CHAPTER 2

Phase Diagrams

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2.1 Phase Change
✓ A phase change is when matter changes from one state (solid, liquid, gas) to another.
✓ These changes occur when sufficient energy is supplied to the system, and can occur
when the pressure is changed.
✓ The energy associated with these transitions is called latent heat.
a) Melting is the transition of a substance from the solid to the liquid state.
b) Sublimation is the transition of a substance from the solid to the gas state, without
passing through the liquid state.
c) Vaporization is the transition of a substance from the liquid to the vapor state.
d) Condensation is the transition of a substance from the gas phase into the liquid phase

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2.2 Phase Change and Gibbs Free Energy
✓ To understand what causes a substance to change from one phase to another requires
an understanding of the Gibbs free energy change associated with the phase change.
✓ We have seen that at constant temperature and pressure, systems tend to move
spontaneously towards the lowest possible Gibbs free energy state.
Case Study we saw in chapter-1:
Assume that you have two reactions, rxn-1 and rxn-2
Both reactions have ΔG less than zero
Question is which one is more spontaneous
ΔGrxn-1 = -5 kJ/mol ΔGrxn-2 = -3 kJ/mol
Answer:
As rxn-1 has more negative ΔG as compared to rxn-2, hence rxn-1 is more spontaneous
than rxn-2. COLLEGE OF
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2.2 Phase Change and Gibbs Free Energy
Example (case study), G vs T (pure substance)

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2.2 Phase Change and Gibbs Free Energy
Example (case study), G vs T (pure substance)
✓ Consider the plot, which shows 𝑮 vs. 𝑻 for a pure substance.
✓ At temperature 𝑻𝟏, 𝑮 for the solid phase is lower than 𝑮 for the liquid phase or 𝑮
for the gas phase.
✓ Therefore, at 𝑻𝟏 the solid state is the most stable, and the system will tend to exist
as a solid ( @ point 𝒄) at this temperature.

✓ As the temperature is raised the 𝑮 of the

solid moves along the line 𝒄 → 𝒅 until the point
𝒅 is reached, at 𝑻𝟐
✓ At 𝑻𝟐 the 𝑮 of the solid has the same value as
the 𝑮 of the liquid, which is lower than the
𝑮 of the gas (or vapor) at this temperature.
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2.2 Phase Change and Gibbs Free Energy
Example (case study), G vs T (pure substance)
✓ Thus, at point 𝒅, 𝑮𝒔𝒐𝒍𝒊𝒅 = 𝑮𝒍𝒊𝒒 < 𝑮𝒈𝒂𝒔 , which means that at 𝑻𝟐 the liquid and solid
are equally stable.
✓ They can coexist in equilibrium, 𝑻𝟐 is the melting point of the solid (or the freezing
point of the liquid).

✓ After sufficient heat input to melt all the

solid to liquid, further heating will start to
raise the temperature.
✓ When the system is further heated past 𝑻𝟐 it
will follow the line 𝒅 → 𝒆.
✓ At any intermediate temperature 𝑻𝟑 the
system exists only as liquid.
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2.2 Phase Change and Gibbs Free Energy
Example (case study), G vs T (pure substance)
✓ When the system’s temperature reaches point 𝒆 at 𝑻𝟒, the 𝑮𝒍𝒊𝒒𝒖𝒊𝒅 = 𝑮𝒈𝒂𝒔 .
✓ Which means that both liquid and vapor phases are equally stable; i.e., they can
coexist in equilibrium with each other.
✓ T4 is the boiling point of the liquid.

✓ After sufficient heating to convert all the

liquid to vapor, further heating will cause the
system to move along the line 𝒆 → 𝒇.
✓ All points on the line 𝒆𝒇 correspond to the
system existing in the gaseous state.

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2.2 Phase Change and Gibbs Free Energy
Example (case study), G vs T (pure substance)
✓ At 𝑻𝟐 (the melting point), 𝑮𝒔𝒐𝒍𝒊𝒅 = 𝑮𝒍𝒊𝒒𝒖𝒊𝒅 , then 𝚫𝑮𝑻,𝑷 = 𝟎 and there is no tendency
for either phase to change to the other, the system is in solid/liquid equilibrium.
✓ Similarly, at 𝑻𝟒 (the boiling point), 𝑮𝒍𝒊𝒒𝒖𝒊𝒅 = 𝑮𝒈𝒂𝒔 , and the system is in liquid/vapor
equilibrium.

