Properties of pure substance

Pure substance is a substance consisting of a single chemical species like H2O, N2

Water, nitrogen, helium, and carbon dioxide etc.
A mixture of constant composition like air which is a mixture of N2 and O2 can be
treated as a pure substance.

Example: Air, steam, Steam+ water,

 Gaseous combustion products and mixture of oil and water are not a pure
substance because it is variable in chemical composition.

1
T-V diagram for a pure substance

2
T-V diagram for a pure substance

3
P-V diagram for a pure substance

4
P-V diagram for a pure substance

5
 Points to remember
Compressed or subcooled liquid:- When a matter exists in a liquid state and is not about to vaporize is called
compressed liquid. State 1 is a compressed liquid state.
Saturated liquid state: A liquid that is about to vaporize is called saturated liquid state. State 2 is a saturated liquid
state.
Saturated Vapour state: A liquid that is about to condense upon removal of heat is called saturated vapour state.
State 4 is a saturated vapour state.
A substance at states 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.
During the process of boiling, the temperature stops rising until the liquid is completely converted to vapour.
The temperature is constant during this period.
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°C; 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°C
A vapor that is not about to condense (i.e., not a saturated vapor) is called a superheated vapor. Therefore,
water at state 5 is a superheated vapor.
6
 Points to remember
Water boils at 100°C” is incorrect. The correct
statement is “water boils at 100°C at 1 atm
If the pressure inside the cylinder were raised to
500 kPa, water would start boiling at 151.8°C. That
is, the temperature at which water starts boiling
depends on the pressure.
As the pressure increases, the boiling temperature
of substances increases (Table 3-1).
Also, the boiling temperature of a substance
decreases with increase in elevation (Table 3-2).
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.

7
8
9
10
11
 THE IDEAL-GAS EQUATION OF STATE
Any equation that relates the pressure, temperature, and specific volume of a
substance is called an equation of state.
Property relations that involve other properties of a substance at equilibrium
states are also referred to as equations of state.
There are several equations of state, some simple and others very complex.
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.
Gas and vapor are often used as synonymous words. The vapor phase of a
substance is customarily called a gas when it is above the critical temperature.
Vapor usually implies a gas that is not far from a state of condensation.
12
 THE IDEAL-GAS EQUATION OF STATE
PV=RT
• In this equation, P is the absolute pressure, T is the absolute temperature, and v
is the specific volume. The gas constant R is different for each gas (Fig. 3–45)
and is determined from

13
 THE IDEAL-GAS EQUATION OF STATE
An ideal gas is an imaginary substance that obeys the relation Pv=RT. It has
been experimentally observed that the ideal-gas relation given closely
approximates the P-v-T behavior of real gases at low densities.
At low pressures and high temperatures, the density of a gas decreases, and
the gas behaves as an ideal gas under these conditions.
In the range of practical interest, many familiar gases such as air, nitrogen,
oxygen, hydrogen, helium, argon, neon, krypton, and even heavier gases such
as carbon dioxide can be treated as ideal gases with negligible error (often less
than 1 percent).
Dense gases such as water vapor in steam power plants and refrigerant vapor
in refrigerators, however, should not be treated as ideal gases. Instead, the
property tables should be used for these substances.

14
 Is Water Vapor an Ideal Gas?

This question cannot be answered with a simple yes

or no. The error involved in treating water vapor as
an ideal gas is calculated and plotted in Fig. 3–49.
It is clear from this figure that at pressures below 10
kPa, water vapor can be treated as an ideal gas,
regardless of its temperature, with negligible error
(less than 0.1 percent).
At higher pressures, however, the ideal gas
assumption yields unacceptable errors, particularly
in the vicinity of the critical point and the saturated
vapor line (over 100 percent).
Therefore, in air-conditioning applications, the water
vapor in the air can be treated as an ideal gas with
essentially no error since the pressure of the water
vapor is very low.
In steam power plant applications, however, the
pressures involved are usually very high; therefore,
ideal-gas relations should not be used.
15
 COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
The ideal-gas equation is very simple and thus very convenient to use.
However, as illustrated in Fig. 3–49, gases deviate from ideal-gas behavior
significantly at states near the saturation region and the critical point.
This deviation from ideal-gas behavior at a given temperature and pressure
can accurately be accounted for by the introduction of a correction factor
called the compressibility factor Z defined as

16
• It can also be expressed as

where videal =RT/P. Obviously, Z =1 for ideal gases.

