Chapter 2 Pure Substance Behavior

 Pure substance: A pure substance is one that has a homogeneous and

invariable chemical composition.

 Air is a mixture of several gases, but it is considered to be a pure substance.

Nitrogen and gaseous air are pure
substances.
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A mixture of liquid and gaseous
water is a pure substance, but a
mixture of liquid and gaseous air
is not.
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 Phase Change Process of Pure Substances

 Compressed liquid (subcooled liquid): A substance that it is not

about to vaporize (not ready yet).
 Saturated liquid: A liquid that is about to vaporize.

At 1 atm and 20°C,

water exists in the liquid
phase (compressed
liquid).

At 1 atm pressure and 100°C,

water exists as a liquid that is
ready to vaporize (saturated
liquid).

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 Saturated vapor: A vapor that is about to condense.
 Saturated liquid–vapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium.
 Superheated vapor: A vapor that is not about to condense.

At 1 atm pressure, the As more heat is

As more heat is transferred, transferred, the
part of the saturated liquid temperature remains
constant at 100°C until the temperature of the
vaporizes (saturated liquid– vapor starts to rise
vapor mixture). last drop of liquid is vaporized
(saturated vapor). (superheated vapor).
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Saturation Temperature and Saturation Pressure
The temperature at which water starts boiling depends on the pressure; therefore, if the
pressure is fixed, so is the boiling temperature.
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 liquid–
vapor
saturation
curve of a
pure
substance
(numerical
values are for
water).

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 saturated liquid the latent heat

saturated vapor

T-v diagram for the heating process of water at constant pressure.

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 The P–v–T Surface

The critical-point data for

more substances are given
in Aksel’s Table 2.1.

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 The P–v–T Surface

The P-v-T surfaces present a great deal of 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.

P-v-T surface of a substance that P-v-T surface of a substance

expands on freezing (like water). that contracts on freezing.
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 Sublimation: Passing from
the solid phase directly into Phase Diagram
the vapor phase.

At low pressures (below the triple-

point value), solids evaporate
without melting first (sublimation).
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P-T diagram of pure substances.
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 Independent Properties of a Pure Substance

The state of a pure substance is fixed by any two independent, intensive

properties

In a saturation state, pressure and

temperature are not independent
properties. Therefore, knowing P & T
is not going to be enough to fix the
state !

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 Tables of Thermodynamic Properties

the saturated-solid and

saturated-liquid region

superheated compressed-
vapor solid region

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 The Two–Phase States

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 By definition Vfg = Vg - Vf

v  vf
x
vg  v f
y  v, u , h, or s
y f  y  yg
You can calculate any specific property ‘y’ in two phase region by
knowing the quality y  y f  x y fg
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 Saturated Liquid and Saturated Vapor States
Table 2.5.1 Properties of Saturated Water (Liquid-Vapor): Temperature Table
Table 2.5.2 Properties of Saturated Water (Liquid-Vapor): Pressure Table
Partial displays of Tables 2.5.1 & 2.5.2

Quality 0    1
Saturation temperature
Saturated Liquid*1000

Saturated Liquid*1000
Saturation pressure at

Specific Volume of

Specific Volume of

Specific Volume of

Specific Volume of
given temperature

in saturated liquid–
at given pressure
Saturated Vapor

Saturated Vapor
vapor mixture region
Temperature

or two phase region

or wet region
Pressure

0: satureted liquid, yf,

1: satureted vapor, yg.
Temperatures are in convenient increments Pressures are in convenient increments 13
Using Table 2.5.1 Using Table 2.5.2
What are the saturated What are the saturated
pressure, specific volume of temperature, specific volume
liquid and vapor at 90°C of liquid and vapor at 100 kPa
temperature? pressure?

Vf = Vs & Vg = Vb

Specific Volume of Specific Volume of Sat. Specific Volume of Specific Volume of Sat.
Sat. Liquid, Vf = Vapor, Vg=2.361 (m3/kg) Sat. Liquid, Vf = Vapor, Vg=1.694 (m3/kg)
1.0361*10-3 (m3/kg) 1.0434*10-3 (m3/kg)

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As an example, let us calculate the specific volume of saturated steam at 200°C
having a quality of 70 %.
specific volume of liquid, Vs=Vf=1.1565*10-3 (m3/s)

specific volume of vapor, Vb=Vg=0.1272 (m3/s)

Vfg=0.126044 (m3/s)

V=0.089387 (m3/s)
or
v  v f  x v fg  v f  x (vg  v f )
3 3
v  1.1565 x10  0.7 * (0.1272  1.1565 x10 )  0.0894 m / kg
3

