Basic Thermodynamics [BME304] By: Mr. Yuvaraj K. B.

Module-5:
Ideal Gases, Real Gases and Thermodynamic Relations

Syllabus
Ideal gases: Ideal gas mixtures, Daltons law of partial pressures, Amagat’s law of additive
volumes, evaluation of properties of perfect and ideal gases, Air- Water mixtures and related
properties (Processes are not to be asked for SEE).
Real gases – Introduction, Van-der Waal's Equation of state, Van-der Waal's constants in terms
of critical properties, Beattie-Bridgeman equation, Law of corresponding states, compressibility
factor; compressibility chart. Difference between Ideal and real gases.
Thermodynamic relations: Maxwell’s equations, TdS equation. Ratio of Heat capacities and
Energy equation, Joule-Kelvin effect, Clausius-Clapeyron equation.

Notes

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Module-3

Introduction and Review of Ideal and Real Gases

Ideal gas mixtures:

An ideal gas is an imaginary gas having no forces of intermolecular attraction so that the
behavior of a molecule is not influenced by the presence of the other molecules and obeys the
law PV = RT at all pressures and temperatures. This relation is called the ideal gas equation
of state.

Daltons law of partial pressures:

Let us consider a closed vessel of volume V at temperature T, which contains a mixture of

perfect gases at a known pressure. If some of the mixture were removed, then the pressure
would be less than the initial value. If the gas removed were the full amount of one of the
constituents then the reduction in pressure would be equal to the contribution of that
constituent to the initial total pressure. Each constituent contributes to the total pressure by an
amount which is known as the partial pressure of the constituent.
The relationship between the partial pressures of the constituents is expressed by Dalton’s
law, as follows:
— The pressure of a mixture of gases is equal to the sum of the partial pressures of the
constituents.
— The partial pressure of each constituent is that pressure which the gas would exert if it
occupied alone that volume occupied by the mixtures at the same temperature.

This is expressed diagrammatically in (Fig. 9.1). The gases A and B, originally occupying
volume V at temperature T are mixed in the third vessel which is of the same volume and is
at the same temperature.

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Amagats Law of Additive Volumes:

Evaluation of Properties of Ideal Gases:

Real Gases:

Introduction

It has been observed that when experiments are performed at relatively low pressures and
temperatures most of the real gases obey Boyle’s and Charle’s laws quite closely. But the
actual behavior of real gases at elevated pressures and at low temperatures deviates
considerably.

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Similarly by dividing equ (7) by CP we get

Psychrometry
Psychrometry is the study of the properties of mixtures of air and water vapour.

5.6 Psychrometric properties:

Dry-bulb temperature (DBT)
The dry-bulb temperature is the temperature indicated by a thermometer exposed to the air in a place
sheltered from direct solar radiation. The term dry-bulb is customarily added to temperature to distinguish
it from wet-bulb and dewpoint temperature

Wet-bulb temperature (WBT)

The thermodynamic wet-bulb temperature is a thermodynamic property of a mixture of air and water
vapor. The value indicated by a wet-bulb thermometer often provides an adequate approximation of the
thermodynamic wet-bulb temperature.

Dew point temperature

The saturation temperature of the moisture present in the sample of air, it can also be defined as the
temperature at which the vapour changes into liquid (condensation)

Specific Humidity
Specific humidity is defined as the proportion of the mass of water vapor and mass of the moist air
sample (including both dry air and the water vapor); it is closely related to humidity ratio and always
lower in value.

Absolute humidity
The mass of water vapor per unit volume of air containing the water vapor. This quantity is also known
as the water vapor density.

Relative humidity
The ratio of the vapor pressure of moisture in the sample to the saturation pressure at the dry bulb
temperature of the sample.

Specific enthalpy
Analogous to the specific enthalpy of a pure substance. In psychrometrics, the term quantifies the total
energy of both the dry air and water vapour per kilogram of dry air

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Specific volume
Analogous to the specific volume of a pure substance. However, in psychrometrics, the term quantifies
the total volume of both the dry air and water vapour per unit mass of dry air.

Psychrometric ratio
The psychrometric ratio is the ratio of the heat transfer coefficient to the product of mass transfer
coefficient and humid heat at a wetted surface. It may be evaluated with the following equation
5.7 Psychrometric chart
A Psychrometric chart raphically represents the thermodynamic properties of moist air. Standard
psychrometric charts are bounded by the dry-bulb temperature line (abscissa) and the vapour pressure or
humidity ratio (ordinate). The Left Hand Side of the psychrometric chart is bounded by the saturation
line. Figur shows the schematic of a psychrometric chart. Psychrometric charts are readily available for
standard barometric pressure of 101.325 kPa at sea level and for normal temperatures (0-50˚C).