For real gases Z can be greater than or less than unity (Fig. 3–50). The
farther away Z is from unity, the more the gas deviates from ideal-gas
behavior.
 Gases behave differently at a given temperature and pressure, but they behave very much the same at
temperatures and pressures normalized with respect to their critical temperatures and pressures. The
normalization is done as

17
18
19
 Properties of a Gas Mixtures
Up to this point, we have limited our consideration to thermodynamic
systems that involve a single pure substance such as water.
Many important thermodynamic applications, however, involve mixtures of
several pure substances rather than a single pure substance.
Therefore, it is important to develop an understanding of mixtures and learn
how to handle them. In this chapter, we deal with non-reacting gas mixtures.
A non-reacting gas mixture can be treated as a pure substance since it is
usually a homogeneous mixture of different gases.
The properties of a gas mixture obviously depend on the properties of the
individual gases (called components or constituents) as well as on the amount
of each gas in the mixture.

20
 MASS AND MOLE FRACTIONS OF A GAS MIXTURE
To determine the properties of a mixture, we need to know
the composition of the mixture as well as the properties of
the individual components.
There are two ways to describe the composition of a
mixture: either by specifying
(a) Molar analysis: The number of moles of each
components is considered.
• A mole is a unit of measurement used to measure the
amount of any fundamental entity (atoms, molecules, ions)
present in the substance.
• A mole is very much similar to the concept of weight, as
both help in understanding the amount of a substance
present.
• One mole of any substance is equal to the value of 6.023 x
1023 (Avagadro number). It can be used to measure the
products obtained from the chemical reaction. The unit is
denoted by mol. 21
 MASS AND MOLE FRACTIONS OF A GAS MIXTURE

Mass of one mole= Molecular wt.

(b) Gravimetric analysis: The mass of each components is considered. 22
 MASS AND MOLE FRACTIONS OF A GAS MIXTURE
Consider a gas mixture composed of k components.
The mass of the mixture mm is the sum of the masses of the individual
components, and the mole number of the mixture Nm is the sum of the mole
numbers of the individual components

 The ratio of the mass of a component to the mass of the mixture is called the
mass fraction mf.
 The ratio of the mole number of a component to the mole number of the
mixture is called the mole fraction y:

23
 MASS AND MOLE FRACTIONS OF A GAS MIXTURE
we can easily show that the sum of the mass fractions or mole fractions for a mixture is
equal to 1

The mass of a substance can be expressed in terms of the mole number N and molar mass M of the substance as
m = NM. Then the apparent (or average) molar mass and the gas constant of a mixture can be expressed as
m = NM.

Mass and mole fractions of a mixture are related by

24
25
26
 P-V-T Behavior of Gas Mixtures
The P-v-T behavior of an ideal gas is expressed by
Pv =RT,
Which is called the ideal-gas equation of state.
The P-v-T behavior of real gases is expressed by
Pv=ZRT,
where Z is the compressibility factor.
In ideal gas the molecules are spaced far apart so that behavior of a molecules
is not influenced by the presence of other molecules i.e., low density.
However, the real gas approximate this behavior closely when they are at low
pressure or high temperature relative to their critical-point values.

27
 P-V-T Behavior of Gas Mixtures
Dalton’s law of additive pressures: The pressure of
a gas mixture is equal to the sum of the pressures
each gas would exert if it existed alone at the
mixture temperature and volume (Fig. 13–5).
Amagat’s law of additive volumes: The volume of a
gas mixture is equal to the sum of the volumes each
gas would occupy if it existed alone at the mixture
temperature and pressure (Fig. 13–6).

28
 P-V-T Behavior of Gas Mixtures
Dalton’s and Amagat’s laws hold exactly for ideal-gas mixtures, but only approximately for
real-gas mixtures.
This is due to intermolecular forces that may be significant for real gases at high densities.
For ideal gases, these two laws are identical and give identical results.

 In these relations, Pi is called the component pressure and Vi is called the

component volume 29
 Ideal-Gas Mixture
• For ideal gases, Pi and Vi can be related to yi by using the ideal-gas relation for
both the components and the gas mixture:

The ratio Pi /Pm is called the pressure fraction and the ratio Vi /Vm is called the volume
fraction of component i.

