or temperature.
o The properties to be obtained are indicated by vg , ug , hg and sg
o The temperature of saturated vapor must be equal to the saturation
temperature corresponding to the existing pressure; and also equal to the
temperature of saturated liquid and wet vapor.
o The quality of saturated vapor is x = 100%
o The moisture content is y = 0 %.
o The properties of saturated vapor are lower than the properties of
superheated vapor and higher than the properties of wet vapor as indicated in
the following relations:

v vg v
u ug u
[ ] < [h ] < [ ]
h g h
s wet sg s sh

o Saturated vapor condition is indicated by point g in the Ts diagram as shown

in the figure.
FME2 – Thermodynamics 1

• For the properties of Superheated Vapor

o To obtain properties v, u, h, and s, pressure and temperature must be given.
o The given temperature must be higher than the saturation temperature
corresponding to the existing pressure or given pressure
o Values of properties of superheated vapor must always be higher than the
properties of saturated vapor as indicated by the following relations:

vg v
ug u
[h ] < [ ]
g h
sg s sh

o If the given substance is water, values of properties are directly obtained from
steam tables.
o If quality x is computed, x> 100%.
o Superheated vapor condition is indicated by point sh on the Ts diagram as
indicated in Figure.

Sample Problems

1. Determine the properties of water for the following conditions:

a) p = 0.5 MPaa
b) t = 200°C
c) p = 2.0 MPaa & x = 90%
d) t = 200°C & 80%
e) t = 103.6°C & x = 90%
f) p = 1 MPaa & 300°C
g) p = 5 MPaa & t = 200°C
h) p = 1 MPaa & t = 353.75°C
i) p = 0.535 MPaa & t = 300°C

Solution:
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2. A 100-liter tank containing a mixture of saturated liquid water and saturated steam
at 370°C. a) find the mass of each phase if their volumes are equal. b) Find the volume
occupied by each phase if their masses are equal.

Given: 100-liter tank with saturated water and steam.

Required:
a) mf & mg if vf = vg
b) vf & vg if mf = mg

Solution:

a) For the values of mf & mg if vf = vg

c) For the Values of vf & vg if mf = mg