Properties of Pure Substances

CHAPTER 4
This chapter covers the basic understanding of properties for
pure substances. It is imperative that you understand the
terminology and how to get the properties. It forms the basics
to be used when analysing thermodynamic systems
This chapter can give you lot of marks if you know how to use
the tables and understand each phase of a substance
At the end of this chapter you should be able to:
• Introduce the concept of a pure substance.
• Discuss the physics of phase-change processes.
• Illustrate the P-v, T-v, and P-T property diagrams.
• Demonstrate the procedures for determining
thermodynamic properties of pure substances from tables
of property data (very NB!).
• Describe the hypothetical substance “ideal gas” and the
ideal-gas equation of state.
• Apply the ideal-gas equation of state in the solution of
typical problems.
 Pure Substance
Pure substance: A substance that has a fixed chemical composition throughout. (water,
nitrogen, helium, carbon dioxide)
Air is a mixture of several gases, but it is considered to be a pure substance, as long as the
mixture is homogeneous (uniform chemical composition) – oil and water does not mix, not
pure substance
A mixture of two or more phases of a pure substance is still pure as long as the chemical
composition of all phases are the same
A substance can only be pure
if the mixture is
homogeneous (the same
composition throughout).
Remember that water and
air mixture is not a pure
substance, the same as oil
FIGURE 4-1 FIGURE 4-2 and water, as the materials
Nitrogen and gaseous air are A mixture of liquid and have different densities and
pure substance gaseous water is pure will freeze/melt at different
substance, but a mixture of temperatures/pressures.
liquid and gaseous air is not
 Phases of a Pure Substance
The molecules in a solid are arranged in a three-dimensional pattern (lattice) that is
repeated throughout
The molecular spacing in the liquid phase is not much different from that of the solid phase,
except the molecules are no longer at fixed positions relative to each other and they can
rotate and translate freely.
In the gas phase, the molecules are far apart from each other, and a molecular order is non-
existent.

We know that molecules are differently spaced for different phases. Knowing the phase of
a substance and how it reacts in certain conditions is imperative to solving some problems.
An example; the viscosity of liquid decreases as temperature increase, but the viscosity of
gas increases with temperature. This is due to how the molecules behave, move and collide
during temperature rises
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases coexist
in equilibrium.
4) Saturated vapor = A vapor that is about to condense.
5) Superheated vapor = A vapor that is not about to condense.
A substance goes through a few stages while changing phases. The ones that we are
focusing on in MTF12A is during the process of a pure substance changing from liquid to
gas. There are 5 stages in the process. A substance can only go from one stage to another if
energy is added/removed from the system. NB: In our daily life, “water” implies liquid
water and steam implies water vapor. In thermodynamics, however, both water and steam
usually mean only one thing: H2O
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases coexist
in equilibrium. A substance in a state of compressed liquid, is not about to
vaporize,
4) Saturated vapor = A vapor thatthat means
is about to ifcondense.
energy (typically in the form of heat, but
can also be work) is added to the system, it will not change phase.
5) Superheated vapor = A vapor that is not about to condense.
Consider a piston-cylinder device with liquid-water at 1 atm, 20°C.
The inside of the cylinder is taken as the system and the liquid is at
state 1. Adding energy will not cause any “boiling”, yet. This state
can be considered as compressed liquid. It can also be determined
with property tables. As energy is added (heat in this example) the
water’s temperature rises. The liquid water expands slightly
(specific volume increases). To accommodate this expansion, the
piston moves up slightly. The pressure in the cylinder remains
constant at 1 atm during this process since it depends on the
outside pressure and the weight of the piston, both of which are
constant. Water is still a compressed liquid at this state since it has
not started to vaporize.
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases coexist
in equilibrium. As more heat is transferred, the temperature keeps
4) Saturated vapor = A vapor thatrising
is about
untiltoitcondense.
reaches 100°C. At this point the water will
startistonot
5) Superheated vapor = A vapor that boil if more
about energy is added. That is, a phase-
to condense.
change process from liquid to vapor is about to take
place. A liquid that is about to vaporize is called a
saturated liquid. Our state 2 in this example is at a
saturated liquid state, any more energy to the system
and the liquid will change phase. Once
vaporizing/boiling starts, the temperature stops rising
until the liquid is completely vaporized. That is, the
temperature will remain constant during the entire
phase-change process if the pressure is held constant.
We will, however, observe a large increase in the total
volume and a decline in the liquid level as more of the
liquid turns to vapor/gas.
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases
coexist in equilibrium.
4) Saturated vapor = A vapor that is about to condense.
Through the vaporization
5) Superheated vapor = A vapor that is not about to condense.
process, the cylinder contains a
mixture of liquid and vapor. As
we continue transferring heat,
the vaporization process
continues until the last drop of
liquid is vaporized. A substance
anywhere between 2 and 4 is
referred to as a saturated
liquid–vapor mixture since the
liquid and vapor phases coexist
in equilibrium at these states.
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases coexist
in equilibrium.
4) Saturated vapor = A vapor that is about to condense.
5) Superheated vapor = A vapor that is not about to condense.