 Dry-bulb temperature (DBT) is that of an air sample, as determined by an ordinary thermometer. It is

typically plotted as the abscissa (horizontal axis) of the graph. The SI units for temperature are kelvins or
degrees Celsius; other units are degrees Fahrenheit and degrees Rankine.
 Wet-bulb temperature (WBT) is that of an air sample after it has passed through a constant-pressure, ideal,
adiabatic saturation process, that is, after the air has passed over a large surface of liquid water in an
insulated channel. In practice this is the reading of a thermometer whose sensing bulb is covered with a wet
sock evaporating into a rapid stream of the sample air (see Hygrometer). When the air sample is pre-
saturated with water, the WBT will read the same as the DBT. The slope of the line of constant WBT
reflects the heat of vaporization of the water required to saturate the air of a given relative humidity.

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 Dew point temperature (DPT) is the temperature at which a moist air sample at the same pressure would
reach water vapor "saturation." At this point further removal of heat would result in water vapor
condensing into liquid water fog or, if below freezing point, solid hoarfrost. The dew point temperature is
measured easily and provides useful information, but is normally not considered an independent property
of the air sample as it duplicates information available via other humidity properties and the saturation
curve.
 Relative humidity (RH) is the ratio of the mole fraction of water vapor to the mole fraction of saturated
moist air at the same temperature and pressure. RH is dimensionless, and is usually expressed as a
percentage. Lines of constant RH reflect the physics of air and water: they are determined via experimental
measurement. The concept that air "holds" moisture, or that moisture "dissolves" in dry air and saturates
the solution at some proportion, is erroneous see relative humidity for further details.
 Humidity ratio is the proportion of mass of water vapor per unit mass of dry air at the given conditions
(DBT, WBT, DPT, RH, etc.). It is also known as the moisture content or mixing ratio. It is typically plotted
as the ordinate (vertical axis) of the graph. For a given DBT there will be a particular humidity ratio for
which the air sample is at 100% relative humidity: the relationship reflects the physics of water and air and
must be determined by measurement. The dimensionless humidity ratio is typically expressed as grams of
water per kilogram of dry air, or grains of water per pound of air (7000 grains equal 1 pound).
 Specific enthalpy, symbolized by h, is the sum of the internal (heat) energy of the moist air in question,
including the heat of the air and water vapor within. Also called heat content per unit mass. In the
approximation of ideal gases, lines of constant enthalpy are parallel to lines of constant WBT. Enthalpy is
given in (SI) joules per kilogram of air, or BTU per pound of dry air.

5.8 Ideal gas mixture:

Consider a mixture of perfect gases A, B C etc existing in equilibrium at pressure P and occupying a
volume V , at temperature T . Each constitutes occupies the same volume that the entire mixture occupies
and each constituent is at same temperature of the mixture
Constituents Properties Mixture
A Pa , V , T , ma , na
B Pb , V , T , mb , nb P,V,T,m,n
C Pc , V , T , mc , nc

From the table it can be seen that (taking mass as an example) the total mass of the mixture is equal to the
sum of the masses of the individual gases, m = ma + mb + mc
 Mass fraction ( mf ) :
Mass fraction of the constituent gas is the ratio of the mass of the constituent gas to the total
mass of the mixture of perfect gases
,
m = ma + mb + mc

1 = mfa + mfb + mfc

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Amagats Law of Additive Volumes:

Evaluation of Properties of Ideal Gases:

Real Gases:

Introduction

It has been observed that when experiments are performed at relatively low pressures and
temperatures most of the real gases obey Boyle’s and Charle’s laws quite closely. But the
actual behavior of real gases at elevated pressures and at low temperatures deviates
considerably.

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The ideal gas equation pv = RT can be derived analytically using the kinetic theory of gases
by making the following assumptions:
(i) A finite volume of gas contains large number of molecules.
(ii) The collision of molecules with one another and with the walls of the container is
perfectly elastic.
(iii)The molecules are separated by large distances compared to their own dimensions.
(iv) The molecules do not exert forces on one another except when they collide.
(v) As long as the above assumptions are valid the behaviour of a real gas approaches
closely that of an ideal gas.

Van-Der Waal’s equation,

The ideal gas law treats the molecules of a gas as point particles with perfectly elastic
collisions. This works well for dilute gases in many experimental circumstances. But gas
molecules are not point masses, and there are circumstances where the properties of the
molecules have an experimentally measurable effect. A modification of the ideal gas law was
proposed by Johannes D. van der Waals in 1873 to take into account molecular size and
molecular interaction forces. It is usually referred to as the van der Waals equation of state.

