PARUL INSTITUTE OF TECHNOLOGY

Thermodynamics I
(303103257)
B.Tech Chemical Engineering

• Prepared by
• Heena N Katariya
• Assistant Professor
• Parul Institite of Technology
Contents
• PVT behavior of pure substances
• Equation of state & Concept of ideal gas
• Characteristics of an ideal gas
• Process involving ideal gases
• Equation of states, Virial, Cubic, Vanderwaals
EOS, Redlich/Kwong (RK) EOS etc.
• Calculation of constants in terms of Pc, Tc,
Vc.
• Generalized Correlations for gases and
liquids.
 PVT behavior of pure substances
The thermodynamic state of a pure fluid can be described in terms of two independent properties. Here the PVT behavior of
pure substances can be well explained by the PV and PT diagram.
• PV diagram:
• Consider the water which is represented in a figure as a function of pressure and
volume.
• The figure shows the variation in molar volume with pressure at various constant
temperatures.
• Here a represents the initial state of the system.
• Curve a-b-d-e shows the change in volume of water with pressure at constant
temperature
• Since liquid water is almost incompressible, the reduction in pressure to change
the state of system from a to b, will result in negligible increase in volume.
• When point b is reached, vaporization begins and this results in a rapid increase
in volume.
• From b to d , the two phases (liquid and vapor) are in equilibrium. The
temperature and pressure remain constant during the change of state from b to d,
represented by horizontal line in figure.
• Point b represents saturated liquid (100 % liquid) and point d represents
saturated vapor (100 % vapour).
• This vaporization of water continued until the point d is reached.
• b-d represents all the possible mixtures of liquid and vapour.
• The vapour and liquid coexisting in equilibrium are called saturated phases, and
the corresponding temperature and pressure are known as saturation temperature
and saturation pressure respectively.
• Further reduction in pressure increases the volume of the system along the curve
d-e
• When the pressure over the system brought down to a value less than the
saturation pressure at constant temperature or when the temperature is increased
above the saturation temperature at constant pressure, the vapour gets
superheated.
PVT behavior of pure substances
• PV isotherm has two discontinuities in its slope at points b and d.
• The isotherm at a higher temperaturewill be similar to that at
temperature but the length of the horizontal section joining saturated
liquid and vapour phases will be smaller.
• The locus of the saturated phases is represented by the dome-shaped
curve b-c-d.
• The area under this dome represents the two phase region, the area to
the left of curve a-c is the liquid region and the area to the right
curve c-d is the vapour region.
• When the entire experiment is conducted at an increased temperature
(critical temperature), the discontinuities in the isotherm disappear
indicating that, at the critical temperature, the saturated liquid and
saturated vapour phases becomes indistinguishable.
• The liquid state changes to vapour state without any discontinuity at
the critical point represented by point c in figure.
• The properties at the critical point are known as critical properties.
• The critical properties of water:
• and represents the highest temperature and pressure respectively at
which a pure material can exist in vapour-liquid equilibrium.
• If T< , the substance to the right of the saturated vapour line is called
a vapour and, if, T> the substance is called a gas.
• A vapour can be condensed to a liquid by compression at constant
temperature or by cooling at constant pressure whereas a gas can be
condensed by a reduction of temperature at constant pressure only.
 PVT behavior of pure substances
PT diagram:
• The phase behavior of pure fluids can be represented on PT
diagram as in Fig.
• Consider unit mass of ice at pressure and temperature
corresponding to point p.
• When it is heated at constant pressure, the temperature
increases and at point q ice starts to melt. The temperature
corresponding to point q is the fusion temperature. The
fusion line represents the state of the system at which the
solid is in equilibrium with the liquid.
• If transfer of heat is continued, the temperature remains
constant till the entire solid is liquefied. The fusion
temperature is a function of the pressure only.
• If heating is continued, the substance enters the liquid
region, and when point r is reached where liquid begins to
vaporise. When all liquid has been vaporised, temperature
increases along the line r-s in the vapour region.
• Heating above , there will be a gas region.
• The fusion curve and the vaporisation curve meet at the
triple point where the three phases coexist in equilibrium.
• For water at triple point, T=273.16 K and P= bar.
• If the pressure of the system is below the triple point
pressure, the heating of the solid results in sublimation.
Equation of state & Concept of ideal gas
What is equation of state? Assumption for an ideal gas:
• The thermodynamic state of a On a molecular level, an ideal
single homogeneous fluid may gas may be treated as the one
be specified by properties such for which,
as pressure, temperature, and 1. The size of the molecules
volume. is very small compared to
• An equation of state is a the distance between them
functional relationship so that the volume of the
between these three variables molecules is negligible in
and it may be written as, comparison with the total
f (P,V,T) = 0 volume of the gas.
• The most simple equation of 2. The intermolecular forces
state is the one applicable for are negligibly small.
ideal gases.
Characteristics of an ideal gas
1. For one mole of an ideal gas the equation of state is given by
PV = RT
2. The internal energy of an ideal gas depends only on temperature . It is
independent of pressure and volume.