Once the phase-change process (from liquid to

vapor/gas) has been completed, the entire cylinder
is filled with vapor and it is on the borderline of the
liquid-vapor-mixture phase (state 4). Any energy
removed from the system will cause some of the
vapor to condense (phase to change from vapor to
liquid/ forming droplets). A vapor that is about to
condense is called a saturated vapor.
 Phases-Change Process of a Pure
Substance
1) Compressed liquid = substance that it is not about to vaporize.
2) Saturated liquid = liquid that is about to vaporize.
3) Saturated liquid - vapor mixture: The state at which the liquid and vapor phases coexist
in equilibrium.
4) Saturated vapor = A vapor that is about to condense.
5) Superheated vapor = A vapor that is not about to condense.

If more energy is supplied to the system at state 4, the temperature

and specific volume will increase (previously the energy was used
to change the liquid to vapor, thus the temperature remained
constant, now that all has changed, the energy increases the
temperature again). At state 5, the vapor in this example is at
300°C, 1atm. If we remove some energy from the vapor, the
temperature may drop, but no condensation will take place as long
as the temperature remains above 100°C (for P = 1 atm). A vapor
that is not about to condense is called a superheated vapor (some
textbooks refer to dry steam).
 Phases-Change Process of a Pure
Using a T-v diagram for the process path, all states
can be plotted. This is a constant pressure process,
Substance
and the line, as you will note is named P=1atm. (for
this example). From state 1 – 2, (compressed liquid
zone) the energy added to the system will cause the
temperature and specific volume to rise. At state 2, This constant-pressure phase-
the liquid is about to vaporize, therefor the substance change process can be
is saturated liquid. From state 2 – 4, (saturated illustrated on a T-v diagram.
mixture zone - passing through 3) the energy added
changes the liquid to vapor, the temperature remains
constant but the specific volume still increases. At
state 4 all liquid has vaporized and the substance is
saturated vapor. Any decrease in energy will cause
the vapor to condense. From state 4 – 5,
(superheated zone) energy added to state 4 will
cause the temperature and specific volume to
increase further. The substance is a superheated
vapor and will not condense if some energy is
removed. The process is completely reversible by
cooling the substance. The substance will go back to
state 1, retracing the same process path, and the
amount of heat released will be the same as the
amount of heat added during the heating process.
 Phases-Change Process of a Pure
Substance
Latent heat: The amount of energy absorbed or released during a phase-change process.
Latent heat of fusion: The amount of energy absorbed during melting. It is equivalent to the
amount of energy released during freezing.
Latent heat of vaporization: The amount of energy absorbed during vaporization and it is
equivalent to the energy released during condensation. The magnitudes of the latent heats
depend on the temperature or pressure at which the phase change occurs.

