Thermo PDF

Thermodynamics
Basic Concepts
Introduction:
Thermodynamics deals with heat inter-action and work inter-action with the
substances called systems. Work and heat are forms of energy. Transfer of heat or work
to a substance brings about certain changes in the substance and whatever change
happens is called a process. Thermo means heat. Since work is also a form of energy,
thermo is taken to mean heat and work. Dynamics refers to the changes that occur as a
result of heat or work transfer.
Biological systems are capable doing work. For example, micro-organism is
capable swimming in the body fluid of its host. It needs to do the work. Where does
energy for doing this work come from? It is the metabolic activity that converts some
form of energy (Nutrition that it takes form host is a form of chemical energy) into work.
It is important then to understand how this happens so that we can exploit this to our
engineering benefit.
In thermodynamics we have work transfer, heat transfer and then we have a
system for interaction which undergoes a process. Let us look at these basic terms.
System:
We need to fix our focus of attention in order to understand heat and work
interaction. The body or assemblage or the space on which our attention is focused is
called system. The system may be having real or imaginary boundaries across which the
interaction occurs. The boundary may be rigid and sometimes take different shapes at
different times. If the system has imaginary boundary then we must properly formulate
the idea of system in our mind.
Surroundings:
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Every thing else apart from system constitutes surroundings. The idea of
surroundings gets formulated the moment we define system. System and surroundings
together form what is known as universe.
Closed system:
If the system has a boundary through which mass or material cannot be
transferred, but only energy can be transferred is called closed system. In an actual
system, there may not be energy transfer. What is essential for the system to be closed is
the inability of the boundary to transfer mass only.
Open system:
If the system has a boundary through which both energy and mass can transfer, then it is
called open system.
Properties:
Variables such as pressure, temperature, volume and mass are properties. A system will
have a single set of all these values.
Intensive properties:
The properties that are independent of amount contained in the system are called
extensive properties. For example, take temperature. We can have a substance with
varying amount but still same temperature. Density is another example of intensive
property because density of water is same no matter how much is the water. Other
intensive properties are pressure, viscosity, surface tension.
Extensive properties:
The properties that depend upon amount contained in the system are called extensive
properties. Mass depends upon how much substance a system has in it therefore mass is
an extensive property.
State:
It is defined as condition of a system in which there are one set of values for all its
properties. The properties that define the state of a system are called state variables.
There is certain minimum number of intensive properties that requires to be specified in
order to define the state of a system and this number is uniquely related to the kind of
system. This relation is phase rule which we shall discuss little later.

Process:
The changes that occur in the system in moving the system from one state to the other is
called a process. During a process the values of some or all state variables change. The
process may be accompanied by heat or work interaction with the system.
Heat:
It is a form of energy that exists only in transit. This transit occurs between two points
which differ in temperature. Since it exists only in transit, it should be accompanied by
changes that occur in the system. The moment this energy cease to move, it appears as
internal energy. We shall discuss internal energy when we deal with I law of
thermodynamics.
Work:
It is also a form energy that exists only in transit. The work cannot be stored. Work is
defined as the product of force and distance through the force moves. Mathematically,
   
W  f d  f d cos 
where f is the force and d the displacement. Work is a scalar quantity.
Let us look at the following piston and cylinder arrangement containing some gas. The
system considered is the gas in the cylinder. It is exerting some pressure on the piston in
the upward direction. This is balanced by the atmospheric pressure plus the weight and

therefore piston though it is free to move, does not move. If the weight is increased, then
dL
the piston moves downwards. The pressure of the gas increases and the movement of the
piston stops when the pressures become equal. The additional weight is doing the work
on the gas. The additional weight has to push the force created by the gas inside to move
the piston. So there is force and distance. But as the piston moves, the pressure
continuously changes. Therefore consider small distance (dL) for which work done (dW)
is also small as shown in the figure which results in small volume change (dV). Then by
definition of work, we have, if A is the cross sectional area of the piston
dW  f  dL
V 
 pA  d  
 A
 pdV
Integrating between the two locations of the piston,
2
W1 2   pdV
1

This is the equation we use to determine the work. Please note that in general p cannot
be taken out of the integral sign as p may be continuously changing as above.
p 1
a b
V
If we have a p vs. V curve, we can determine the integral as area under the curve.
The area under the curve a21b is the work done on the gas.
We can carry out a process differently with the same initial and final states given
by the points 1 and 2. Since it is a different process, the curve will be different. In that
case the area under the curve will also be different which means to say the work done is
different though the initial and final states are same. Thus the work depends upon the
process or path or how the state is changing. Such quantities are called path functions.
Since heat is also energy in transit as the work is, heat must also be a path function. No
matter what process, as long we have same initial and final states, it brings about the
same pressure difference. Such properties which depend only on state are called state
properties.
Equilibrium state:
A system is said to be in thermodynamic equilibrium if it satisfies the condition for
thermal equilibrium, mechanical equilibrium and also chemical equilibrium. If it is in
equilibrium, there are no changes occurring or there is no process taking place.
Thermal equilibrium:
There should not be any temperature difference between different regions or locations
within the system. If there are, then there is no way a process of heat transfer does not

take place. Uniformity of temperature throughout the system is the requirement for a
system to be in thermal equilibrium.
Surroundings and the system may be at different temperatures and still system may be in
thermal equilibrium.
Mechanical equilibrium:
There should not be any pressure difference between different regions or locations within
the system. If there are, then there is no way a process of work transfer does not take
place. Uniformity of pressure throughout the system is the requirement for a system to be
in mechanical equilibrium.
Surroundings and the system may be at pressures and still system may be in mechanical
equilibrium.
Chemical equilibrium:
There should not be any chemical reaction taking place anywhere in the system, then it is
said to be in chemical equilibrium. Uniformity of chemical potential throughout the
system is the requirement for a system to be in chemical equilibrium.
Surroundings and the system may have different chemical potential and still system may
be in chemical equilibrium.
Thermodynamic process:
A system in thermodynamic equilibrium is disturbed by imposing some driving force; it
undergoes changes to attain a state of new equilibrium. Whatever is happening to the
system between these two equilibrium state is called a process. It may be represented by a
path which is the locus all the states in between on a p-V diagram as shown in the figure
below.

