CHE1003: PROCESS ENGINEERING

THERMODYNAMICS

Faculty name: Dr. Dharmendra Kumar Bal

Office room: SJT-313-A23A
Email id : [email protected]
Mobile : 9406957419
References

1. KV Narayanan, A Textbook of Chemical Engineering Thermodynamics,

Prentice Hall India, New Delhi, 2006.

2. P. Ahuja, Chemical Engineering Thermodynamics, PHI Learning Pvt. Ltd.,

2009

3. JM Smith, HC Van Ness and MM. Abbott, Introduction to Chemical

Engineering Thermodynamics, 6th Edn., McGraw-Hill, New York, 2008

4. Y V C Rao, Chemical Engineering Thermodynamics, University Press, New

Delhi, 2005

5. J M Honig, “Thermodynamics: Principles Characterizing Physical and

Chemical Processes”, Elsevier Science & Technology Books March 2007
 VIT ,Vellore

THERMODYNAMICS
Deals with the study of interrelation of various physical properties ( such as
temperature, pressure, volume and entropy) and their relation to process
properties ( such as heat and work)
 is used to describe processes that involve changes in temperature, transformation
of energy, and the relationships between heat and work.
 to deal with problems that require calculation of heat and work requirements for
physical and chemical processes.
CHEMICAL ENGINEERING THERMODYNAMICS:
Deals with estimating the physical properties ( i.e energy, entropy) for a given set off
conditions (usually temperature, pressure, composition) and their use in process
calculations (material & energy balances)
 To determine equilibrium conditions for the transfer of chemical species between
phases. Enthalpy data for design of distillation columns, absorption columns,
evaporators, condensers and other units where heat exchange is involved.
 For unit processes, where chemical reactions are involved, thermodynamics
provide information regarding heat effects, maximum conversion, and other
parameters.
Classification of Thermodynamics

Classical Thermodynamics
is an experimental science which deals with
macroscopic or large scale properties of matter

Kinetic theory
deals with molecular model in which individual
molecules follow the laws of mechanics.

Statistical Thermodynamics
applies statistical considerations to find the distribution of the very large number of
molecules that make up a macroscopic piece of matter

Irreversible thermodynamics is another branch of thermodynamics dealing with

non-equilibrium, irreversible processes.
 Fundamental concepts and notation

System: A thermodynamic system is defined as the quantity of matter or a region in

space upon which attention is concentrated in the analysis of a problem. Here quantity
of matter may be gas, solid or liquid, magnetic field, electric field or even photons.
Minimum quantity of matter required to analyze a thermodynamic system is the order
of Avogadro’s number.
closed system: fixed mass (solid or fluid),
open system: A volume with partly solid boundaries and imaginary
boundary sections through which fluid passes. Eg. Multiphase system
Surroundings:
Boundary:
• Adiabatic (insulated) does not allow heat to pass
• Rigid cannot expand or contract (no work done)
• Isolated exchanges neither heat nor work with the surroundings (rigid and
adiabatic)
 SYSTEMS AND Surroundings
CONTROL VOLUMES
Light Bulb System

System
Boundary
Universe

Isolated system
 Systems:
Transferred Across
System Boundary
Type of System Mass Energy Example
Open System/ Yes Yes Jet Engine
Control Volume (CV)

Closed System/ No Yes Light Bulb

Control Mass (CM)

Isolated System No No Ice Chest/ Cooler for small

Dt
 Properties:
• Thermodynamic Properties: These are characteristic features of a system, by
which it can be specified. Describe mass and energy of system (using state
variables like T, P and V).
• Extensive Properties: Vary with system size or depends on mass (e.g., V).
• Intensive Properties: Independent of system size or mass (e.g., T and P).
• Specific Properties: Divide extensive property by mass is Intensive Property E.g.,
Specific Volume, v = V/m = 1/r [m3/kg]

