ME2121E/TME2121

Engineering Thermodynamics
Dr SNG Wei Meng, Daniel
daniel.sng@nus.edu.sg, E2-02-32

Department of Mechanical Engineering

Faculty of Engineering
Aug 2017

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Chapter 3. Thermodynamic
Properties of Pure Substances

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 A Pure Substance
• A pure substance is one where its properties remain invariant (or no
change) when it undergoes state changes, from gaseous to liquid or
to solid phase.

• Water is available in abundance, and its behavior, when subjected to changes in P, T and v, is of interest to engineers.
• Other pure substances such as air (a mixture but we made an exception), methane (CH4), ammonia (NH3), carbon
dioxide (CO2), etc.
State Diagrams
• The states of water (a condensable substance) can be plotted on a
2 or 3-dimensional state diagram using suitable axes such as P-v, T-v
or P-T diagrams.
State Diagrams
• In Fig. 3.1, the line “A-B-C-D”
represents a constant pressure line
(isobar), at an atmospheric pressure of
1 bar (=105Pa).
• Assuming a certain amount of liquid
(water) is initially contained in a piston-
cylinder assembly and the heat (dQ)
could be transferred across the system
boundary (shown by red arrow below).
State Diagrams
• State “A” – is termed a sub-cooled water
because its temperature is below the
saturation temperature, T< Tsat.
• When heat is further added from the
environment, its temperature rises but
pressure remains constant (as the piston
is free to move up). As the temperature
reaches its saturation temperature, T=Tsat,
the state point is indicated by, “B”, is
termed a saturated liquid. It lies on the “f”
line, demarcating the liquid and 2-phase
(liquid-vapor) region
State Diagrams
• On further heating, the energy input to
the environment leads to a phase
transformation, i.e., boiling occurs in the
water, leading to a two-phase mixture
(vapor-liquid phase). The state points lie
on the path “B to C”, and its position in
the state diagram depends on the
amount of heat added. In a two-phase
mixture regime, the pressure (Psat) and
temperature (Tsat) are coupled (no longer
independent of each other). Secondly,
They (Psat and Tsat ) remain unchanged
from states “B” to “C”.
State Diagrams
• When state point “C” is reached, boiling has
ended (all liquid in cylinder has been
evaporated). A dry-saturated vapour state is
achieved.
• From this point, further addition of heat
from surroundings causes a rise in
temperature of vapour, T > Tsat, leading to a
superheated state, as indicated by point
“D”. The system pressure remains constant
in the heating processes (as the piston is
free to move), accommodating the increase
in volume of steam.
State Diagrams
• Similar arguments are said for other isobars
(P> or < 1 bar). The highest pressure within
the vapor+liquid region is called the critical
pressure of water, which is at 220.9 bar. Any
isobar above the critical pressure is termed
the super-critical state.
State Diagrams
State Diagrams
• In the two-phase region (denoted by region under an “envelop”
region), P & T are no longer independent properties. To define a state
in this region, an additional variable is required, e.g., T-v or P-v or P-x,
etc.
• We define “x” as the quality or dryness fraction of the mixtures, i.e.,