1
p
2
V
For a system of gas in piston and cylinder arrangement which is in equilibrium, altering
pressure on the piston may be driving force which triggers a process shown above in
which the volume decreases and pressure increases. This happens until the increasing
pressure of the gas equalizes that of the surroundings. If we locate the values of all
intermediate states, we get the path on a p-V diagram.
Phase rule:
The two gas samples below have the same density, viscosity and all other intensive
properties.
1 m3 of nitrogen at a pressure of 2 atmosphere and 300 K

2 m3 of nitrogen at a pressure of 2 atmosphere and 300 K
If a gas behaves ideally, then
pV  nRT
n p

V RT
If M is the molecular weight of the gas, then

m nM pM
  
V V RT
pM

RT
Thus the density of an ideal gas depends upon only temperature and pressure as all other
quantities are constants. Since p and T are same for the above nitrogen samples, density is

same. If we take out 1 cc of sample from any of those two, by observing only this 1 cc
sample we can never from where we took the sample. This means to say the samples are
exactly same and indistinguishable. They are said to be in the same state.
In order to define this state of nitrogen, we need only T and p. Thus we need minimum
two variables to specify the state. This number is given by Gibb‘s phase rule which is
given by
F  2   N
where
F : degrees of freedom
 : Number of phases
N : Number of components
For the above example, number of phases is one; number of components is one therefore
the degrees of freedom are two. For a system containing liquid water and its vapor in
equilibrium, we get the degrees of freedom to be one.
Following is the phase diagram of water which describes in what phase or phases
it can exist for different temperature and temperature.

Liquid
p Solid
Vapor
For the system to have two phases, if we mention the temperature alone given by
the vertical line, the pressure has to be the one given by horizontal line. Given the
pressure, its temperature gets fixed. Thus we have a freedom of fixing only one of them
which amounts to say degrees of freedom is one.
Heat reservoirs:
If the temperature of the system does not change if we remove a finite quantity of heat
from it, then the system is said to be heat reservoir. If the temperature of the system does
not change if we add a finite quantity of heat to it, then the system is said to be heat sink.
Ocean can be made to act either as heat reservoir or heat sink.
Heat Engine:

Work and heat are forms of energy and are inter-convertible. Any device which converts
continuous supply of heat into useful work continuously is called heat engine. For any
system to undergo continuous process, it should be cyclic. The detailed mathematical
treatment of heat engines will follow in 5th chapter on second law of thermodynamics.
Irreversible process:
If a thermodynamic process takes place in such a way that we can retrace the path
exactly, the process is called reversible. Consider a piston and cylinder arrangement with
piston free to move at some pressure and temperature in equilibrium. The pressure of the
gas is balanced by a pressure equal to sum of atmospheric pressure and the weight on the
piston pan as shown. If the weight on the piston is reduced, then the piston moves up. Let
us just displace the part of the weight horizontally. This involves work. The piston moves
up as it is free to move until the pressures again become equal.

State -1 State -2
Following is the p-V diagram for the process.
2
p
1
Looking at the sequencing of the events, it is

1. Removal of part of weight on the piston which takes some work.
2. Moving of piston upward following some path on p-V diagram as shown.
Reaching a new steady position called state – 2.
Reversal of these events will mean

1. Piston moving downward from state-2 to state-1.
2. Weight moving on to the piston.
Can this reversal be possible? During expansion step, the system does work on the
surroundings. In reverse then, the surroundings should do the work at state – 2. This is
not possible as the system and the surroundings have the same pressure. Exact reversing
is not possible. The process of bringing the weight on the piston pan is also not possible
as we need to do only by moving horizontally. The pan level is higher than that of the
weight. This requires extra work to be done. Further, in moving the weight work was
done on the weight. In reverse then, the weight should do the work, go and sit on the pan!
Clearly this is ridiculous which is not possible.
In order for a process to be reversible, the driving force must be infinitesimally small. If
we remove the weight bit by bit and place it horizontally, every bit would be placed one
above the other and then piston moves upward. At any point, the piston and the bit
removed are at the same level. As a result, at any point, we can move the bit horizontally,
making the piston move a bit down where the next bit of weight is available at the same
level. Reversing is thus possible.
However there is one work that can never be reversed even in this process. That is the
work done on the bit to move it horizontally. But this is less irreversible compared to the
earlier process where large part of the weight was removed. Look at the state-2, in order
to reverse; the weight has to be lifted by some vertical distance which is missing in the bit
by bit process. We can only strive to make a process only closer to reversibility.

First law is a statement of law of conservation of energy. For a closed system, since there
is no mass exchange with the surroundings, the total energy of the system must be always
a constant. One form of energy may be converted into another. The system may possess
several forms of energy such as kinetic energy, potential energy, internal energy.
Potential energy:
It is the energy possessed by a body by virtue of its position. An object kept at a height z,
possesses energy to do the work. A spring kept in a compressed state is also capable of
doing work. A body is said to be possessing energy only if it can lift weight by some
mechanical means. If we tie a rope to a body at higher level, pass the rope over a pulley
and tie the other end to another body whose mass is slightly lower, the second body will
be lifted. To one end of the compressed spring in the vertical position, tie a weight and
then release the spring. The weight goes up. Thus a body at higher level or spring in its
compressed state possesses energy. The potential energy of a body of mass m at height of
z from some arbitrary level (reference level) is given by
EP  mgz
Arbitrary level may by any level. As long as the same, the changes in energy will also be
same. The changes in potential energy as the level changes will be
EP  mg( z f  zi )  mgz
Kinetic energy:
It is defined as the energy possessed by a body by virtue of its velocity. For a body of
mass m which is moving with a velocity u, the kinetic energy is given by,
1 2
EK  mu
2
Change in kinetic energy is
1 1
EK  m(u f  ui )  mu 2
2 2
2 2