Property Extensive Intensive

Mass m -
Temperature - T
Pressure - P
Volume V v = V/m (specific volume)
Internal Energy U u = U/m (specific internal
energy)
Enthalpy H h = H/m (specific enthalpy)
 Test yourself
Density is an intensive property, How the ratio of two extensive properties is an
intensive property
Viscosity an intensive property

acceleration (I) Mass (E)

chemical potential (I) melting point and boiling point (I)
Compressibility (I) Momentum (E)
concentration (I) number of moles (E)
Diffusivity (I) particle number (E)
electrical charge (E) pressure (I)
Energy (E) specific heat capacity (I)
Enthaply. (E) specific volume (I)
Entropy (E) temperature (I)
Fugacity (I) Thermal conductivity (I)
Gas constant (I) velocity (I)
Gibbs energy (E) Volume (E)
Heat capacity (E) Weight (E)
Height (E) Work / heat (E)
number of moles (E).
 Phase:
It is a quantity of mass that is homogeneous throughout in chemical
composition and physical structure.
e.g. solid, liquid, vapour, gas.

Phase consisting of more than one phase is known as heterogenous

system .
Homogeneous system:
The properties are same throughout the system, no discontinuity in the
properties.

Heterogeneous system:
System consists of two or more distinct homogeneous regions or phases The
properties are same throughout the system, no discontinuity in the properties.

Water – water vapour; two immiscible liquids

 State
• Thermodynamic State:
– It is the condition of a system as defined by the values of all its
properties.
– It gives a complete description of the system.
– Any operation in which one or more properties of a system change is
called a change of state.
– Using state variables, and with limited set of data it is able to
determine all thermodynamic properties of the system.
– Condition of the system is defined by state variables.
Equilibrium state:
in a closed system deals with Control mass

The properties are same throughout the system and do not

change with time, and have fixed values as long as external
conditions are unchanged.
Thermodynamics deals with equilibrium state
Equilibrium state: at this condition all the properties of the system will have
fixed values and are uniform throughout the system and equilibrium with
the surroundings. If the value of one property changes, the equilibrium state
will change to a different one.

Thermal Equilibrium exists when temperature is same

throughout the system and there is no change in temp at any point of
the system with time.
Mechanical Equilibrium: Pressure is same throughout the
entire system and there is no change in pressure at any point of the
system with time.

Phase Equilibrium exists when different phases are present

and the mass and composition of each phase should not change with
time.

Chemical Equilibrium exists when chemical composition does

not change with time, ie chemical reactions have occurred and
equilibrium compositions of the reactants and products is achieved.
 Gibb’s Phase Rule

f= c-p+2
Where, f= number of independent intensive properties of the system
c= no of components
p= no of phases
Consider a single liquid or gas, where c=1, p=1, then f=2

That means only 2 independent intensive properties are required to describe the
state of the system.
Now if c=1 ,and p=2, then f= 1. that means only one intensive property is sufficient
to describe the state of the system. E.g. ----------------
For c=1, p=3, f=?
 Zeroth Law of thermodynamics
Thermometers with liquid working fluids are usually used for measurement of
temperature. When such a device is brought in contact with a body whose temperature
is to be measured, the liquid column inside the thermometer expands due to heat
conducted from the body. The expanded length can be said to represent the degree of
hotness in a somewhat quantitative manner.

1. The Zeroth Law of Thermodynamics states that if two bodies are in thermal
equilibrium with a third body, then the two given bodies will be in thermal equilibrium
with each other.
2. The zeroth law of thermodynamics is used for measurement of temperature. In the
Celsius temperature scale, two fixed points – ice point and steam point – are used to
devise the scale.
3. The freezing point of water (at standard atmospheric pressure) is assigned a value of
zero, while the boiling point of pure water (at standard atmospheric pressure) denoted
as 100.
4. However for introducing detail, the distance between the two end points of the liquid
column marks is arbitrarily divided into 100 equal spaces called degrees. This exercise
can be extended both below zero and above 100 to expand the range of the
thermometer.
the temperature scale of the SI system is described by the
Kelvin unit (T0K). Its relation to the Celsius (t0C) scale is
given by:

Thus the lower limit of temperature, called absolute zero

on the Kelvin scale, occurs at –273.150C.
Ideal gas:
1. A thermodynamic system typically encloses a fluid (pure gas, liquid
or solid or a mixture) within its boundary.
2. The simplest of the intensive variables that can be used to define its
state are temperature, pressure and molar volume (or density), and
composition (in case of mixtures).
3. Let us consider for example a pure gas in a vessel. By phase rule the
system has two degrees of freedom.