where “f” and “g” denote the saturated liquid and vapor states. In the saturated liquid region, x
= 0, and in the dry or superheated vapor regions, x = 1.
State Diagrams
Extending the Diagrams to Include the Solid Phase
• The two equilibrium diagrams developed so far represent the
equilibrium states involving the liquid and the vapor phases only.
However, these diagrams can easily be extended to include the solid
phase as well as the solid-liquid and the solid-vapor saturation
regions.
State Diagrams
Extending the Diagrams to Include the Solid Phase
• Most substances contract during a solidification (i.e., freezing)
process. Others, like water, expand as they freeze. The P-v diagrams
for both groups of substances are given below. These two diagrams
differ only in the solid-liquid saturation region.
State Diagrams
• We are all familiar with two phases being in equilibrium ,
but under some conditions all three phases of a pure
substance coexist in equilibrium.
• On P-v or T-v diagrams, these triple-phase states form a
line called the triple line. The states on the triple line of a
substance have the same pressure and temperature but
different specific volumes. The triple line appears as a
point on the P-T diagrams and, therefore, is often called
the triple point.
State Diagrams
• For water, the triple-point temperature and pressure are 0.01°C and 0.6117
kPa, respectively. That is, all three phases o f water coexist in equilibrium
only if the temperature and pressure have precisely these values.
• No substance can exist in the liquid phase in stable equilibrium at pressures
below the triple-point pressure. The same can be said for temperature for
substances that contract on freezing.
• However, substances at high pressures can exist in the liquid phase at
temperatures below the triple-point temperature.
• For example, water cannot exist in liquid form in equilibrium at
atmospheric pressure at temperatures below 0°C, but it can exist as a liquid
at -20°C at 200 MPa pressure. Also, ice exists at seven different solid phases
at pressures above 100 MPa.
State Diagrams
• There are two ways a substance can pass from the solid to vapor
phase: either it melts first into a liquid and subsequently evaporates,
or it evaporates directly without melting first.
• The latter occurs at pressures below the triple-point value, since a
pure substance cannot exist in the liquid phase at those pressures.
• Passing from the solid phase directly into the vapor phase is called
sublimation. For substances that have a triple-point pressure above
the atmospheric pressure such as solid C02 (dry ice), sublimation is
the only way to change from the solid to vapor phase at atmospheric
conditions.
State Diagrams
The P-T Diagram
• The P-T diagram is often called the phase
diagram since all three phases are
separated from each other by three lines.
• The sublimation line separates the solid
and vapor regions, the vaporization line
separates the liquid and vapor regions,
and the melting (or fusion) line separates
the solid and liquid regions.
• These three lines meet at the triple point,
where all three phases coexist in
equilibrium.
State Diagrams
The P-T Diagram
• The vaporization line ends at the critical point
because no distinction can be made between
liquid and vapor phases above the critical
point.
• Substances that expand and contract on
freezing differ only in the melting line on the
P-T diagram.
• For a substance that expands on freezing,
such as water, the melting line “leans
backward” to the P axis. Thus, an increase in
the pressure on the solid phase (ice) will lead
to the formation of a liquid phase at the point
where the pressure is exerted.
• However, for a substance that contracts on
freezing, increasing pressure on a solid phase
would remain unchanged.
State Diagrams
The following features worth mentioning:
• Note the regions in the state diagram indicating the solid, solid+liquid,
solid+vapour, liquid+vapour and vapor regions,
• When view from the P-T plane, one sees a triple-phase line and a
point where all three phases of water could co-exist - vapor, liquid
and ice.
• The sublimation line is where solid phase changes to vapor phase
directly.
• The melting line is where solid changes to liquid when heat is added.
State Diagrams
The P-v-T Surface
• The state o f a simple compressible substance is fixed by any two
independent, intensive properties.
• Once the two appropriate properties are fixed, all the other properties
become dependent properties.
• Remembering that any equation with two independent variables in the
form z = z(x, y) represents a surface in space, we can represent the P-v-T
behavior of a substance as a surface in space.
 P-v-T surface of a
substance that
State Diagrams contracts on
freezing.

The P-v-T Surface

• Here T and v may be viewed as the independent
variables (the base) and P as the dependent vari-
able (the height).
• All the points on the surface represent
equilibrium states. All states along the path of a P-v-T surface of a
quasi-equilibrium process lie on the P-v-T surface substance that
since such a process must pass through
equilibrium states. expands on
freezing (like
• The single-phase regions appear as curved water)
surfaces on the P-v-T surface, and the two-phase
regions as surfaces perpendicular to the P-T
plane. This is expected since the projections of
two-phase regions on the P-T plane are lines.
 P-v-T surface of a
substance that
State Diagrams contracts on
freezing.

The P-v-T Surface

• All the two-dimensional diagrams we have
discussed so far are merely projections of this
three-dimensional surface onto the appropriate
planes.
• A P-v diagram is just a projection of the P-v-T P-v-T surface of a
surface on the P-v plane, and a T-v diagram is substance that
nothing more than the bird’s-eye view of this
surface. expands on
freezing (like
• The P-v-T surfaces present a great deal of water)
information at once, but in a thermodynamic
analysis it is more convenient to work with two-
dimensional diagrams, such as the P-v and T-v
diagrams.
State Diagrams
 P-v-T surface of a
substance that
State Diagrams contracts on
freezing.