Internal energy:
When some external work is transferred to a body, its temperature increases indicating
rise in internal energy. Internal energy is due to molecular energy of vibration and
rotation.
First law of thermodynamics for a closed system:

If Q is the amount of heat transfer to a system which does W amount of work (work
transfer form the system), then the change in the total energy of the system will be Q –
W. This change will have its implications on the kinetic, potential and internal energy.
Since law of conservation is to be valid, the change in internal energy Q – W must be
equal to the changes occurring in all forms energy. Mathematically,
Q  W  U  EP  EK
Generally, the changes in kinetic and potential energy will be negligible compared to heat
and work interaction,
Q  W  U
This is first law of thermodynamics. Note that Q is the heat transfer to the system and W
is work done by the system.
Cyclic process:
If the process occurs in such a way that periodically its state repeats then the process is
called cyclic process. The following p – V diagram represents a cyclic process.

3
p
1
2
The states 1, 2 and 3 keep repeating in the process in that order. Not only this, all the
states in between also will repeat. Every time process state changes from 1 to 2, 2 to 3
and 3 to 1 following the same paths. During such processes, there will be heat and work
interaction. All the properties will get the same values at state 1 regardless of number of
times cycle repeats. Thus
U1 2 31  V1 2 31  p1 2 31  T1 2 31  0
First law applied to a cyclic process:

Since the change in internal energy is zero,
U  Q  W
Q W  0
Q W
This means that net heat transfer to the system is the net work done by the system.
Cyclic process consists of several steps. In the cyclic process shown in the diagram, there
are three steps viz., 1-2, 2-3 and 3-1.

Let us have another cyclic process for which heat and work interaction are known as
below.
Step Heat interaction Work interaction

1-2 Q1-2 is added to the system No work interaction
2-3 Q2-3 is removed form the system W2-3 is the work done by the system
3-1 Q3-1 is added to the system W3-1 is the work done on the system
Net heat transfer to the system, Q  Q1 2  Q2 3  Q31
Net work done by the system, W  W2 3  W31 and Q  W
Flow processes:
So far we considered closed systems only. Let us look at open systems. Mass exchange
can occur. If the process variables do not change with respect to time for the system, the
process is said to be under steady state conditions. Under such conditions the mass of the
system is constant. This is due to the equality of mass entering and leaving.

If the system as a whole is moving undergoing changes, it constitutes steady state flow
process only when the system at a fixed location will have fixed values.
Heat in, Q
z1
A z2
Work output, Ws
This diagram shows an open and steady state flow process. The equipment considered is
between 1 and 2. The gas enters at 1 and leaves at 2. Steady state flow process requires
mass entering at 1 is equal to mass leaving at 2. If certain mass of gas considered to be
the system, such as cylindrical shaped gas at 1, when it reaches a particular location such
as A, it will be at a state (having certain fixed values for all the properties). No matter
what time, the system at A will be in the same state. This is true for all locations.
However, state of the system differs from location to location. There is no variation of the
state with respect to time at a given location.
First law applied to flow process:

Following is the equipment through which the steam is flowing.

1
Heat in, Q
z1
z2
Work output, Ws
Steam enters at 1 and leaves at 2. There is a heat exchanger which adds heat Q to the
steam making it superheated. The superheated steam runs the turbine and shaft work is
obtained. Thus the gas does the work Ws. The kinetic, potential and internal energy of the
gas changes as it goes from one location to the other. The entrance 1 is at height z1 and
exit is at height z2 from some reference datum. The velocity of the gas varies as the flow
area varies along the path.
Let us consider unit mass of steam whose volume is the volume of cylinder shown at
location 1. This steam element enters the equipment, goes through it receiving heat Q in
the exchanger, doing work at the turbine and comes out at 2. There are changes
occurring in potential (as the height at which the steam element is present changes),
kinetic energy (as the velocity changes) and internal energy. Let u1 and u2 be the
velocities at location 1 and 2. Change in kinetic energy, since m =1, is
1 2
E K  (u 2  u1 )
2
2
Change in potential energy of the steam from 1 to 2 is

E P  mg( z 2  z1 )
Let the change in internal energy be U . We must account for all heat and work
interaction that occur during the process of steam element moving form 1 to 2. The heat
Q is getting transferred in the heat exchanger to the steam element. Apart from work
output of the turbine, there are other fork forms. At location 1, the surrounding has to do
the work on the steam element to push it into the equipment. If the pressure of the steam
is p1, and the cross sectional area of the pipe is a1, then the distance moved by the steam
element is V1 / a1 where V1 is the specific volume of the steam at 1. The work done at the
entrance on the steam element at 1 is then,
V1
W1  ( p1a1 )  p1V1 (Work done on the system)
a1
Similarly work needs to be done by the steam element at section 2 as it has to push the
surrounding which is given by
V2
W2  ( p2 a2 )  p2V2 (Work done by the system)
a2
The entrance and exit work are also called as flow work. The product of pressure and
volume is the flow work.
If the steam element gets into the equipment, it receives work done by the previous steam
element and uses it to push the element next to it. Thus the net work is zero for all the
locations inside the equipment.
Thus the net work done by the element,
W  WS  W2  W1
W  WS  P2V2  P1V1
Substituting in first law of thermodynamics,
Q  W  E K  E P  U
Q  (WS  p 2V2  p1V1 )  E K  E P  
Q  WS  E K  E P  U 2  U 1  p 2V2  p1V1
Q  WS  E K  E P  (U 2  p 2V2 )  (U 1  p1V1 )