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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)

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2.3 Phase Diagram (P-T diagram)
Vapor Pressure
✓ It is a measure of the tendency of a material to change into the gaseous or vapor
state.
✓ It is dependent upon temperature.
✓ When the liquid in a closed container is heated, more molecules escape the liquid
phase and evaporate.
✓ The greater number of vapor molecules strike the container walls more frequently,
resulting in an increase in pressure.
✓ The boiling point of a substance is the temperature at which the vapor pressure
equals the environmental pressure surrounding the substance.

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2.3 Phase Diagram (P-T diagram)
Supercritical Fluid
✓ A supercritical fluid (SCF) is any substance at
a temperature and pressure above its critical
point.
Critical point
✓ It is a point on a phase diagram at which both
the liquid and gas phases of a substance have
the same density and are therefore
indistinguishable.

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2.3 Phase Diagram (P-T diagram)

Source: https://www.youtube.com/watch?v=GemthMqZ84s

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 2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)

✓ Consider point 𝒂 on the diagram: At this low

temperature and pressure the system will
tend to exist as a solid.
✓ Keeping the pressure constant at 𝟏 𝒂𝒕𝒎 and
slowly increasing the temperature, the
system moves along the horizontal line
𝒂𝒃𝒄𝒅𝒆𝒇𝒈𝒉.
✓ At point 𝒃 the system is still solid, but at
a higher temperature than at point 𝒂.
✓ Point 𝒄 is the normal melting point for
the solid; further heating doesn’t raise
the temperature; instead, the solid
starts to melt to form liquid. 13
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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)
✓ At point 𝒄 the system exists as an
equilibrium mixture of solid and liquid.
✓ After sufficient heating has been
applied to convert all the solid to
liquid, further heating raises the
temperature of the liquid.
✓ At point 𝒅 the system is all liquid.
✓ At point 𝒆, which is the normal boiling
point of the liquid, both liquid and vapor
coexist in equilibrium until sufficient
heating has converted all the liquid to
vapor.
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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)
✓ At point 𝒇 the system exists only as gas.
✓ Beyond point 𝒈 the system exists only as a supercritical fluid.

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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)
✓ Now consider a gas at 𝑻𝟏 (point 𝒊).
✓ When the pressure is increased to point 𝒋
the gas will start to condense to form
liquid.
✓ At this temperature and pressure, we
have vapor in equilibrium with liquid.
✓ This pressure is the equilibrium vapor
pressure of the liquid at temperature 𝑻𝟏.
✓ When we try to increase the pressure at
point 𝒋 , instead of the pressure
increasing, it stays at the same value
until all the gas has condensed to form
liquid. 16
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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)
✓ After complete liquefaction, the pressure
then starts to increase again. At point 𝒌,
for example, the system exists as
pressurized liquid.
✓ When point 𝒍 is reached the liquid starts to
solidify.
✓ T1 is the freezing point of the liquid when it
is at the pressure at point 𝒍.
✓ As we try to increase the pressure above
the pressure at point 𝒍, the pressure doesn’t
increase.
✓ Instead, the liquid converts to solid at the
temperature and pressure at point 𝒍. COLLEGE OF
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2.3 Phase Diagram (P-T diagram)
Example (case study), P vs T (pure substance)
✓ After all the liquid has been converted to
solid, then the pressure again can rise. At
point 𝒎 the system exists only as a solid
under high pressure.
✓ Point 𝒏 is the triple point for the
substance, the temperature and
pressure at which all three phases can
coexist in equilibrium.

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2.4 Phase Rule
✓ The Phase Rule was derived by Josiah Willard Gibbs after whom the Gibbs free
energy was named.
✓ This rule states that for any chemical system in equilibrium,

𝑭=𝑪−𝑷+𝟐 Gibbs Phase Rule

✓ 𝑪 is the number of components in the system.

✓ 𝑷 is the number of phases in the system.
✓ 𝑭 is the number of degrees of freedom for the system.
✓ 𝑭 refers to the number of intensive variables or properties that can be changed
independently without changing the number of phases in equilibrium.
✓ An intensive property is a property that is independent of the mass of the system. For
example, temperature, pressure, the mole fractions, etc.
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2.4 Phase Rule
✓ Consider point 𝑨. At this temperature and pressure the phase diagram tells us that
the system will exist as solid.
✓ In this region, there is only one phase (solid); that is, 𝑷 = 𝟏.
𝑭=𝑪−𝑷+𝟐
=𝟏−𝟏+𝟐
=𝟐
✓ Two degrees of freedom means that we can
vary both 𝑻 and 𝑷 independently in this region
and still have the same phase.
✓ Similar arguments can be made for the points 𝑩
and 𝑪 , both of which also are single phase
regions.
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2.4 Phase Rule
✓ Now consider point 𝑫: This point places the system on one of the boundaries
between two phases: in this case solid and liquid.
✓ For point 𝑫, now we have two phases (solid and liquid), so 𝑷 = 𝟐.
𝑭=𝑪−𝑷+𝟐
=𝟏−𝟐+𝟐
=𝟏
✓ The system now has only one degree of
freedom.
✓ In practical terms what this means is that if
we want to have two phases present at the
same time, we are free to independently
choose either the pressure or the
temperature, but not both. 21
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2.4 Phase Rule
✓ Thus, if we choose some specific value of 𝑻, then, in order to be on the melting point
curve the value of 𝑷 is fixed (we don’t have the choice to decide).
✓ Alternatively, if we arbitrarily choose 𝑷, then we have no choice in 𝑻.
✓ The same arguments apply to points 𝑬 and 𝑭.