The P-v-T Surface

P-v-T surface of a
substance that
expands on
freezing (like
water)
Tables of Thermodynamic Properties
of Fluids
• For engineering applications,
one would either use a “steam
table” to determine accurately
the thermodynamic states, such
as P, T, u (internal energy), h
(enthalpy), s (entropy) of pure
substances or mixtures.
 Tables of Thermodynamic Properties
of Fluids Subscript “f” for saturated water
Subscript “g” for dry saturated steam
Subscript “fg” for the difference between the vapour to liquid properties
at saturated conditions, e.g., sfg = sg - sf at saturated conditions.

Subscript “s”
for saturation
temperature

• For most practical purpose, the value of vf is generally taken

1 as 0.001 m3/kg.
Tables of Thermodynamic Properties
of Fluids
Example
• Determine the temperature, specific enthalpy, specific internal energy
and specific volume of saturated steam at p=0.34 bar.
Tables of Thermodynamic Properties
of Fluids
Subscript “g” for saturated steam

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Tables of Thermodynamic Properties
of Fluids
Properties of compressed water

• Water at a temperature below the boiling point (ts)corresponding to

the pressure.

• Assumption: For normal pressure, it is sufficiently accurate to take

the properties of compressed water, as being equal to those of
saturated water at the same temperature.
Tables of Thermodynamic Properties
of Fluids
Example
• Determine the specific internal energy, specific enthalpy and specific
volume of compressed water at p=20 bar and t=179.9ºC
Same as “f” saturated water at the same temp.
Tables of Thermodynamic Properties
of Fluids
Tables of Thermodynamic Properties
of Fluids
• Tabulated separately

• Temperature and pressure are independent properties. i.e. only when

the temperature and pressure are given for superheated steam, then
the state is defined and all the other properties can be found.
Tables of Thermodynamic Properties
of Fluids
Example
• Determine the specific enthalpy, specific internal energy and specific
volume of superheated steam at p=2 bar and t=200°C.
Tables of Thermodynamic Properties
of Fluids
Properties of the two-phase mixture
The specific properties of the two-phase mixture can be obtained using
the dryness fraction, x:

The dryness fraction of the two-phase mixture is x

Then 1 kg of the two-phase mixture contains:
X kg of dry saturated steam, and
(1-x) kg of saturated water
Tables of Thermodynamic Properties
of Fluids
Therefore, the specific enthalpy of the two-phase mixture
h=xhg+(1-x)hf=hf+xhfg

Similarly, the specific internal energy of the two-phase mixture

u=xug+(1-x)uf=uf+xufg

And the specific entropy of the two-phase mixture

s=xsg+(1-x)sf=sf+xsfg
Tables of Thermodynamic Properties
of Fluids
And the specific volume of the two-phase mixture
v=xvg+(1-x)vf

Since (1-x)vf≈0 • For most practical purpose,

the value of vf is generally
taken as 0.001 m3/kg.

Hence v=xvg

Or x=v/vg
Tables of Thermodynamic Properties
of Fluids
• Using the linear rule, the quality (x), can also be obtained from other
given values of u, or h or s., e.g.,
Tables of Thermodynamic Properties
of Fluids
Example
• Determine the temperature, specific enthalpy, specific internal energy
and specific volume of the two-phase mixture at p=10 bar with a
dryness fraction of 0.5.
Tables of Thermodynamic Properties
of Fluids
Applying hx=xhg+(1-x)hf
Hence hx=0.5=0.5×2778+(1-0.5)×763
=1770.5 kJ/kg

Applying ux=xug+(1-x)uf
Hence u0.5=0.5×2584+(1-0.5)×762
=1673 kJ/kg

Applying vx=xvg
Hence v0.5=0.5×0.1944
=0.0972 m3/kg
Tables of Thermodynamic Properties
of Fluids
Example
• A cylinder contains 0.113 m3 of the two-phase mixture at 11 bar. If
the mass of the steam is 0.9 kg, determine its dryness fraction,
enthalpy and internal energy.

Solution:
Tables of Thermodynamic Properties
of Fluids
Tables of Thermodynamic Properties
of Fluids
Applying

Applying hx=xhg+(1-x)hf
Hence hx=0.708=0.708×2781+(1-0.708)×781
=2197 kJ/kg
Hence, the enthalpy of the the two-phase mixtures
Tables of Thermodynamic Properties
of Fluids
Applying ux=xug+(1-x)uf
Hence u0.708=0.708×2586+(1-0.708)×781
=2058.94 kJ/kg

Hence, the internal energy of the the two-phase

mixtures
Thank you!
Q & A

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