The group U  pV occurs frequently in flow processes and is called enthalpy denoted by
the letter H.
H  U  pV
Since internal energy, pressure and volume are state functions, enthalpy is also state
function. The above equation becomes,
Q  WS  E K  E P  H 2  H 1
Q  WS  E K  E P  H
This equation is first law of thermodynamics applied to flow processes. If the changes in
potential and kinetic energy are very small then,
Q  WS  H
Heat capacity:
Heat capacity of a substance is defined as the heat transfer necessary to bring about a
change in the temperature of unit amount of substance by one degree centigrade. Since it
is heat transfer which is a path function, it depends upon the way heating is done. For
example gases can be heated to increase the temperature by two different methods. The
unit quantity of gas taken in container with rigid wall, when heated its volume remains
constant. Another method is to have the wall which is flexible. If the piston is movable in
the piston and cylinder arrangement, gas when heated pushes piston and pressure will be
constant. Even if we take unit amount of gas in both these heating methods, it is observed
the heat transfer is not the same. Thus we have heat capacity and constant volume and
heat capacity at constant pressure. Mathematically,
dQ
C
dT
dQ
Cp 
dT p
dQ
CV 
dT V
The heat capacity at constant volume will not be equal to that at constant pressure.

PVT Behavior of fluids
Pressure, temperature and volume of gases vary in a definite manner. Based upon the
conditions, matter can exist in solid, liquid and gas phase. This is represented in graphical
form as below. This diagram is for pure water. All pure substances will have more or less
similar diagrams.
p – T diagram for pure water
Fluid
Liquid Critical Point.
Solid
p
d Gas
a b
Vapor
Based upon the values of pressure and temperature, if the point lies in a region, the
substance will exist in the corresponding state represented. For example the point a
represents solid state and b represents vapor state. Any point lying on the curve
represents both the phases which are in equilibrium. For example, the point d represents
liquid water and its vapor in equilibrium. Thus there are numerous pair of pressure and
temperature values on the curve and all those points represent liquid and vapor in
equilibrium. Each curve will have always two phases in equilibrium.
The point where all the curves meet is called triple point and at this condition, all the
three phase exist in equilibrium. Critical point is the highest temperature and highest
pressure where the liquid and its vapor can exist in equilibrium.

For all pressures and temperatures higher than those at critical point, the liquid and vapor
properties become similar. This state is called fluid.
Phase is considered liquid if it can be vaporized by reduction in pressure keeping T
constant. This is represented by vertical downward arrow in the figure. The initial point is
in liquid phase region. Phase is considered gas if it can be condensed by reduction in T
keeping p constant. This is shown by horizontal arrow pointing towards left. The point a
represents solid state which on increasing the temperature at constant pressure, only the
temperature of the solid increases until it reaches curve where first drop of liquid appears
and beyond this only vapor exists. This is shown as arrow a  b.
The other way is representation using p – V diagram for pure substance which is given in
the next figure.
S/L
fluid
pC C
S L
Gas
p
L/V V
TC
S/V
VC V
p – V diagram for pure substance
There are regions where two phases co-exist in equilibrium. The dashed curve labeled Tc
represents an isotherm at critical temperature.
In thermodynamics, we deal largely with either vapor or gases. The significant portion of
the diagram is given below.

p – V diagram for pure substance
1 fluid
pC C
L Gas
p
2 3 4
V
TC
L/V
T1
VC V
The substance at point 1 is in liquid state. If we decrease pressure keeping temperature

constant, the volume decreases along the dashed curve. But this change is very small and
this is why liquids are considered incompressible. Volume change with pressure at
constant temperature is negligible for liquids. Decreasing pressure from 1 at constant
temperature (T1), a point 2 will be reached where first bubble of vapor appears. Any
further attempt to decrease the pressure fails bringing pressure down, instead more and
more liquid becomes vapor and the pressure and temperature remain constant represented
by dashed horizontal line. Thus point such as 3 represent liquid and vapor in equilibrium.
Further attempt in decreasing the pressure brings the state to the point 4 where all the
liquid becomes vapor. Further decrease in pressure at constant will follow the dashed
curve in the gas region. Thus the dashed line represents an isotherm (T1). Given in the
figure there is one more isotherm at a temperature less than T1. The dumb bell shaped
curve represents the locus of all points on all isotherms where the points similar to 2 and
3 lie. The isotherms of higher temperature lie on higher and saturated liquid and vapor
volume become closer and closer and finally merge at the critical point. This is point
where liquid and vapor cannot be distinguished. Isotherm TC has a point of inflexion at
the critical point.

A point on the curve is called point of inflexion if there is a tangent at that point which
lies on either side of the curve as shown below.
How do we represent this complicated behavior mathematically? This is a challenge

which led to lot of research and we have several mathematical equations. All these
equations do have limitations. We will use simple mathematical equation. This is not a
limitation as no matter what equation all it does is relate pressure, temperature and
volume of gases.
Ideal gas equation: For one mol of any gas,

pV  RT
Internal energy is a function of temperature only.
T2 T2
U   CV dT H   C P dT
T1 T1
No matter what process, the changes in internal energy and enthalpy are given by the
above expression not only for ideal gases even for real gases.
This law is valid for low pressures, large volumes and low temperatures.
At constant pressure
 dQ 
CP   
 dT  p
 dQ  C P dT ,
At constant volume
 dQ 
CV   
 dT V
 dQ  CV dT ,
Isochoric Process:

Any process in which volume of the system does not change is called isochoric process.
Work done is zero.
U  Q  W
U  Q
T2
U   CV dT  CV (T2  T1 )
T1
T2
H   C P dT  C P (T2  T1 )  Q
T1
Isobaric process:
dU  dQ  pdV
dQ  CP dT
dU  C P dT  pdV
 C P (T2  T1 )  p(V2  V1 )
H  Q  C P (T2  T1 )
W  p(V2  V1 )
Relation between heat capacities:
H  U  PV
H  U  RT
dH  dU  RdT
CP dT  CV dT  RdT
CP  CV  R
CP  CV  R
CP  CV
Isothermal Process:
Since the temperature is constant there will not be any change in internal energy.