It is an experimentally observed phenomenon that in an equilibrium

state the intensive variables such as pressure, temperature and
volume obey a definitive inter-relationship, which in its simplest form
is expressed mathematically by the Boyle’s and Charles’s laws. These
laws are compositely expressed in the form of the following equation
that is said to represent a behavior termed as Ideal Gas Law:
Where, P = system pressure (say, Pa = N/m2),
T = system temperature (in K), V = gas molar volume (mol/m3) and, R =
universal gas constant.

The above relation is said to represent an equation of state, and may

alternately be written as:

Where, Vt = total system volume; n = total moles of gas in the system.

 State Variable: If the gas is heated or cooled, compressed or
expanded, and then returned to its initial temperature and pressure, its
intensive properties are restored to their initial values. It is evident that such
properties do not depend on the past history of the fluid or on the path by
which it reaches a given state. They depend only on present state,
irrespective of how they are attained. Such quantities are thus defined
as state variables. It is also called point function.

Mathematically, this idea may be expressed as follows:

 Path function or path dependent variables:
Let us next consider the case of thermodynamic work.
It may be readily evident that if one can depict the exact variation of pressure and
volume during a change of state of a system on a two-dimensional P-V graph, the area
under the curve between the initial and final volumes equal the work associated with
process.

The more appropriate relation

for such variables may be
written as:

Depiction of thermodynamic work on P-V plot

 Different Forms of Stored Energy
Basically there are two models in which energy (E) may be stored in a system

(i) Macroscopic energy mode : The macroscopic energy mode includes the macroscopic
kinetic energy and potential energy of a system.

(ii) Microscopic energy mode

consider a fluid element of mass m having the
center of mass velocity
The macroscopic kinetic energy EK
by virtue of its motion is

the macroscopic potential energy Ep

by virtue of its position
Ep = mgz
Macroscopic and Microscopic
energy in a system
Microscopic energy in a system

The microscopic energy mode refers to the energy stored in the molecules and atomic
structure of the system, which is called the molecular internal energy or simply internal
energy U.

Matter is composed of molecules. Molecules are in random thermal motion with an

average velocity v, constantly colliding with one another and with the walls.

Due to a collision, the molecules may subjected to rotation as well as vibration.

They can have translational kinetic energy, rotational kinetic energy, vibrational energy,
electronic energy, chemical energy and nuclear energy
 Energy Within a System Boundary
Kinetic and Potential 1 mv2 PE 
mgz
KE  gc
2 gc
INTERNAL ENERGY

Translational Rotation Vibrational Chemical,

Nuclear &
Electrical

 KE and PE: Macroscopic Properties

 Internal Energy (U): Microscopic Property
 INTERNAL ENERGY, U
• The energy stored in the system by virtue of the
configuration and motion of the molecules constituting
the system
• The internal energy of a system can be changed by
heating the system or by doing work on it
• First law of thermodynamics states that the increase in
internal energy is equal to the total heat added and
work done by the surroundings
• The internal energy is an intrinsic property, a state
function of a system, because its value depends only
on the current state of the system and not on the path
taken or process undergone to arrive at this state
• It is an extensive quantity. Unit : Joule (j)
 Enthalpy, H
• A thermodynamic quantity equivalent to the total
heat content of a system. It is equal to the internal
energy of the system plus the product of pressure
and volume.
where
H is the enthalpy of the system
U is the internal energy of the system
p is the pressure of the system
V is the volume of the system.
The U term can be interpreted as the energy required to create the system, and the pV
term as the energy that would be required to "make room" for the system if the
pressure of the environment remained constant

For systems at constant pressure, the change in enthalpy is the heat received by the
system.
The enthalpy is an extensive property. Unit : Joule (j)
The total enthalpy of a system cannot be measured directly; the enthalpy change of
a system is measured instead.