The energy taken to change phase is known

as latent heat (energy to go from state 1 to
2). The value of latent heat are also given in
property tables and it depends on
temperature and pressure.
Using the same technique for a pure
substance at different pressures, the
process curves can be created on the same
graph.
 Property Diagrams
The horizontal line that connects the saturated liquid and saturated vapor states is much
shorter as pressure is increased
Critical point: The point at which the saturated liquid and saturated vapor states are
identical.
If the process is repeated at different
constant pressures and the processes
are drawn on the same T-v diagram, we
will see that the energy required to
change phase decreases as the
pressures increases. At a certain point,
there is no longer energy required to
change from liquid to vapor, this is
known as the critical point.
By connecting all the saturated liquid
points and all the saturated vapor
points, the property diagram can be
found (next page). The saturated liquid
line and the saturated vapor line meet
at the critical point
 Property Diagrams
Saturated liquid line – connects saturated liquid states
Saturated vapor line – connects saturated vapor states
Compressed liquid region, Superheated vapor region, Saturated liquid–vapor mixture region
(wet region)

With the property diagram, the

zones can clearly be identified. To
the left of the curve is the
compressed liquid zone/region.
In the middle of the curve is the
saturated-liquid-vapor zone, and
to the right of the curve is the
superheated vapor zone.
 Property Diagrams
The general shape of the P-v diagram of a pure substance is very much like the T-v diagram,
but the T = constant lines on this diagram have a down-ward trend

The process can be repeated with a fixed temperature and changing pressure. Since the
pressure is changing, the graph is drawn on a P-v diagram. It results in a similar property
𝑃𝑉
diagram, however the temperature lines go downward. This mirrors the formula 𝑇 = 𝑘, if
pressure is constant (T-v diagram), then an increase in temperature equal increase in volume,
however if the temperature is constant (P-v diagram) then an increase in pressure equal a
decrease in volume. Likewise, a decrease in pressure will cause expansion
 Property Diagrams

The triple point can be found by extending

the diagram to include the solid phase.
Under certain conditions all three phases
can co-exist. 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.
For water, the triple-point temperature and
pressure are 0.01°C and 0.6117 kPa,
respectively. That is, all three phases of
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.
 Property Diagrams
There are two ways a substance can pass from the solid to vapor phase:
Melts first into a liquid and subsequently evaporates
Evaporates directly without melting first (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.

P-T diagram = phase diagram

(all 3 phases present at the triple point)
 Property Tables
For most substances, the relationships among thermodynamic properties are too complex
to be expressed by simple equations, therefor properties are frequently presented in the
form of tables.
Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
The results of these measurements and calculations are presented in tables in a convenient
format.
• For each substance, the thermodynamic properties are listed in more than one table - a
separate table is prepared for each region of interest such as the superheated vapor,
compressed liquid, and saturated (mixture) regions.
SI Tables and charts – at back of textbook (also uploaded to ethuto for your convenience)
Use the tables when working through the examples and supplied problems. Ensure that you
understand the tables, how to get the values from the tables, which tables to use when. If
you don’t understand, ask, it is important. (page numbers may be different in your
textbooks, please check that you are using the SI tables and not the English unit tables)
 Phases-Change Process of a Pure
Substance
The temperature at which water starts boiling depends on the pressure; therefore, if the
pressure is fixed, so is the boiling temperature.
Water boils at 100⁰C at 1 atm pressure.
Saturation temperature Tsat: The temperature at which a
pure substance changes phase at a given pressure.
Saturation pressure Psat: The pressure at which a pure
substance changes phase at a given temperature.
The property tables enables us to gain information about
certain states in the phase-change process. The
temperature at which water starts boiling depends on
the pressure; therefore, if the pressure is fixed, so is
the boiling temperature. At a given pressure, the
temperature at which a pure substance changes phase is
called the saturation temperature Tsat. Likewise, at a
given temperature, the pressure at which a pure
substance changes phase is called the saturation
pressure Psat. We use Psat and Tsat when looking up
properties of a state
 Property Tables