dU  dQ  dW
dQ  dW
V2
Q W 
V1
 pdV
V2
  pdV
V1
V2
RT
 
V1
V
dV
p1 p1V1 p2V2
 RT ln 
p2 T1 T2
p
 RT ln 1
p2
V2 p
Q  W  RT ln  RT ln 1
V1 p2
H  U  0
Adiabatic Process:
There will not any heat exchange, Q = 0.
dU  dW
RT
CV dT   dV
V
RT
CV dT   dV
V
dT R dV

T CV V
CP R
1 
CV CV
CP R
1 
CV CV
R
  1
CV

dT dV
 (  1)
T V
dT dV
 (  1)
T V
T2 2 V
dT dV
T T   (  1) V V
1 1
T2 V
ln  (  1) ln 2
T1 V1
 1
T V 
ln 2  ln  1 
T1  V2 
 1
T2 V 
  1 
T1  V2 
The temperature and volume change according to the above equation.

The pressure, temperature and volume all vary in the adiabatic process.
Let us get a relation between the other variables.
Since the gas is ideal,
p1V1 pV
 2 2
T1 T2
T2 p2V2

T1 p1V1
 1
p2 V1  V1 
  
p1 V2  V2 
 
 p1V1  p2V2
pV   const
dU  dW
T2
U  W   CV dT
T1
 W  CV (T2  T1 )

R
 (T2  T1 )
 1
RT2  RT1

 1
p2V2  p1V1

 1
 
p1V1  p2V2

p1  V2 
 
p2  V1 
1
V2  p1  
 
  V1  p2 
1
p1V1  p2  p1   
W 1   
  1  p1  p2  
 
  
1
p1V1  p2  p2   
 1  
  1  p1  p1  
 
 1 
1
p1V1   p 2   
W 1  
  1   p1  
 
 1 /   1 / 
p1V1   p2   p1V1   p2  
U   1     W 1    ;
  1   p1     1   p1  
 
2
H   C P dT
1
2
U   CV dT
1
Polytropic Process:

It is a representation of all the processes in a mathematical form as below.
pV n  const
Sl. No n Process
1. 0 Isobaric
2. 1 Isothermal
3.  Isochoric
Generally n lies between 1 and .
Guidelines to represent processes on p – V diagram:
T2
T1
In the figure above there are two isotherms shown. For these isotherms, T2  T1. There is
one isotherm passing through every point on p – V diagram. Higher the temperature
higher will be location of the isotherm. As they go downwards they converge as shown.
No two isotherms will ever intersect.

Similarly every point has an adiabatic curve passing through it. The adiabatic curve
follows the relation pV   const . Thus every point is an intersection of an isotherm and
an adiabatic curve as shown below. The adiabatic curve is steeper.
Adiabatic curve
Isotherm
No two adiabatic curves will ever intersect.
The mathematical relation between pressure, volume and temperature applicable all
ranges of values has not been possible. However, there are equations which are valid over
certain ranges.
Conditions for any equation to be equation of state:
1. The equation should reduce to
pV  RT
As p  0.
2. p-V curve should have a point of inflexion for isothermal at critical point C,
 p   2 p 
   0 and  2   0
 V C  V C
Van der Waals equation of state:
 a 
 p  2 V  b   RT
 V 
Here a and b are constants that depend upon the gas. If we apply the partial derivative
conditions, we get,

2
27 R 2TC RT
a ;b  C
64 pC 8 pC
The Van der Waals equation is cubic in V. Therefore it should have three roots for a
given set of values of pressure and temperature and for a given substance. For any
temperature higher than critical temperature, there is one positive root. For critical
temperature and critical pressure, all the three roots will be equal which gives critical
volume. For temperature and pressure less than critical values, there will be three roots,
least one gives the molar volume of saturated liquid and highest gives that of saturated
vapor which are volumes given by the two ends of horizontal section of the isotherm.
Redlich – Kwong Equation:
RT a
p 
V  b V (V  b) T
Applying the partial derivative condition, we get
5/ 2
0.4278R 2TC 0.0867 RTC
a ;b 
pC pC
Note that the above equations reduce to the equation pV  RT , as p  0.

Other equations of state are Peng – Robinson and Virial equations.
Numerical problem:
Air is compressed from an initial state of 1 bar and 298 K to a final state of 5 bar and 298
K through two mechanically reversible processes in a closed system. First heating at
constant volume followed by cooling at constant pressure. Calculate W, Q, change in
7R 5R
enthalpy and internal energy. Use CP  , CV  .
2 2

2
a
p
Isotherm at 298 K
1
The path is shown in the figure. 1 - a represents heating at constant volume and a - 2
represents cooling at constant pressure. Note that initial and final states lie on a single
isotherm.
Let us do the calculations for one mol of gas.
For the path 1 – a, since volume is constant, work done is zero.
dU  dQ
dU  CV dT
Ta
U1 a   CV dT
T1
To use this we need to know temperature at a. Since it is closed system and volume is
same at 1 and a,
paTa  p1T1
Since pressure at a is same as that at 2,

p1T1 p1T1 5(298)
Ta     1490 K
pa p2 1
Ta
U1 a   CV dT
T1

1490
5R
 
298
2
dT
5R
 (1490  298)
2
5(8.314)
 (1490  298)
2
 24775.7 J
 24.775kJ
Thus Q1-a = U1-a = 24.775 kJ.
1490
7(8.314)
H1 a   C dT 
298
P
2
(1490  298)  34686 J  34.686kJ
You can use the formula