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 The Liquid and Solid States
The compressed liquid specific properties depend on
Compressed liquid (or temperature much strongly than they do on pressure.
subcooled) is characterized by Therefore, a compressed liquid specific property may
be approximated as a saturated liquid specific
at a givenT if P  Psat @ T
property at the given temperature, i.e.,
at a given P if T  Tsat @ P
@ a given T & P y  y f @T
at a given P or T if y  y f Suppose that we want to know v at 10 MPa & 100°C.
From tables its exact value is 0.001 0386 m3/kg & vf =
0.001 0437 m3/kg at 100°C.
Therefore, if we take 𝑣 ≅ 𝑣𝑓@100°𝐶 less than 1 % error
would be introduced !
The properties of a solid are mainly a function of
temperature, as the solid is nearly incompressible,
meaning that the pressure cannot change the
inermolecular distances and the volume is unaffected
by pressure. Thus,

@ a given T & P y  yi @T
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 Saturated Solid and Saturated Vapor
Table 2.5.4 of the steam tables gives the
properties of saturated solid and
saturated vapor that are in equilibrium.
The first column gives the temperature,
and the second column gives the
corresponding saturation pressure.

As would be expected, all these

pressures are less than the triple-point
pressure.

saturated solid and

saturated vapor

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 The Superheated Vapor States
Compared to saturated vapor, superheated
vapor is characterized by
at a givenT if P  Psat @ T
at a given P if T  Tsat @ P
at a given P or T if y  y g
A partial display of Table 2.5.3.
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The region to the right of the saturated
vapor line and the temperatures above
the critical point temperature is called as
the superheated vapor region.
Table 2.5.3 also includes
compressed liquid properties.
Above the line, the
properties are given for
the compressed liquid or
subcooled region
Below the line, the
properties are given for
the superheated region
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 Other Property Tables

Property tables also includes thermodynamic tables for several

other substances; refrigerants such as ammonia, R-12, and R-
134a and the cryogenic fluids such as nitrogen and methane.

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 Linear Interpolation
Example 2.5
Determine the pressure for water at 200°C with v = 0.4 m3/kg.

Solution
Starting with Table B.1.1 with 200°C and note that v > vg = 0.127 36 m3/kg, so we have
superheated vapor. Proceed to Table B.1.3 at any subsection with 200°C; suppose we
start at 200 kPa. There v = 1.08034 m3/kg, which is too large, so the pressure must be
higher. For 500 kPa, v = 0.42492 m3/kg, and for 600 kPa v = 0.35202 m3/kg, so it is
bracketed. This is shown in the figures given below.
A linear interpolation, between the two
pressures is done to get P at the desired v.

0.4  0.42492
P  500  (600  500)  534.2 kPa
0.35202  0.42492
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 The Ideal Gas States
Equation of state: Any equation that relates the pressure, temperature, and specific
volume of a substance.
The simplest and best-known equation of state for substances in the gas phase is the
ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas quite
accurately within some properly selected region.

Pv  RT & RR/M

R: gas constant (kJ/kg.K)

M: molar mass (kg/kmol)
𝑅: universal gas constant (kJ/kmol.K)

𝑅: 8.31447 (kJ/kmol.K)

Different substances have different gas constants.

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 Various Forms of Ideal Gas Equation

𝑃 = 𝜌𝑅𝑇

𝑉 = 𝑚𝑣 → 𝑃𝑉 = 𝑚𝑅𝑇

𝑚𝑅 = 𝑀𝑁 𝑅 = 𝑁𝑅 → 𝑃𝑉 = 𝑁𝑅𝑇

𝑉 = 𝑁𝑣 → 𝑃𝑣 = 𝑅𝑇

P = absolute pressure (kPa)

𝑣 = molar specific volume (m3/kmol)
T = absolute temperature (K)
𝑅 = universal gas constant 8.31447 (kJ/lmol.K)

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 The Compressibility Factor

Compressibility factor Z A factor that accounts for the deviation of real gases from
ideal-gas behavior at a given temperature and pressure.

The compressibility factor is unity for an ideal gas.

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 T–v Diagram for Water

03-21

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The General Compressibility Chart for Gasses

Reduced
pressure

Reduced
temperature

Pseudo-reduced
specific volume

Comparison of Z factors for various gases.

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 A
B
Ideal Gas Assumption
Region of Z~1

A) If the pressure is very low (that is, P « Pc), the ideal-gas model can be assumed with
good accuracy, regardless of the temperature
B) at high temperatures (that is, greater than about T  2 Tc ) pressures as high as four
or five times P  4  5 Pc
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 Other Equations of State

Many such equations have been proposed and

used to correlate the observed behavior of
gases. As an example, the class of relatively
simple equation known as cubic equations of
state

Equation of state accurately represents the P-v-T behavior for a particular gas over the
entire superheated vapor region

As an example, the class of relatively simple equation known as cubic equations of state

RT a
P  2
v  b v  cbv  db 2
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 Computerized Tables

Most of the tables in the booklet are supplied in a computer program which operates
with a visual interface in the Windows environment on a PC–type computer.

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