Screenshot of saturation tables for water. Properties given on tables are: Temperature,
pressure, specific volume, internal energy, enthalpy and entropy(not used in MTF12A)
 Property Tables
Enthalpy – h —A Combination Property

The combination u + Pv is frequently encountered in the analysis of control volumes (the

product pressure x volume has energy units).
Enthalpy of vaporization, hfg (Latent heat of vaporization):
The amount of energy needed to vaporize a unit mass of saturated
liquid at a given temperature or pressure. (hfg = 0 at critical point)

The enthalpy (h) in kJ/kg indicates the heat content of a certain state and is depended
on the internal energy and Pv energy (which you will later see is defined as boundary
work).
hf is the enthalpy at saturated liquid point, hg is the enthalpy at saturated vapor point,
hfg is the difference between hg and hf, which is also the energy required to go from
saturated liquid to saturated vapor (latent heat). Can also be determined by hg - hf
 Property Tables
Use the following tables for states between saturated liquid and saturated vapor points
Table A–4: Saturation properties of water under temperature.
Table A–5: Saturation properties of water under pressure.

The specific volume (m3/kg) of a substance is also given on

the tables. vf is the specific volume of saturated liquid (fluid),
vg is the specific volume of saturated vapor (gas). To
determine the specific volume of a state somewhere between
the points, one requires vfg which is not given on tables but is
the difference between vg and vf.
 Saturated
liquid
Property Tables
Example 4-1 A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine
the pressure in the tank and the volume of the tank.
Write it
like this The pressure must be the saturation pressure at 90°C:
P = Psat @ 90°C = 70.183 kPa (Table A-4)
The specific volume of the saturated liquid at 90°C is
v = vf @ 90°C = 0.001036 m3/kg (Table A-4)
The total volume of the tank
V = mv = (50)(0.001036) = 0.0518 m3
The temperature is given, one will therefor refer to the temperature property table A4.
1) Since the water is saturated liquid, the pressure equals the saturation pressure at the
given temperature (90°C). Find the saturation pressure on table A4
2) The water is at saturated liquid state therefor the specific volume v = vf on the property
tables.
3) Using mass, the volume of the tank can be determined.
Nb: a rigid tank will not expand, therefor if we add energy, the pressure will increase. It will
therefor not follow the constant pressure line provided in the sketch, it should have rather
been plotted on a P-v diagram
 Saturated liquid
to saturated
Property Tables vapor

Example 4-3 A mass of 200 g of saturated liquid water is completely vaporized at a constant
pressure of 100 kPa. Determine (a) the volume change
and (b) the amount of energy transferred to the water.
(a) Values from Table A–5 at 100 kPa
Volume change: vfg = vg – vf = 1.6941 - 0.001043 = 1.6931 m3/kg
ΔV = mvfg = (0.2)(1.6931) = 0.3386 m3
(b) Enthalpy of vaporization = hfg = 2257.5 kJ/kg for water at 100 kPa.
Amount of energy transferred: mhfg = (0.2)(2257.5) = 451.5 kJ

In this example the water starts as saturated liquid (given) and is completely vaporized, thus
saturated vapor, while pressure remains constant. Since pressure is given, it is easier to work
with table A5 than A4. You can draw the process on a P-v or T-v diagram with the property
curve indicating saturation points.
1) The specific volume changes during the process from vf to vg, the values found on table
A5 at 100 kPa.
2) The amount of energy transferred in this example is equal to the latent heat hfg.
3) Since mass is given, it is wise to convert your answers. But in the event that mass is not
supplied you can leave the answer per unit mass
 Property Tables
Saturated Liquid–Vapor Mixture
Quality, x : The ratio of the mass of vapor to the total mass of the mixture. Quality is
between 0 and 1 - 0 = sat. liquid, 1 = sat. vapor.

The properties of the saturated liquid are the same

whether it exists alone or in a mixture with saturated
vapor.