3. The joule-Thomsan coefficient is zero for an ideal gas,

• The Joule-Thomson coefficient is defined as the change in temperature

resulting from the expansion of a gas between two constant pressures under
adiabatic condition and with no exchange of work with the surroundings.
• Gases, like hydrogen, helium, nitrogen, and oxygen at room temperatures,
follow the perfect gas law very closely and they can be treated as ideal gases.
• However, the only state at which the real gases follow ideal behavior is at
zero pressure.
• For engineering purposes, all gases in the neighborhood of atmospheric
pressure are treated as ideal.
 Process involving ideal gases
Constant volume process: Constant pressure process:
• From the general statement of first law of thermodynamics, • From the general statement of first law of
------------------------(1) thermodynamics,
• For the constant volume process, work done ------------------------(1)
• Heat capacity at constant volume, • For the constant pressure process, work done is due to
expansion of gas,
------------------------------(2) • Heat capacity at constant pressure,
• From equation (1) and (2) and taking dW=0,
------------------------------(2)
• From equation (1) and (2) and taking dW=P dV,
------------------------(3)
• Consider the change of state of ideal gas from state 1 to ----------------------(3)
state 2: • Enthalpy is defined as
• At constant pressure (dP=0), change in enthalpy

---------------------------(4)
• Putting value of dU in equation (4)
• For such process change in internal energy is given as from ---------------(5)
equation (3) -----------------------------------(6)
• Consider the change of state of ideal gas from state 1 to
state 2:

• For such process change in enthalpy is given as from

equation (6)
Show that for an ideal gas.
• Enthalpy is defined as,

-------------------(1)
• For ideal gas, PV=RT,
----------------------(2)
• For constant volume process,
-------------------------(3)
• For constant pressure process,
-------------------------(4)
• Putting value of dU and dH in equation (2)
-------------(5)
• On rearrangement,
--------------(6)
--------------(7)
 Process involving ideal gases
Constant Temperature Process
• Internal energy of an ideal gas will change only if the temperature changes.
• In an isothermal process involving an ideal gas, the change in internal energy and the change in enthalpy
would be zero (dU=0).
• From the general statement of first law of thermodynamics,
------------------------(1)
--------------------------------(2)
• The above equation can be integrated to determine the heat and work effects in an isothermal process
involving ideal gases.
-----------------------(3)
• Putting P=RT/V, in the equation (3)
-----------------------(4)
-----------------------(5)
• Where