✓ Thus, any point located on one of the phase

boundary lines represents a condition of
phase equilibrium with only one degree of
freedom.

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2.4 Phase Rule
✓ The exception is at the triple point, point 𝑮, where we have three phases––solid,
liquid, and vapor––all existing together at the same time. 𝑷 = 𝟑

𝑭=𝑪−𝑷+𝟐
=𝟏−𝟑+𝟐
=𝟎
✓ If we want all three phases together in
equilibrium at the same time we have no
choice.
✓ There is only one 𝑻 and 𝑷 for which this is
possible.
✓ We cannot vary either the temperature or
the pressure as we have zero degrees of
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2.5 Phase Diagram (P-T) for CO2
✓ The 𝑷 − 𝑻 phase diagram for 𝑪𝑶𝟐, has the shape typical for most substances.
✓ The melting point curve slopes steeply upward to the right. That is, the melting point
increases as the pressure increases.
✓ The diagram shows that no liquid exists at pressures below 𝟓. 𝟎𝟕 𝒃𝒂𝒓.
✓ Therefore, at 𝟏 𝒂𝒕𝒎 pressure (𝟏. 𝟎𝟏𝟑𝟐𝟓 𝒃𝒂𝒓) the solid sublimes to form vapor at – 𝟕𝟖℃,
which is called the normal sublimation point.

✓ In order to form liquid 𝑪𝑶𝟐 the system must be

pressurized to 𝟓. 𝟎𝟕 𝒃𝒂𝒓 or greater.
✓ The contents of a 𝑪𝑶𝟐 fire extinguisher at 𝟐𝟓℃
consist of liquid 𝑪𝑶𝟐 in equilibrium with gaseous
𝑪𝑶𝟐 under an equilibrium pressure of 𝟔𝟕 𝒃𝒂𝒓.

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2.5 Phase Diagram (P-T) for CO2
✓ The triple point of the 𝑪𝑶𝟐 is at −𝟓𝟔℃ and 𝟓. 𝟎𝟕 𝒃𝒂𝒓.
✓ The critical point of the 𝑪𝑶𝟐 is at 𝟑𝟏℃ and 𝟕𝟑. 𝟖 𝒃𝒂𝒓.

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2.6 Phase Diagram (P-T) for Water
✓ The phase diagram for 𝑯𝟐𝑶 is atypical in that the melting point curve slopes steeply to
the left instead of to the right.
✓ At 𝟏 𝒂𝒕𝒎 (𝟏. 𝟎𝟏𝟑𝟐𝟓 𝒃𝒂𝒓), ice turns into liquid water at 𝟎℃ and liquid water turns into
water vapor at 𝟏𝟎𝟎℃.
✓ The triple point of the water is at 𝟎. 𝟎𝟏℃ and 𝟎. 𝟎𝟎𝟔𝟏𝟏 𝒃𝒂𝒓.
✓ The critical point of the 𝐇𝟐 𝐎 is at 𝟑𝟕𝟒℃ and 𝟐𝟐𝟎. 𝟓 𝒃𝒂𝒓.

✓ If the pressure is decreased to 𝟎. 𝟎𝟑𝟏𝟔𝟗

𝒃𝒂𝒓 , the liquid water can be converted
into water vapor at 𝟐𝟓℃.

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2.7 Phase Diagram (P-T) for Helium
✓ Helium displays interesting behavior at low temperatures.
✓ For one thing, there is no equilibrium between the solid and the gas, even at very low
temperatures.
✓ A solid phase can be obtained only by increasing the pressure to more than 𝟏𝟎 𝒃𝒂𝒓.