Enthalpy change is defined by the following equation:

H = Hf - Hi

An enthalpy change describes the change in enthalpy observed in the constituents of

a thermodynamic system when undergoing a transformation or chemical reaction

Heat of reaction
For an exothermic reaction at constant pressure, the system's change in enthalpy
equals the energy released in the reaction, including the energy retained in the system
and lost through expansion against its surroundings.

For an endothermic reaction, the system's change in enthalpy is equal to the

energy absorbed in the reaction, including the energy lost by the system and
gained from compression from its surroundings.
ΔH is positive, the reaction is endothermic, that is heat is absorbed by the system
due to the products of the reaction having a greater enthalpy than the reactants.
 Enthalpy cannot be measured directly, It needs datum (reference point)
Chemical properties:
Enthalpy of formation, the enthalpy change observed in a constituent of a
thermodynamic system when one mole of a compound is formed from its
elementary antecedents.
Enthalpy of combustion, the enthalpy change observed in a constituent of a
thermodynamic system when one mole of a substance combusts completely
with oxygen.
Enthalpy of hydrogenation, the enthalpy change observed in a constituent of
a thermodynamic system when one mole of an unsaturated compound
reacts completely with an excess of hydrogen to form a saturated
compound.
Enthalpy of neutralization, the enthalpy change observed in a constituent of
a thermodynamic system when one mole of water is produced when an acid
and a base react.
Standard Enthalpy of solution, the enthalpy change observed in a
constituent of a thermodynamic system when one mole of an solute is
dissolved completely in an excess of solvent.
Enthalpy of hydration, the enthalpy change observed when one mole of
gaseous ions are completely dissolved in water forming one mole of
aqueous ions.
Physical properties:

Enthalpy of fusion, defined as the enthalpy change required to completely

change the state of one mole of substance between solid and liquid states.
Enthalpy of vaporization, defined as the enthalpy change required to
completely change the state of one mole of substance between liquid and
gaseous states.
Enthalpy of sublimation, defined as the enthalpy change required to
completely change the state of one mole of substance between solid and
gaseous states.
 Total Volume Depends on the system

Both , molar or specific

Molar Volume  Total Volum e
Num ber of Moles volume is a property
of the fluid, Intensive property
Specific Volume  Total Volum e
Mass of the System

PV t  nRT ; V t  Total Volume

PV  RT ; V  Molar Volume

Cylinder (1) : Volume V1 (m3) T, P is Fixed. Calculate the moles, (i.e ) = n1 moles
Cylinder (2) : Volume V2 ( =2V1) Same T, P. Now calculate the moles = 2 n1 moles

V2 2V1 V1

Molar volume of gas in both cylinder is same V   
n2 2n1 n1
Thermodynamic Processes
 Process : Any change that a system undergoes from one equilibrium state to
another is called a process.
The series of states through which a system passes during a process is called
the path of the process.
Properties like heat and work interactions are functions of path. Changes
in enthalpy and internal energy are functions of only state and not of the
path taken between the two states.
• Common Processes:
– Isothermal: Constant Temperature
– Isobaric: Constant Pressure
– Isometric: Constant Volume
– Adiabatic: No Heat Transfer
P = constant T = constant
(isobaric) (isothermal)

P T
v =constant v =constant
(isometric) (isometric)

v v
Sl Parameter Held Equation of state
Name of the process
No Constant for simple system

1 Constant pressure(Isobaric) p = constant v = (mR/P)T

Constant volume(isochoric)
2 V = constant p = (mR/V)T
process
Constant temperature
3 T = constant pV = constant
(isothermal) process
4 Polytropic process n pVn = constant
no heat flow
5 Adiabatic process across the system pvγ = constant
boundary
6 Isoenthalpic process h = constant h=c
Reversible Process:
When reversed the process the system
and surroundings will come back to
the same initial state.
Equilibrium at
all points along the path
Internally Reversible Process:
When reversed the process only the system
will come back to the same initial state

Irreversible Process:
Is the one in which only initial and final
states are known. Path is not known as
equilibrium is not maintained during the
process.
 Quasi-static Processes
A quasi-static process is one in which
 The deviation from thermodynamic equilibrium is infinitesimal.
 All states of the system passes through are equilibrium states.