• For an ideal gas,

----------------------------------(6)
• For constant temperature, . Therefore equation (6) becomes,
=
----------------------------------(7)
• Substituting equation (7) into equation (5),
-----------------------(8)
 Adiabatic process
• Prove that for an adiabatic process, • Let, at initial state, Pressure , temp and vol
• Adiabatic process: there is no heat interaction • At final state , Pressure , temp and vol
between system and surroundings. • On integration of equation () between these limits,
dQ= 0 ----(9)
• First law of thermodynamics: ----(10)
----(11)
----(1) ----(12)
• We know that • For an ideal gas,
• Therefore equation (1) becomes, ----(13)
----(2) ----(14)
• Considering and taking p= RT/V, equation (2) • From equation (12) and (14),
becomes ----(15)
----(3) ----(16)
----(4) ----(17)
----(5) ----(18)
• We know that , ----(19)
• Dividing this equation by ----(20)
----(6)
----(7)
• From the equation (5) and (7),
----(8)
 Adiabatic process
• The work done in an adiabatic process is given by
----------(1)
• Integrating equation (1),
----------(2)
• We know the relation,
----------(3)
----------(4)
• Putting the value of in equation (2),
----------(5)
----------(6)
• Equation (5) gives the work done in an adiabatic process involving ideal gas. This can be put into a more
useful form as follows:
----------(7)
• For adiabatic process,
----------(8)
• From equation (7) and (8),
----------(9)
----------(10)
 Polytropic process
• In a polytropic process, the relationship
between pressure and volume is assumed to be
.
• If n=0, the process is isobaric (constant
pressure process).
• If n=1, process is isothermal (constant
temperature process).
• If n= process is isochoric (constant volume
process).
• If n=, process is adiabtic process.
 Equation of state for real gases
• Perfect gas law is insufficient to explain the behaviour of real gases.
• For real gases to behave ideally, the molecular interactions should be negligible.
• At low molar volumes or high pressures, molecules come very close to each other and molecular
interactions cannot be neglected.
• The perfect gas law may be viewed as an approximation to describe the behaviour of real gases at
ordinary pressures or as the limiting behaviour of real gases at low pressures.
• Many equations of state have been proposed to explain the actual behaviour of gases.
• Limiting conditions: An equation of state, in general, should satisfy certain limiting
conditions. They are:
1. All equations reduce to the ideal gas equation at low pressures. That is PV=RT as .
2. The slope of the PV isotherm against P may be equal to, greater than, or less than zero as
pressure tends to zero.

Or

3. The P-V curve at constant temperature should exhibit a point of inflection at the critical point.

4. The P-T curves are linear except at very high densities.

 Cubical equation of state
 Van der Waals equation of state:
• Perfect gas equation fails to explain the P-V-T behaviour of real gases as the volume occupied by the molecules of a real gas
and the forces of interaction between them are not negligible as in an ideal gas.
• Therefore for real gas it is necessary to take into account the certain correction in pressure and volume term of ideal gas
equation.
For the correction factor in pressure term: For the correction factor in volume term:
• consider the forces of attraction on a molecule hitting the wall of • The centers of two identical molecules are at a distance
the container. equal to the molecular diameter at the instant of their
• When the molecule hits the wall it experiences a net attractive collision with each other.
force towards the surrounding molecules, thereby, reducing the • The molecular separation at collision cannot be smaller
pressure that would have been exerted by the molecule on the wall than this distance.
in the absence of intermolecular attraction. • Since each molecule is surrounded by a forbidden volume,
• This attractive force is directly related to the number of molecules the effective volume of the gas will be less than the actual
per unit volume and the frequency of molecular collision, the volume.
latter in turn being proportional to the number of molecules per
unit volume. •where V
• In short the net attractive force is proportional to where V is the s
molar volume of the gas. ------(4)
(where Y is the volume correction term)
•where P •As Y proportional to number of moles n,
s -----(5)
----(6)

• As per the above explanation, , • From equation (4) and(7), ------(8)

-(2) • Now as per ideal gas law,

• Putting the value of x in equation (1), • Putting the value of and , from equation (3) and (8) into
--------------------(3) ideal gas equation,

This equation is known as Van der Waals equation of state for real gas. Where a and b are Van der Waal’s constants.
 Derive Van der waal’s constants in terms of critical properties.
From the Van der Waal equation of state,
Putting value of in equation (4)

Writing equation (1) in terms of critical properties

Putting the value of and in equation (2),

Taking limiting condition,

Differentiating equation (2) with respect to volume,

Dividing equation (9) by (10),

Differentiating equation (3) with respect to volume

Now,

From equation (4) and (5),

 Redlich–Kwong equation
• The Redlich–Kwong equation (1949) is a two-parameter
equation of state widely used in engineering calculations.