✓ Helium is the only known substance that has two liquid

phases in equilibrium: 𝑳𝒊𝒒𝒖𝒊𝒅 𝑰 is a normal type of
liquid; but 𝑳𝒊𝒒𝒖𝒊𝒅 𝑰𝑰 is a “superfluid,” which flows
without viscosity (no friction).
✓ The critical temperature is 𝟓. 𝟐 𝑲 ; at temperatures
greater than this helium exists only as a gas,
regardless of how much pressure is applied.

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2.8 Phases Change Processes of Pure Substance
✓ There are many practical situations where two phases of a pure substance coexist
in equilibrium.
✓ Water exists as a mixture of liquid and vapor in the boiler and the condenser of a
steam power plant.
Terminologies:
1. Compressed liquid -- not about to evaporate
2. Saturated liquid -- about to evaporate
3. Saturated liquid-vapor mixture --two phase
4. Saturated Vapor -- about to condense
5. Superheated Vapor -- not about to condense

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2.8 Phases Change Processes of Pure Substance
Compressed Liquid and Saturated Liquid
✓ Consider a piston–cylinder device containing liquid water at 𝟐𝟎℃ and 𝟏 𝒂𝒕𝒎 pressure
(state 1).
✓ Under these conditions, water exists in the liquid phase, and it is called a compressed
liquid, or a sub cooled liquid, meaning that it is not about to vaporize.

✓ Heat is now transferred to the water until its temperature rises to,
say, 𝟒𝟎℃.
✓ As the temperature rises, the liquid water expands slightly, and so
its specific volume increases.
✓ To accommodate this expansion, the piston moves up slightly.
✓ Water is still a compressed liquid at this state since it has not
started to vaporize.
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2.8 Phases Change Processes of Pure Substance
Compressed Liquid and Saturated Liquid….continue
✓ As more heat is transferred, the temperature keeps rising until it reaches 𝟏𝟎𝟎℃.
✓ At this point water is still a liquid, but any heat addition will cause some of the liquid to
vaporize.

✓ That is, a phase-change process from liquid to vapor is about to take

place.
✓ A liquid that is about to vaporize is called a saturated liquid.
Therefore, state 2 is a saturated liquid state.

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2.8 Phases Change Processes of Pure Substance
Saturated Liquid-Vapor Mixture
✓ Once 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.
✓ Midway about the vaporization line (state 3), the cylinder
contains equal amounts of liquid and vapor.
✓ This state is called as the saturated liquid-vapor mixture.

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2.8 Phases Change Processes of Pure Substance
Saturated Vapor
✓ As we continue transferring heat, the vaporization process
continues until the last drop of liquid is vaporized (state 4).
✓ At this point, the entire cylinder is filled with vapor that is on
the borderline of the liquid phase.
✓ Any heat loss from this vapor will cause some of the vapor to
condense (phase change from vapor to liquid).
✓ A vapor that is about to condense is called a saturated vapor.

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2.8 Phases Change Processes of Pure Substance
Superheated Vapor
✓ Once the phase-change process is completed, we are back to
a single phase region again (this time vapor), and further
transfer of heat results in an increase in both the
temperature and the specific volume.
✓ At state 5, the temperature of the vapor is, let us say, 𝟑𝟎𝟎℃;
and if we transfer some heat from the vapor, the
temperature may drop somewhat but no condensation will take
place as long as the temperature remains above 𝟏𝟎𝟎℃.
✓ A vapor that is not about to condense is called a superheated
vapor. Therefore, water at state 5 is a superheated vapor.

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2.8 Phases Change Processes of Pure Substance
T-v diagram for the heating process of water at constant pressure (𝑷 = 𝟏 𝒂𝒕𝒎)

1. Compressed liquid (not about to evaporate)

2. Saturated liquid (about to evaporate)
3. Saturated liquid-vapor mixture (two phase)
4. Saturated Vapor (about to condense)
5. Superheated Vapor (not about to
condense)

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2.9 Effect of Pressure on Boiling Point
✓ It probably came as no surprise to you that water started to boil at 𝟏𝟎𝟎℃.
✓ Strictly speaking, the statement “water boils at 𝟏𝟎𝟎℃” is incorrect.
✓ The correct statement is “water boils at 𝟏𝟎𝟎℃ at 𝟏 𝒂𝒕𝒎 pressure.”
✓ The only reason water started boiling at 𝟏𝟎𝟎℃ was because we held the pressure
constant at 𝟏 𝒂𝒕𝒎 (𝟏𝟎𝟏. 𝟑𝟐𝟓 𝒌𝑷𝒂).
✓ If the pressure inside the cylinder was raised to 𝟓𝟎𝟎 𝒌𝑷𝒂 by adding weights on top
of the piston, water would start boiling at 𝟏𝟓𝟏. 𝟖°𝑪.
✓ That is, the temperature at which water starts boiling depends on the pressure;
therefore, if the pressure is fixed, so is the boiling temperature.