The constants ‘a’ and ‘b’ have positive values and are characteristic of the individual gas. The
van der Waals equation of state approaches the ideal gas law PV=nRT as the values of these
constants approach zero.
The constant a provides a correction for the intermolecular forces. Constant b is a correction
for finite molecular size and its value is the volume of one mole of the atoms or molecules.

Van-Der Waal’s constants in terms of critical properties.

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Compressibility Factor:

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Compressibility Chart and Applications:

From the Z chart, one can conclude:

at very low pressure (PR <<1), the gases behave as an ideal gas regardless of temperature
at high temperatures (TR>2), ideal gas behavior can be assumed.
the deviation is highest in the vicinity of the critical point.

COMPRESSIBILITY CHART:

 This chart is the low-pressure chart, for reduced pressures between 0 and 1 as you can
see on the x-axis.
 Z is plotted on the y-axis.

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 The solid curves on this diagram are the family of curves for constant reduced
temperature. These curves generally run from the upper left-hand corner downwards
and towards the right-hand edge of the diagram.
 You can tell the solid curves represent constant TR by reading the labels on the curves
for TR = 1.0 and TR = 5.0 highlighted on the chart with yellow circles.
 The dashed curves on this diagram are the family of curves for constant ideal reduced
molar volume.
 You can tell the dashed curves represent constant VR-ideal by reading the label on the
curve for VR-ideal = 0.07, highlighted on the chart with a light blue circle.
 Inset on this diagram and highlighted in pale green is a very handy enlargement of the
top corner of the chart, where reduced pressure is between 0 and 0.1.

Where,
 P is the gas pressure
 R is the gas constant,
 T is temperature,
 Vm is the molar volume (V/n),
 a is a constant that corrects for attractive potential of molecules, and
 b is a constant that corrects for volume.

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 Basic Thermodynamics [BME304] By: Mr. Yuvaraj K. B.

BEATTIE-BRIDGEMAN EQUATION

REDUCED PROPERTIES

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LAW OF CORRESPONDING STATES

If any two gases have equal values of reduced pressure and reduced temperature, then they have
same values of reduced volume; i.e., vR = f(Tr , pr) for all gases and the function is the same.

This law is most accurate in the vicinity of the critical point.

Difference between Ideal and real gases:

Characteristic Ideal Gases Real Gases

Negligible (Assumed point Finite (Molecules have volume and
Molecular Size particles) interact with each other)
No intermolecular forces Intermolecular forces may be present
Molecular Attraction considered (e.g., van der Waals forces)
Volume of Particles Zero Non-zero (considerable volume)
Pressure-Volume Follows ideal gas law (PV = Deviates from ideal gas law, especially
Behavior nRT) at high pressures and low temperatures
Temperature-Volume Follows ideal gas law (PV = Deviates from ideal behavior at low
Behavior nRT) temperatures
Compressibility Z is not always equal to 1, varies with
Factor (Z) Z=1 conditions
Exhibits critical behavior, may
Critical Point Undergoes an ideal gas phase undergo phase transition with non-
Behavior transition at critical point ideal effects
Van der Waals Equation, Redlich-
Equation of State Ideal Gas Law (PV = nRT) Kwong Equation, etc.

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THERMODYNAMIC RELATIONS
Maxwell’s Equations:

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ENTROPY EQUATIONS (TdS Equation)

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Ratio of Heat Capacities and Energy Equation:

Joule-Kelvin Effect:

A gas is made to undergo continuous throttling process by a valve, as shown in Fig. 11.2. The
pressures and temperatures of the gas in the insulated pipe upstream and downstream of the
valve are measured with suitable manometers and thermometers.

Let Pi and Ti be the arbitrarily chosen pressure and temperature before throttling and let them
be kept constant. By operating the valve manually, the gas is throttled successively to
different pressures and temperatures Pf1, Tf1, Pf2, Tf2, Pf3, T f3 and so on. These are then plotted
on the T-p coordinates as shown in Fig. 11.3. All the points represent equilibrium states of
some constant mass of gas, say, 1 kg, at which the gas has the same enthalpy.

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The curve passing through all these points is an isenthalpic curve or an isenthalpe. It is not
the graph of a throttling process, but the graph through points of equal enthalpy.