The same tables are used for states that is a mixture. These
are not saturated liquid, nor saturated vapor and their
properties can’t be read directly from the tables. For the
mixture states, one has to define the quality (x) of the
substance, i.e how much of it has vaporised. If x=0, then
none has vaporised, if x=1, then it is vaporised completely. x
is the ratio of vapor mass to the total mass of the system. (no
quality for compressed or superheated!)
 Property Tables
Saturated Liquid–Vapor Mixture
Quality is related to the horizontal distances on P-v and T-v
diagrams.

Once the quality has been determined (can be given as a %),

the properties of the state can be determined. The
temperature/pressure of the point is the saturation
temperature/pressure. The specific volume equals vf + the
fraction of the difference vfg (see formula above).
The formula can also be adapted to find the internal energy
and enthalpy of the state.
 Saturated
liquid-vapor
Property Tables mixture

Example 4-4 A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the liquid
form and the rest is in the vapor form, determine (a) the pressure in the tank and (b) the
volume of the tank.
(a) P = Psat @ 90°C = 70.183 kPa (Table A– 4)
(b) At 90°C (Table A–4)
x = mg/mt = 2/10 = 0.2
v = vf + xvfg (vf = 0.001036 m3/kg and vg = 2.3593 m3/kg)
= 0.001036 + (0.2)[(2.3593 - 0.001036) = 0.473 m3/kg
V = mv = (10)(0.473)= 4.73 m3
In this example, you are told that there is liquid and vapor,
thus a saturated mixture. When working with mixtures, you
will always require the quality (determine it if it isn’t given).
The vapor mass = 10kg – 8kg, thus x can be calculated. The
pressure is independent of the quality and = saturated
pressure. The specific volume depends on the quality and Exercise drawing the graphs
can be determined by the ratio formula. Once the specific with your problems, in
volume is found the volume of the tank can be determined. some cases they are
required
 Saturated
liquid-vapor
Property Tables mixture

Example 4-5 An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.

Determine (a) the temperature, (b) the quality, (c) the enthalpy of the refrigerant, and (d)
the volume occupied by the vapor phase.
v = V/m = 0.080/4 = 0.02 m3/kg
At 160 kPa (Table A–12)
vf = 0.0007435 m3/kg & vg = 0.12355 m3/kg
vf < v < vg, conclusion: saturated mixture
T = Tsat@160 kPa = -15.60°C
x = (v – vf)/vfg
= (0.02 - 0.0007435)/(0.12355 - 0.0007435) = 0.157

The tables for refrigerant works with the same principle as the ones for water, the
temperatures are much lower though. In this example the specific volume must first be
determined. Then check the tables (A12) at 160kPa. If the specific volume was equal to vf,
then the refrigerant would be saturated liquid. If it was equal to vg, then it would be
saturated vapor. But it is in-between, thus it is a saturated mixture. Using the formula for
specific volume, the quality can be determined
 Saturated
liquid-vapor
Property Tables mixture

Example 4-5 An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.

Determine (a) the temperature, (b) the quality, (c) the enthalpy of the refrigerant, and (d)
the volume occupied by the vapor phase.
At 160 kPa (Table A–12)
hf = 31.18 kJ/kg and hfg = 209.96 kJ/kg.
h = hf + xhfg = 31.18 + (0.157)(209.96) = 64.1 kJ/kg
mg = xmt
= (0.157)(4) = 0.628 kg
Vg = mgvg
= (0.628)(0.12355) = 0.0776 m3 (or 77.6 L)

With the quality known, the enthalpy can be determined. Read of the values of hf, hfg and
determine h at the state in question.
Since this is a mixture, the total volume is not occupied by the vapor. The volume occupied
by vapor can be determined with the mass of vapor multiplied by specific volume of
saturated vapor
 Properties of Pure Substances
CHAPTER 4
This concludes our first lesson for Unit 3 – chapter 4. Here are four problems to complete to
check if you can use the saturation tables. These problems are also listed on Teams
Problems for HW Lesson 5:
• 4-28
• 4-32
• 4-41
• 4-50