 If we remove the weights slowly one by one the pressure of the gas will
displace the piston gradually. It is quasistatic.
 On the other hand if we remove all the weights at once the piston will be
kicked up by the gas pressure.(This is unrestrained expansion) but we don’t
consider that the work is done -because it is not in a sustained manner
 In both cases the systems have undergone a change of state.
 Another eg: if a person climbs down a ladder from roof to ground, it is a
quasistatic process. On the other hand if he jumps then it is not a
quasistatic process.

A reversible state is a quasi-static process without any dissipation.

Work: It is performed whenever a force acts through a distance.
By definition, the quantity of work is given by the equation: dW = Fdl
Where F is the component of force acting along the line of displacement dl.
When integrated, this equation yields the work of a finite process.
By convention, work is considered as +ve, when the displacement is in the same
direction as the applied force and –ve when they are in opposite direction.

The work , which accompanies a change in volume of fluid is often used in

thermodynamics.
A common example is compression or expansion of a fluid in a cylinder resulting from
a movement of piston.
The force exterted by the piston on the fluid = piston area × pressure of the fluid.
The displacement of the piston = total volume change of the fluid / area of the piston
dW= -PA dV/A
dW= -PdV
 PVT Relation

 Pure component state variable

 Degree of freedom
 P-T and P-V diagrams
 Triple Point and Critical Point
 PVT Relations
Phase Change and P-v-T Surface

Regions on T-v Diagram

directions of Isobars
Liquid water: at 1 atm 99 oC

One mole of water is 18.015 grams

Density (1000 kg/m3) = 1 gm/ml = 1 gm /cc

Volume occupied by on mole of water = 18.015 gm of water

= 18.015 ml
Water Vapour: at 1 atm 100 oC

One mole of water is 18.015 grams

Use Ideal gas relation :

vapor is considered an ideal gas and all ideal gases of one

mole at STP will occupy 22.4 L = 22400 ml
1 mol of water vapor will also occupy 22.4 L

Or 1 ml of water expands to 1.24 L

Regions on P-v Diagram
Note directions of Isotherms

The range of coexistence of liquid

and vapour phases in equilibrium
decreases
 Critical Point
Critical state, is an inflection point,
specifies the conditions (i.e temperature, pressure) at which
liquid state of matter ceases to exist
Liquid is heated in a confined system ( closed system)

•Its density decreases

•Press and den of vapor increases
•Both liquid and vapor den closes to each other
•At critical Temperature both densities are equal
•Liquid gas interphase layer (or) phase boundary disappear
•The heat of vaporization approaches zero
•The point of termination of phase equilibrium curve
At critical point
Phase behavior of pure fluids

DOF
@ triple point is invariant,
we have no choice in the
selection of externally
controllable variables
Temperature Vapor –Pressure
curve of a pure substance

The triple point of water is 0.01oC, 0.6117 kPa

The critical point of water is 373.95oC, 22.064 MPa
Boiling Point of Pure Substance:
1. At a given pressure, a pure substance in the liquid phase boils at fixed
temperature. This temp. is called boiling point.
2. A pure substance under saturated conditions has one degree of freedom.
Therefore, if pressure is fixed, all other variables become fixed.
3. Boiling point temperature is the temperature at which the vapour
pressure of the substance equals to the atmospheric pressure or external
pressure.
4. At a given pressure, boiling takes place at a fixed temperature, whereas
at a given temperature, boiling takes place at fixed pressure.
5. e.g. Boiling point temperature of water at 1 atm is 1000C and boiling
point pressure at 250C is 3.169 kPa. Therefore if we want to boil water at
250C, the pressure of the system has to be reduced to 3.169 kPa. Both
change in temperature and pressure can lead to boiling.
The relation between vapour pressure and
temperature is given by

where p is the vapor pressure, T is Temperature

and A, B and C are component-specific constants.