The initial temperature and pressure of the gas (before throttling) arc then set to new values,
and by throttling to different states, a family of isenthalpes is obtained for the gas, as shown
in Figs 11.4 and 11.5. The curve passing through the maxima of these isenthalpes is called
the inversion curve. The numerical value of the slope of an isentbalpe on a T-p diagram at
any point is called the Joule-Kelvin coefficient and is denoted by μ1. Thus the locus of all
points at which μ, is zero is the inversion curve. The region inside the inversion curve where
μ1 is positive is called the cooling region and the region outside where μ1 is negative is called
the hearing region. So,

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There is no change in temperature when an ideal gas is made to undergo a Joule-

Kelvin expansion (i.e. throttling).
For achieving the effect of cooling by Joule-Kelvin expansion, the initial temperature
of the gas must be below the point where the inversion curve intersects the temperature axis,
i.e. below the maximum inversion temperature.
For nearly all substances, the maximum inversion temperature is above the normal
ambient temperature, and hence cooling can be obtained by the Joule Kelvin effect. In the
case of hydrogen and helium, however, the gas is to be precooled in heat exchangers below
the maximum inversion temperature before it is throttled. For liquefaction the gas has to be
cooled below the critical temperature.
Let the initial state of gas before throttling be at A (Fig. 11.6). The change in
temperature may be positive, zero, or negative, depending upon the final pressure after
throttling. If the final pressure lies between A and B, there will be a rise in temperature or
heating effect. If it is at C, there will be no change in temperature. If the final pressure is
below Pc there will be a cooling effect, and if the final pressure is Po, the temperature drop
will be (TA - T D).
Maximum temperature drop will occur if the initial state lies on tire inversion curve.
In Fig. 11.6, it is (TB -TD).
The volume expansivity is

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Clausius-Clapeyron Equation:

Clausius-Claperyon equation is a relationship between the saturation pressures,

temperature, the enthalpy of evaporation, and the specific volume of the two phases involved.
This equation provides a basis for calculations of properties in a two-phase region. It gives
the slope of a curve separating the two phases in the p-T diagram.

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COMBUSTION THERMODYNAMICS
Theoretical (Stoichiometric) Air for Combustion of Fuels:

Stoichiometric (or chemically correct) mixture of air and fuel is one that contains just
sufficient oxygen for complete combustion of the fuel.
 A weak mixture is one which has an excess of air.
 A rich mixture is one which has a deficiency of air.
The percentage of excess air is given as under:

Excess Air:

The minimum amount of air that supplies sufficient oxygen for the complete
combustion of all the carbon, hydrogen, and any other elements in the fuel that may oxidise is

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Module-3
Introduction and Review of Ideal and Real Gases
1. One kg of CO2 has a volume of 1 m3 at 100°C. Compute the pressure by
(i) Van der Waals’ equation
(ii) Perfect gas equation.

2. A container of 3 m3 capacity contains 10 kg of CO2 at 27°C. Estimate the pressure exerted

by CO2 by using :
(i) Perfect gas equation
(ii) Van der Waals’ equation
(iii) Beattie Bridgeman equation.

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3. A spherical shaped balloon of 12 m diameter contains H2 at 30°C and 1.21 bar. Find the
mass of H2 in the balloon using real gas equation.

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4. One kg-mol of oxygen undergoes a reversible non-flow isothermal compression and the
volume decreases from 0.2 m3/kg to 0.08 m3/kg and the initial temperature is 60°C. If the gas
obeys Van der Waals’ equation find:
(i) The work done during the process (ii) The final pressure.

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5. Calculate the density of N2 at 260 bar and 15°C by using the compressibility chart.

6. What should be the temperature of 1.3 kg of CO2 gas in a container at a pressure of 200
bar to behave as an ideal?

7. If the values for reduced pressure and compressibility factor for ethylene are 20 and 1.25
respectively, compute the temperature.

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Thermodynamic Relations:
1. Find the expression for ds in terms of dT and dp.

2. Derive the following relations:

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3. Derive the third Tds equation

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4. Using Maxwell relation derive the following Tds equation

5. Using Clausius-Claperyon’s equation, estimate the enthalpy of vaporization. The following

data is given:
At 200°C : vg = 0.1274 m3/kg ; vf = 0.001157 m3/kg ;

6.

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7. The Joule-Kelvin coefficient μ, is a measure of the temperature change during a throttling

process. A similar measure of the temperature change produced by an isentropic change of
pressure is provided by the coefficient μ,, where

8. Over a certain range of pressures and temperatures, the equation of a certain substance is
given by the relation

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where C is a constant. Derive an expression for (a) the change of enthalpy and
(b) The change of entropy, of this substance in an isothermal process.

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Combustion thermodynamics:
1. Calculate the theoretical air-fuel ratio for the combustion of octane, C8H18.

2. Methane (CH4) is burned with atmospheric air. The analysis of the products on a ‘dry’
basis is as follows :
CO2 = 10.00%, O2 = 2.37%, CO = 0.53%, N2 = 87.10%.
(i) Determine the combustion equation ; (ii) Calculate the air-fuel ratio ;
(iii) Percent theoretical air.

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