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2.10 Saturation Temperature and Pressure
✓ 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.

✓ At a pressure of 𝟏𝟎𝟏. 𝟑𝟐𝟓 𝒌𝑷𝒂, 𝑻𝒔𝒂𝒕 is 𝟗𝟗. 𝟗𝟕℃ (for water).

✓ Conversely, at a temperature of 𝟗𝟗. 𝟗𝟕℃, 𝑷𝒔𝒂𝒕 is 𝟏𝟎𝟏. 𝟑𝟐𝟓 𝒌𝑷𝒂 (for water).

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2.11 Phases Change Processes of Pure Substance
Latent Heat
✓ It takes a large amount of energy to melt a solid or vaporize a liquid.
✓ The amount of energy absorbed or released during a phase-change process is
called the latent heat.
✓ More specifically, the amount of energy absorbed during melting is called the
latent heat of fusion (latent heat of fusion of water is 𝟑𝟑𝟑. 𝟕 𝒌𝑱/𝒌𝒈).
✓ Similarly, the amount of energy absorbed during vaporization is called the latent
heat of vaporization (latent heat of vaporization of water is 𝟐𝟐𝟓𝟔. 𝟓 𝒌𝑱/𝒌𝒈).

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2.12 T-V Diagram for Water
T-V Diagram

The phase-change process of water

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2.12 T-V Diagram for Water
T-V Diagram
✓ As heat is transferred to the water at 𝑷 = 𝟏 𝑴𝑷𝒂, the process follows a path that looks
very much like the process path at 𝟎. 𝟏 𝑴𝑷𝒂 (𝟏 𝒂𝒕𝒎) pressure, as shown in Fig, but there are
some noticeable differences.
✓ First, water starts boiling at a much higher temperature
(𝟏𝟕𝟗. 𝟗℃) at this pressure (𝟏 𝑴𝑷𝒂) (as compared to 𝟏𝟎𝟎℃
at 𝟏 𝒂𝒕𝒎).
✓ Second, the specific volume of the saturated liquid is
larger and the specific volume of the saturated vapor is
smaller than the corresponding values at 𝟏 𝒂𝒕𝒎 pressure.
✓ That is, the horizontal line that connects the saturated
liquid and saturated vapor states is much shorter.

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2.12 T-V Diagram for Water
T-V Diagram
✓ As the pressure is increased further, this saturation
line continues to shrink, as shown in Fig., and it becomes
a point when the pressure reaches 𝟐𝟐. 𝟎𝟔 𝑴𝑷𝒂 in case of
water.
✓ This point is called the critical point, and it is defined
as the point at which the saturated liquid and saturated
vapor states are identical.
✓ The temperature, pressure, and specific volume of a
substance at the critical point are called, respectively,
the critical temperature 𝑻𝒄𝒓 , critical pressure 𝑷𝒄𝒓 , and
critical specific volume 𝒗𝒄𝒓 .

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2.12 T-V Diagram for Water
T-V Diagram All the superheated
vapor states are
located to the right
of the saturated
vapor line, called the
superheated vapor
saturated liquid line region.

All the compressed In these two regions,

liquid states are the substance exists
located in the region in a single phase, a
to the left of the liquid or a vapor.
saturated liquid line,
called the compressed saturated vapor line
liquid region.

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2.12 T-V Diagram for Water
T-V Diagram

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2.13 P-V Diagram for Water
P-V Diagram
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 downward trend, as shown in this
Fig.

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2.13 P-V Diagram for Water
P-V Diagram
✓ Consider again a piston–cylinder device that contains liquid
water at 𝟏 𝑴𝑷𝒂 and 𝟏𝟓𝟎°𝑪. Water at this state exists as a
compressed liquid.
✓ Now the weights on top of the piston are removed one by one
so that the pressure inside the cylinder decreases gradually
(by keeping the temperature constant).
✓ As the pressure decreases, the volume of the water increases
slightly.
✓ When the pressure reaches the saturation-pressure value at
the specified temperature (𝟎. 𝟒𝟕𝟔𝟐 𝑴𝑷𝒂), the water starts to
boil.

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2.13 P-V Diagram for Water
P-V Diagram
✓ During this vaporization process, the
temperature remain constant, but the
specific volume increases.
✓ Once the last drop of liquid is vaporized,
further reduction in pressure results in a
further increase in specific volume.
✓ When the process is repeated for other
temperatures, similar paths are obtained for
the phase-change processes.

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QUESTIONS ?? COLLEGE OF
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