H1 a  U1 a  ( pV )1 a  U1 a  ( paVa  p1V1 )
to calculate change in enthalpy.
For the step a – 2,

dU  dQ  dW
T2
U a  2   CV dT
Ta
298
5R
 
1490
2
dT
5R
 (298  1490)
2
 24775.7 J
 24.775kJ
298
7(8.314)
H a  2   C dT 
1490
P
2
(298  1490)  34686 J  34.686kJ
dW  pdV

2
Wa  2   pdV
a
Along the path a – 2, since pressure is constant and equal to 5 bar,

2
Wa  2   pdV
a
 5x105 (V2  Va )
We should know the volume at a.
8.314(198)
From gas law, at the initial condition, V1  5
 0.02477m3
1x10
Note that we have taken one mol.
p2V2 p1V1

T2 T1
The temperatures are equal,
p1V1
V2 
p2
1(0.02477)

5
 0.004954m3
Similarly,
RTa 8.314(1498)
Va    0.1245m3
pa 1x105
Wa  2  p(V2  Va )  5x105 (0.004954  0.1245)  59773J  59.773kJ

Since the volume is decreasing, work is done on the system.
U a  2  Qa  2  Wa  2
 24.775  Qa  2  (59.773)
Qa  2  84.548kJ
For the entire process,
Q1 2  Q1 a  Qa  2  24.775  (84.548)  59.773kJ

U1 2  U1 a  U a  2  24.775  24.775  0
H1 2  H1 a  H a  2  34.686  34.686  0
W1 2  W1 a  Wa  2  0  (59.773)  59.773kJ

Since there are no changes in internal energy and enthalpy, work done on the system is
given out as heat.
Determination of changes in internal energy and enthalpy:
No matter what is the process the internal energy and enthalpy are determined using the
following formulae.
dU  CV dT
dH  CP dT
If the process is isochoric, then dU  CV dT  dQ.

If the process is isobaric, then dH  CP dT  dQ.
Let us recall that

1. For ideal gases internal energy is a function of temperature only.
2. The change in internal energy is a state function.
Let us take an adiabatic process and determine change in internal energy.

2
p
Consider two states (1) and (2) on an adiabatic path. There is one isotherm for each state
as shown. Adiabatic curve at (1) is steeper than the isotherm. Whether the process
follows adiabatic path or another curve shown in the figure or any arbitrary path, as long
the initial and final state are same, we get the same change in internal energy.

2
p a
Let us replace adiabatic path by two steps –

1. 1 – a constant volume process followed by
2. a – 2 isothermal process
to accomplish the same change in the state.
ΔU12  ΔU1a  ΔU a 2
Since step 1 – a is a constant volume process, dU  CV dT will have to be used. The step
a – 2 is isothermal and therefore dU = 0.

Ta
ΔU12   CV dT  0
T1
Since Ta  T2 ,

T2
ΔU12   CV dT
T1
Any process between any two states can be replaced by either an isothermal process
followed by constant volume process or constant volume process followed by an
isothermal process. The total change in internal energy is the change in internal energy
for constant volume step only. Thus no matter what process the change in internal energy
is given by dU  CV dT .
Same idea may be extended to change in enthalpy.
Deviations of real gases form ideal behavior:

The deviation from ideal behavior is measured using what is known as
compressibility factor defined as the ratio of volume determined using ideal gas law
to the actual volume at any given temperature and pressure.
Vactual pV
Z 
Videal RT
For ideal gases, Z = 1. Higher the value Z away from one higher will be the non-ideality.
Following figure gives the value of Z as a function pressure for different gases. All gases
approach ideal gas behavior at low pressures. This figure is called compressibility chart.
There will be as many curves as there are number of gases. The chart that is given here is
for one temperature. Therefore this figure becomes highly cumbersome if applied for all
gases and all temperatures.

N2 CH4
1.0
C2H6
p
Theory of corresponding states:
It states that all fluids, when compared at the same reduced temperature and reduced
pressure, will have same compressibility factor and all deviate from ideal behavior to the
same extent.
The reduced pressure and temperature are defined by
p
pr 
pC
T
Tr 
TC

Tr  1.5
Tr  2.5
Z
Tr  1.0
pr
Here all gases with the same reduced temperature and pressure lie on the same curve.
This chart is called generalized compressibility chart. Different gases are indicated by
different points on the curve. There will be as many curves as there are temperatures.
This is less cumbersome compared to compressibility chart.
T p Tc p T pr
N2 189. 83.7 126. c 33. r
1. 2.
CH4 3
286.0 5
114. 2
190. 5
45. 5
1. 5
2.
5 5 7 8 5 5
The above table gives two gases with the same Z for different T and p. The reason is that
the critical values are different.

Standard Heat of reaction:
It is defined as the enthalpy change accompanying a reaction when both reactants and
products are at their standard states at 298 K and is denoted by ΔH 0 298 .
2C( s )  O2 ( g )  2CO( g ) ΔH 0 298  221.2 kJ
If the stoichiometry of the above reaction is represented as
1
C( s )  O2 ( g )  CO( g )
2
Then,
 221.2 kJ
ΔH 0 298   110.6 kJ
2
Standard Heat of Combustion:

The standard heat of combustion of a substance is defined as the enthalpy change
accompanying the reaction when one mol of the substance undergoes combustion when
both reactants and products are at 298K.
2CH 3 CHO( l )  5O2 ( g )  4CO2 ( g )  4 H 2 O; ΔH 0 298  2336.24kJ
The heat of combustion is – 1168.12 kJ.
The standard heat of formation:

Standard heat of formation of a substance is defined as the change in enthalpy
accompanying the formation of 1 mol of the substance from the constituent elements
when the reactants and products are at 298K.
2C( s )  O2 ( g )  2CO( g ) ΔH 0 298  221.2 kJ
Standard Heat of Formation of Carbon monoxide is ΔH

0
f  110.6 kJ .