The simplified form with C set to zero:

is named Antoine equations Tsat =(B/(A-lnP))-C

Antoine Constants for Water

Water Temperature A B C

1 to 100 degrees 8.07131 1730.63 233.426

Celsius
99 to 374 degrees 8.14019 1810.94 244.485
Celsius
 PVT Relations
Ideal gas
An ideal gas is a gas having no
forces of intermolecular attraction.
The gases which follow the gas laws
at all range of pressures and
temperatures are considered as
‘ideal gases’. An ideal gas obeys the Internal energy- only function of Temp
and independent of P,V
perfect gas equation Pv = RT and
has constant specific heat
capacities.
Joules Thomson coefficient is zero
for ideal gas
Equation of state: It relates the variables that
represent the thermodynamic state of a system
in the simplest possible manner.
 PVT Relation
f ( P,V , T )  0 V  V (T , P)

Total Derivative

 V   V 
dV    dT    dP
.  T  P  P T
, Volume expansion,
1  V 
  
V  T  P
Isothermal compressibility,
1  V 
   
V  P  T
dV
The generic firm of EOS for pure substance is  dT  kdP
V
 Virial Equation of state
Generally applicable to moderate deviations from ideal gas behavior, the virial EOS is
given by two alternate forms:

PV B C
 1   2  .....
RT V V
Where B, C = second and third virial coefficients

Or:
It may be shown that the following relations hold further:

Cubic Equation of state RT a

P  2
V b V
 Ideal Gas Law

The equality for the four variables involved in Boyle’s Law, Charles’ Law,
and Avogadro’s law can be written

PV = nRT
R is known as the universal gas constant
Using STP conditions
R = PV = (1.00 atm)(22.4 L)
nT (1mol) (273K)
= 0.0821 L-atm
mol-K

Very simple and accurate relation

No similar relation exists for liquids, saturated liquid vapor mixtures or
superheated vapors
Typically superheated vapors do not obey the ideal gas law
 A real gas is a gas having forces of inter molecular attraction. At very
low pressure relative to the critical pressure or at very high
temperatures relative to the critical temperature, real gases behave
nearly the same way as a perfect gas. But since at high pressure or at
low temperatures the deviation of real gases from the perfect gas
relation is appreciable. These conditions must be observed carefully,
otherwise errors are likely to result from inappropriate application of
the perfect gas laws.

Due to these facts, numerous equations of state for real gas have been
developed, the derivation of which is either analytical, based on the
kinetic theory of gases, or empirical, derived from an experimental data.
 Van der Waals’ Equation of State
In deriving the equation of state for perfect gases it is assumed that the volume
occupied by the molecules of the gas in comparison to the volume occupied by the
gas and the force of attraction between the adjacent molecules is very small and
hence the molecules of gas are neglected.

At low pressures, where the mean free path is large compared to the size
of the molecules, these assumptions are quite reasonable. But at high
pressure, where the molecules come close to each other, these are far
from correct.
Van der waals’ equation introduces terms to take into account of these two
modifying factors into the equation of state for a perfect gas.
The Van der Waals’ equation of state is given by,
 a
 P  v 2  v  b   RT
 
RT a
or P  2
vb v
where a and b are constants for any one gas, which can be determined
experimentally, the constants account for the intermolecular attractions and
finite size of the molecules which were assumed to be non-existent in an
ideal gas.
 If the volume of one mole is considered, then the
above equation can be written as,
 a
 P  v  b   R T
v 
2

Units P (N/m2), 
v m / kg  mole
3

R 8314 Nm / kg  mol 0 K Or R  0.083143 bar m 3 / kg  mol 0 K

a ( Nm / kg  mol 
4 2

b m / kg  mol
3
Determination of Van der Waals’ constants
in terms of critical properties

The determination of two constants a and b in the

Van der Waals’ equation is based on the fact that the
critical isotherm on a p-v diagram has a horizontal
inflexion point at the critical point. Therefore the first
and second derivative of P with respect v at the
critical point must be zero.
  p   2 p 
i.e.,    0 and 2  0
 v T Tc  v T Tc

RT a
From equation (1) we have, P  2
v b v
 p   RT 2a
    3
 v T v  b 
2
v
  p
2
2 RT 6a
and  2    4
 v  T v  b 
3
v
At critical points the above equation reduces to