30
 Ideal-Gas Mixture

The quantity yiPm is called the partial pressure and the quantity yiVm is called
the partial volume (identical to the component volume for ideal gases).
For an ideal-gas mixture, the mole fraction, the pressure fraction, and the
volume fraction of a component are identical.
31
 Real-Gas Mixtures
Dalton’s law of additive pressures and Amagat’s law of additive volumes can also be
used for real gases but with some approximation.

For real gas mixture the component pressures or component volumes can be
evaluated from relations that take into account the deviation of each component from
ideal-gas behaviour.

 One way of analyzing is to use more exact equations of state (van der Waals, Beattie–
Bridgeman, Benedict–Webb–Rubin, etc.) instead of the ideal-gas equation of state.
Another way is to use the compressibility factor.

32
 Van der Waals Equation of State
The van der Waals equation has two constants that are determined from the
behavior of a substance at the critical point. It is given by

• Van der Waals improves the ideal-gas equation of state by including two of the
effects not considered in the ideal-gas model: the intermolecular attraction
forces and the volume occupied by the molecules themselves.
• The term a/v2 accounts for the intermolecular forces, and b accounts for the
volume occupied by the gas molecules.

33
 Van der Waals Equation of State
• In a room at atmospheric pressure and temperature, the volume actually occupied by
molecules is only about one-thousandth of the volume of the room.
• As the pressure increases, the volume occupied by the molecules becomes an increasingly
significant part of the total volume.
• Van der Waals proposed to correct this by replacing v in the ideal-gas relation with the
quantity v -b, where b represents the volume occupied by the gas molecules per unit mass.

34
 Representing using the compressibility factor

The compressibility factor of the mixture Zm can be

expressed in terms of the compressibility factors of the
individual gases Zi by applying Eq. 13–9 to both sides of
Dalton’s law or Amagat’s law expression and simplifying. We
obtain

where Zi is determined either at Tm and Vm (Dalton’s law) or at Tm and

Pm (Amagat’s law) for each individual gas.

35
 Representing using the compressibility factor
There is a significant difference between using the compressibility factor for a single gas and
for a mixture of gases.
The compressibility factor predicts the P-v-T behavior of single gases rather accurately, as
discussed in Chapter 3, but not for mixtures of gases.
When we use compressibility factors for the components of a gas mixture, we account for
the influence of like molecules on each other; the influence of dissimilar molecules remains
largely unaccounted for.
Consequently, a property value predicted by this approach may be considerably different
from the experimentally determined value.
Another approach for predicting the P-v-T behavior of a gas mixture is to treat the gas
mixture as a pseudopure substance.
One such method, proposed by W. B. Kay in 1936 and called Kay’s rule, involves the use of
a pseudocritical pressure Pcr,m and pseudocritical temperature Tcr,m for the mixture,
defined in terms of the critical pressures and temperatures of the mixture components as
36
 Representing using the compressibility factor

The compressibility factor of the mixture Zm is then easily determined by using these
pseudocritical properties.

37
 P-T diagram of a pure substance
 The state change of a pure substance upon
slow heating at different pressure on the P-V
plane was studied.
 If these states changes are plotted on P-T
coordinate the diagram will be like as shown
in Figure 9.8.
 The curve passes through 2-3 points is called
the fusion curve (ice changes into vapour).
 The curve passes through 4-5 points is called
the Vaporisation curve (Vaporisation or
condensation at different temperature and
pressure).
 At lower pressure, the solid can directly
changes to vapour and the curve separating
the solid and vapour state is called the
sublimation curve. 38
 Triple point
Triple point is a point of intersection of
sublimation line, vaporisation line and fusion
line where all the phases coexists in
Equilibrium.
On other property diagram (P-V and T-V
diagrams), such a condition are represented by
a line called triple line.
Triple point is a point in the P-T diagram,
while it is a line in P-V and it is a triangle on
U-V diagram.
Fusion line have (-ve) slope because the
melting point of ice decreases with increasing
pressure.
Only three substances (Water, antimony and
Bismuth) have (-ve) slope whereas all
remaining substance have (+ve) slope. 39
 P-V-T Surface
The relation between specific volume, pressure and temperature can be understood using the
P-V-T surface plot

40