Hess’s Law of constant heat summation:
The net enthalpy involved in a reaction is the same whether the reaction takes place in a
single step or in a series of steps.
A B C ΔH
Let A and B react to form C with heat of reaction H. Let there be one more method of
carrying out this reaction in two steps as given below.
A  B  AB ΔH1
AB  C ΔH 2
Treating arrow as an equal sign, adding these two reactions gives,
A B C , ΔH1  ΔH 2
It has been found that ΔH1  ΔH 2 is same as ΔH .
This idea is used to determine heat of reaction from heat of formation or heat of
combustion data.
For example if we want to determine heat of formation of sulfuric acid, we must
determine this from the reaction,
H 2  S  2O2  H 2 SO4
No matter what we do, the above reaction cannot be carried out. Let us carry out other
possible reactions such that the over-all reaction is the formation reaction as below.
S  O2  SO2 ΔH1 ----------(1)
2 SO2  O2  2 SO3 ΔH 2 ----------(2)

SO3  H 2 O  H 2 SO4 ΔH 3 -----------(3)
1
H2  O2  H 2 O ΔH 4 ----------(4)
2
2(1), 2(3) and 2(4) gives,
2 S  2O2  2 SO2 2 ΔH1 ----------(1)
2 SO2  O2  2 SO3 ΔH 2 ----------(2)
2 SO3  2 H 2 O  2 H 2 SO4 2 ΔH 3 -----------(3)
2 H 2  O2  2 H 2 O 2 ΔH 4 ----------(4)
Adding these equations along with heat of reactions,
2 H 2  2 S  4O2  2 H 2 SO4
and heat of this reaction will be 2( ΔH1  ΔH 3  ΔH 4 )  ΔH 2
ΔH 2
Therefore heat of formation of sulfuric acid is ΔH1  ΔH 3  ΔH 4 
2
This is how Hess‘s law can be used to determine the heat of reaction of a reaction from
heat of reaction of other reactions.
First deals with law of conservation of energy and defines internal energy.
A stone falls decreasing its potential energy and converting it into kinetic energy. Just
before it strikes the ground, it has maximum kinetic energy. From there why does it not
go up decreasing its kinetic energy and converting it into potential energy?
If we keep two bodies at different temperature in contact, why there is no heat transfer
from a body of low temperature to a body at higher temperature?

When we remove the wall which separates two gases, the two gases mix together without
any external work done on them. Why then the two gases in a mixed state separate
themselves without any external work?
For all the processes mentioned above there is absolutely no violation of I law. In spite of
that, we do not observe these processes. It appears that there is some sense of direction
for spontaneous processes. There is nothing in the first law to indicate any such direction
to any process.
Is there any difference between heat and work though they are both forms of energy? If
they inter-convertible, then any cyclic process should be able to convert all the heat
supplied into work completely as change in internal energy is zero. Does it happen? It has
been found that we cannot have a device whose sole effect is conversion of heat supplied
into work completely. Let us look at why this is so with an example of a process.
In the following figure, there is a heat exchanger where heat is supplied (Q1) to the
system which is water in this case and generates steam at high pressure. The steam flows
into a turbine and rotates it producing useful work WS. From the turbine, we get steam at
relatively lower pressure than with which it entered. The objective here is to convert heat
Q1 into work. Since this heat is available, can we send the steam from turbine directly
into the heat exchanger in order to make it work continuously so that we get continuous
supply of work? This is shown by a dotted arrow.
The moment we establish this connection, whole process comes to an abrupt stop! We
have lower pressure steam line going into the heat exchanger in which there is higher
pressure steam. If there is connection like this, why does steam preferentially go into the
turbine line? It will enter into both the lines and stop the turbine. Therefore, in order to
have this going on, we must condense the steam bring about a change in its state so that it
can be fed to the heat exchanger. This state must be same as that of feed water to the heat
exchanger.

Turbine
WS
Heat Exchanger
Q1
Condenser
Q2
Thus there is no way Q2 = 0. We cannot device any process which converts Q1

completely into work. The work obtained Ws is less than Q1 by an amount equal to Q2.
By first law, since for a cycle change in internal energy is zero,
WS  Q1  Q2
Practically Q2 cannot be zero.
If we analyze any cyclic process, there will be several heat and work interactions, such
that net work done is equal to net heat supplied. There will be always one step in which
there is heat removed which brings down the amount of heat that is getting converted into
work.
This fact is the basis of statement of II law of thermodynamics. There are several
statements for the II law which are equivalent. In fact we can deduce one from any other.
All the statements are given below.
Second law of thermodynamics:

1. Heat cannot by itself pass from a cold to a hot body.
2. All spontaneous processes are to some extent irreversible and are
accompanied by degradation of energy.

3. It is impossible to construct a heat engine that operates continuously in a cycle
to produce no effect other than conversion of heat supplied completely into
work. This is called Kelvin – Planck statement.
4. It is impossible to construct a heat pump (reverse heat engine) that operates
continuously to produce no effect other than transfer of heat from low
temperature body to a high temperature body.
Carnot cycle and Carnot engine:

The Carnot cycle consists of four steps and all the four steps are reversible. The cycle is
shown in the diagram below.
TH
TC
A
p
B
D
C
There are two isotherms and two adiabatic processes as shown. The isotherms are at TH
and TC.
AB – Reversible isothermal expansion
BC – Reversible adiabatic expansion
CD – Reversible isothermal compression
DA – Reversible adiabatic compression
According to first law, it can be shown that
pA
QAB  WAB  RTH ln
pB
WBC  CV ( TH  TC )

pC
QCD  WCD  RTC ln
pD
WDA  CV ( TC  TH )
The net work done is given by
Wnet  WAB  WBC  WCD  WDA
pA p
 RTH ln  CV ( TH  TC )  RTC ln C  CV ( TC  TH )
pB pD
For adiabatic process BC,
( γ 1 ) / γ
TH  pB 
 
TC  pC 
And for the adiabatic process DA,

( γ 1 ) / γ
TC  pD 
 
TH  pA 
From these two,

pD pA

pC pB
Net work done becomes,
pA
Wnet  R( TH  TC ) ln
pB
Heat supplied with an objective of converting into work is

pA
QAB  W AB  RTH ln
pB
The efficiency is defined as
pA
R( TH  TC ) ln
Wnet pB TH  TC
η  
QAB pA TH
RTH ln
pB
It is clear that efficiency of Carnot engine depends upon only the temperatures between
which it is operating and not on the working substance undergoing the cycle. Since
Carnot engine is reversible, it must have maximum efficiency.