 RT 2a
 3 0 --- (2a)
v  b  v
2

2 RT 6a
and  4 0 --- (2b)
v  b  v
3
Also from equation (1) we have,

RTc a
Pc   2 --- (2c)
vb v
Dividing equation (2a) by equation (2b) and
simplifying we get
vc
b
3
Substituting for b and solving for ‘a’
from equation (2b) we get, a = 9RTcvc

Substituting these expressions for a and b in

equation (2c) and solving for vc, we get
 27  R T
2 2
3RTc RTc and a    c
vc  b 
8 pc 8 pc  64  p c
Note: Usually constants a and b for different gases are
given.
Table: Van Der Waals’ Constant
Gas a b Z = pv/RT
kN m4/(kg-mol)2 m3/kg-mol
Air 135.8 0.0365 0.284
Oxygen 138.0 0.0318 0.29
Nitrogen 136.7 0.0386 0.291
Water 551.7 0.0304 0.23
Methane 228.6 0.0427 0.29
Carbon monoxide 147.9 0.0393 0.293
Carbon Dioxide 365.6 0.0428 0.276
Ammonia 424.9 0.0373 0.242
Hydrogen 24.8 0.0266 0.304
Helium 3.42 0.0235 0.30
Compressibility Factor and
Compressibility Chart:
The specific volume of a gas becomes very large
when the pressure is low or temperature is high. Thus
it is not possible to conveniently represent the
behaviour of real gases at low pressure and high
temperature.
For a perfect gas, the equation of state is Pv = RT. But,
for a real gas, a correction factor has to be introduced
in the perfect gas to take into account the deviation of
the real gas from the perfect gas equation. This factor
is known as the compressibility factor, Z and is defined
as, Pv
Z
RT
Z = 1 for a perfect gas. For real gases the value of Z
is finite and it may be less or more than unity
depending on the temperature and pressure of the
gas.
 Reduced Properties:
The real gases follow closely the ideal gas equation
only at low pressures and high temperatures. The
pressures and temperatures depend on the critical
pressure and critical temperature of the real gases. For
example – 1000C is a low temperature for most of the
gases, but not for air or nitrogen. Air or nitrogen can be
treated as ideal gas at this temperature and
atmospheric pressure with an error which is <1%. This
is because nitrogen is well over its critical temperature
of -1470C and away from the saturation region.
Table: Critical Point Data of Gases
Gas Chemical Pressure Temperature Specific Volume
Formula Pc bar Tc K
v m / kg  mole
c
3

Air --- 37.7 132.8 0.083

Ammonia NH3 112.8 405.8 0.073
Argon A 44.7 151.0 0.075
Carbon dioxide CO2 73.8 304.2 0.094
Carbon monoxide CO 35.0 133.0 0.093
Freon-12 CCl2F2 40.3 385.0 0.215
Helium He 2.3 5.2 0.058
Hydrogen H2 13.0 33.2 0.065
Nitrogen N2 33.9 126.1 0.090
Oxygen O2 50.6 154.5 0.075
Sulphurdioxide SO2 78.8 430.5 0.0123
Steam H2O 220.9 647.3 0.056
Determination of volume using Van der Waals Equation:

 a 
2 
 P  V  b   RT
 V 
Given p, a, b and T, how to find V?
This equation may be simplified to

PV 3  ( Pb  RT )V 2  aV  ab  0

This is third degree polynomial in V.

The root or the value of V is found by numerical method called
Newton Raphson method.

The equation, f ( x)  0
has successive approximation to the root given by
f ( xn )
xn 1  xn 
f ( xn )
PV 3  ( Pb  RT )V 2  aV  ab  0

f (V )  PV 3  ( Pb  RT )V 2  aV  ab  0

f (Vn )
Vn 1  Vn 
f (Vn )

f (V )  3PV 2  2( Pb  RT )V  a  0

f (V0 )
V1  V0  V0 
RT
f (V0 ) p
 Problems
1. A rigid vessel of volume 0.3 m3 contains 10 kg of
air at 3000K. Using (a) the perfect gas equation,
(b) the Vander Walls’ equation of state determine
the pressure which would be exerted by the air on
the vessel.