• The constants a and b are calculated by using limiting

conditions same as in case of van der Waal’s constant.
 Redlich–Kwong–Soave Equation
and Acentric factor
• Soave (1972) proposed a modification to the Redlich–Kwong equation. The Soave modification is given below:

• Where

• is known depends upon the temperature and acentric factor.

• The acentric factor “” is a concept that was introduced by Pitzer in 1955, and has proven to be very useful in the
characterization of substances.
• It has become a standard for the proper characterization of any single pure component, along with other common
properties, such as molecular weight, critical temperature, critical pressure, and critical volume.
• For simple fluids , it has been observed that at temperature equal to 7/10 of critical temperature, the reduced vapour
pressure closely follows the following empirical result.

• Where is the vapour pressure

• The acentric factor is said to a measure of the non sphericity (centricity) of molecules.
• It is defined as:

• For simple fluids, =0.

• For more complex fluid >0.
 Virial equation of state
• It has been observed experimentally that the product PV for a gas or vapour along an isotherm is
almost constant and it equals RT, as pressure tends to zero or volume tends to infinity.
• This suggests the possibility of expressing PV/RT as a power series in P or 1/V. The ratio PV/RT,
which is the ratio of the volume of a real gas (V) to the volume if the gas behaved ideally at the
stated temperature and pressure (RT/P) is called the compressibility factor and is denoted by Z.
• Virial equations express the compressibility factor of a gas or vapour as a power series expansion in
P or 1/V.
------------ (1)
------------ (2)
• Equation (1) and (2) are known as virial equations.
• B, C, D and B’, C’, D’ are known as virial coefficients.
• B and B’ are called second virial coefficients.
• C and C’ are called third virial coefficients, and so on.
• Finds its application at low to moderate presuure.
• The virial coefficients account for the molecular interactions.
• The second virial coefficients take into account deviations from ideal behaviour which results from
interactions between two molecules.
• The third virial coefficients take into account the deviations from ideal behaviour that results from
the interactions of three molecules, and so on.
• The two sets of virial coefficients are related as:
 Compressibility Charts
• the compressibility factor measures the deviation of a real gas from ideal behaviour.
• It is defined as Z = PV/RT.
• It is the ratio of the volume of a real gas at a set of specified temperature and pressure to the
volume occupied by the gas at the same temperature and pressure if it were an ideal gas.
• The compressibility factor of a perfect gas has a value of unity at all conditions.
• Since a real gas behaves ideally as pressure is reduced, the compressibility factor of a real gas
approaches unity as the pressure is reduced to zero.

• Figure schematically shows a plot of compressibility factor of nitrogen at 273 K and carbon
dioxide at 323 K plotted against pressure.
• The compressibility factor may be less than or more than unity depending on the temperature
and pressure of the gas.
 Principle of Corresponding States
• This principle states that all gases when compared at the same reduced temperature and the reduced
pressure, have approximately the same compressibility factor and all deviate from the ideal behaviour
to the same extent.
• The critical properties are used as basis for setting up a scale for comparing the properties of
substances.
• The reduced variables are obtained by dividing the actual variables by the corresponding critical
constants.

• Applying the principle of corresponding state to the methane (at temperature of 382 K, pressure of 69
bar) and nitrogen (at temperature of 252 K, pressure of 51 bar).

Component T (K) (K) P (bar) (bar)

Methane 382 191 69 46 2 1.5

Nitrogen 252 126 51 34 2 1.5
• The compressibility factor of any single component substance is thus a function of only two properties,
usually the reduced temperature and reduced pressure. The principle of corresponding states can be
stated mathematically as

• It is to be noted that this principle is only an approximation and works the best for gases composed of
spherical molecules; for non-spherical or polar molecules it fails.
References:
• “Introduction to Chemical Engineering Thermodynamics”; J.
M. Smith, H. C. Vanness, M. M. Abbott, The McGraw-Hill
Companies, Inc.
• “A text book of Chemical Engineering Thermodynamics”; K.
V. Narayanan, Prentice-Hall of India Pvt. Ltd.