Solution: (a) The perfect gas equation is Pv = RT

RT R T
or P 
v Mv
Specific volume of the gas = Units
Values of R
(V P T −1 n−1)
0.3 8.314 472 J K−1 mol−1
v  0.03m3 / kg
10 1.985 8775 s K−1 mol−1
8.3143 x10 3 x300 8.314 472 m3 Pa K−1 mol−1
P   28.67 bar8.314 472 × 10−5 m3 bar K−1 mol−1
290.0310 5

8.205 746 × 10−5 m3 atm K−1 mol−1

8.314 472 × 10−2 L  bar K−1 mol−1
0.082 057 46(14) L atm K−1 mol−1
(b) Vander Waals’ equation

 a 
 P  2 v  b   R T
 v 
 27  R T
2 2

We have a  c

 64  Pc
From the critical point data of gases, we have Tc
= 132.8 K, Pc = 37.7 bar
a = 1.364 bar (m3/kg-mole)2
 R Tc 0.083143 x132 .8
b 
8Pc 8 x37.7
= 0.0366m3/kg-mole
Substituting the constants a and b in the Van der
Waals’ equation of state, we get
Noting v = 0.03 m3/kg,

v  0.03 x 29  0.87 m / kg  mole

3

0.083143 x300 1.364

P    28.13 bar
0.87  0.0366 0.87 2
 Problem 4

Find the pressure exerted by methane in a container

of capacity 2m3, when it contains 3 kg at 3000K.
Using (a) Ideal gas equation (b) Vander Waals’
equation.
Solution: Molecular weight of methane is McH4 = 16
v v 2(16)
 Molar Volume, v     10.67 m / kg  mol
3

n m 3
M
Characteristic gas constant,
R 8.3143
R   0.5196 kJ / kg 0 K
M 16
(a) Using ideal gas equation

We have, Pv = mRT

30.5196 10 300 

3
P   2.34 bar
2 x10 5
RT a
(b) We have P  2
v b v
From table, a = 228.6 & b = 0.0427

Substituting in the above equation

8.3143300  228 .6
P 
10.67  0.0427 10.67 2

 232 .7 KPa or 2.32 bar

 Problem 5

Determine the mass of N2 contained in a 30 m3

vessel at 20 MPa and 200 K by using (a) the ideal
gas equation (b) the generalized comp. chart.
(a) Ideal gas equation Pv = mRT

Pv 20 x106 x30
m    10103 .07 kg
RT 296.9200 
(b) From table for N2, Pc = 33.94 bar
Tc = - 147.10C = 125.90K
 P 20
 PR    0.589
Pc 33.94
T 200
TR    1.59
TR 125.9
For PR = 0.589 & TR = 1.59 from chart Z = 0.9
Pv ZRT
but Z  v   0.00268 m / kg
3

RT P
V 30
m    11194 .03kg
v 0.00268
Determine the pressure exerted by oxygen in a container of 2 m3 capacity
when it contains 5 kg at 27oC using ideal gas equation and Van der Waals
equation.

For one mol of any gas, pV  RT

Here V is molar volume.
For n mol, pV  nRT
weight 5000
n    156 . 25
M 32
w
pV  nRT

p(2)  (0.15625 )(8.314)(273  27)

Unit of R here is m3.kPa / kmol. K
p  194.86kPa
  n2a 
2
27 R 2TC RT
 p  2 V  nb  nRT a
64 pC
;b  C
8 pC
 V 

TC  154 .4 K ;
pC  49.7atm  101 .325(49.7)kPa  5035 .8kPa

27(8.314) 2 (154.4) 2
a  138.047
64(5035 .8)
8.314(154.4)
b  0.03186
8(5035 .8)

77 L.Muruganandam
  n2a 
 p  2 V  nb  nRT
 V 

 (0.15625 ) 2 (138.047 ) 
 p  2
2  0.15625 (0.03186 )
 2 
 0.15625 (8.314)(300)

 p  0.84257 1.99502   389.71

p  194.5kPa
p  194.86kPa Ideal gas
p  194.5kPa Van der Waals
78