From first law,
Wnet  QAB  QCD
Wnet QAB  QCD Q T

η   1  CD  1  C
QAB QAB QAB TH
QCD T
1 1 C
QAB TH
QCD TC

QAB TH
Let QCD is heat removed, and be equal to QC; and heat added as QH, with sign
convention,
 QC TC
 which can be simplified to
QH TH
QH QC
 0
TH TC
This equation is applicable to the complete cycle and any quantity that adds to zero for
the cycle is a state property. Thus Q/T is a state property called entropy. Thus second law
of thermodynamics brings in the idea of entropy.

Efficiency of engines:
The efficiency of reversible Carnot Engine is given by
QH  QC TH  TC
η 
QH TH
The maximum efficiency of any engine operated between two temperatures is always
given by
TH  TC
η
TH
as the efficiency of a reversible engine is maximum.
Efficiency of real engine is always less than that of reversible engine. If the engine is
irreversible then efficiency is calculated from
QH  QC
η
QH
and not from temperatures.
For any irreversible engine,
dQH  dQC TH  TC

dQH TH
 dQC  TC

dQH TH
 dQC  dQH

TC TH
Applying sign convention,
dQC dQH
 0
TC TH

Thus for irreversible engine,
dQ
 T
0
If the processes are all reversible, then

dQ
 T
0
In general,
dQ
 T
0
This is called Clausius inequality. The sum of dQ / T terms over a cycle is less than or
equal to zero depending upon whether the cycle is irreversible or reversible.
The changes in entropy are always determined using,
dQRe v
dS 
T
B
1
p
A 2
Let A1B Represent irreversible process and A2B represent reversible process between
the same states.
dQRe v
dS 
T
dQ dQ
ΔSAB 
A2 B
 T
 
A1B
T

To determine entropy change we must have only reversible path. However the entropy
change between the states 1 and 2 is same regardless of the path as it is a state function.
What the above equation says is entropy is not equal to dQ/T along an irreversible path.
To determine entropy change for any irreversible path between two states, replace the
path by a reversible path with the same states, and find the entropy of the reversible path.
Entropy and irreversibility:

Let us look at a cyclic process given below.
B
1
p
A 2
Let A1B Represent reversible process and B2A represent irreversible process between
the same states. Therefore A2B is also irreversible. Since A1B is reversible,
dQ
ΔSA1B  
A1B
T
Since cycle as a whole is irreversible and as per Clausius inequality,
dQ
 T
0

dQ dQ

A1B
T
 
B2 A
T
0
dQ
ΔSA1B  
B2 A
T
0
dQ
 ΔSB 2 A 
B2 A
 T
0
dQ

B2 A
T
 ΔSB 2 A
RHS is independent of the path which will be equal to  ΔSA1B .
LHS is dQ / T term and it is along an irreversible path and therefore it does not represent
entropy change.
Mathematical Statement of II law:

For a process involving transfer of heat Q from heat source at T1 to a heat sink at T2,
Q Q
( ΔS )total  
T1 T2
 T  T2 
( ΔS )total  Q 1 
 T1T2 
The process can be made less and less irreversible by lowering the temperature T1 closer
and closer to T2.
As the temperatures become closer and closer, irreversibility decreases and ΔStotal  0.
For any heat transfer there has to be some temperature difference. Therefore T1 > T2 and
hence,
ΔStotal  0.
This is the mathematical statement of II law of thermodynamics. Thus the entropy of the
universe always increases and the energy is conserved.

Because of irreversibility, there will be some dissipation and degradation of energy which
will not be available as work. This is called lost work which is given by
Wlost  T0 ΔStotal
Where T0 refers to the temperature of the sink to which heat is rejected.
etermination of entropy changes:

dQR
dS 
T
This is the basic equation. The heat transfer term may replaced by any term using first
law or any equation applicable to the process for which entropy change is to be
determined. This is applicable only the process is reversible. For example, for an ideal
gas undergoing isothermal reversible process,
dQ  dW  pdV
pdV
dS 
T
RdV
dS 
V
V
ΔS  R ln 2
V1
This is how entropy changes may be determined
Fundamental Property Relations:

Apart from enthalpy, internal energy and entropy, there are other thermodynamic
properties which are necessary to apply to phase equilibria and reaction equilibria. So far
we have treated only closed systems which consist of single phase without any reaction.
In order treat the systems we need to know other energy terms involved with reaction and
phase equilibria. The use these properties will get clearer when we do the chapters on
these areas.
Let us derive the fundamental property relations from basics.

Enthalpy:
From I law,
dU  dQ  dW
dU  TdS  pdV
H  U  pV
dH  dU  d(pV)
 dU  pdV  Vdp
 TdS  pdV  pdV  Vdp
dH  TdS  Vdp
Helmholtz free energy:

It is defined as
A = U – TS
Differentiating,
dA = dU-d(TS)
= TdS – pdV – TdS – SdT
dA= - pdV – SdT
Gibb‘s Free energy:

It is defined as G = H – TS
Differentiating, dG= dH –TdS – SdT

= TdS +Vdp – TdS – SdT
dG = Vdp - SdT

These four equations are called fundamental property relations as many equations are
derived from these equations.
Maxwell’s relations
As some of the thermodynamic properties are not directly measurable, we must write the
equations in terms of measurable properties. The measurable and determinable (by
experiment) properties are temperature, pressure, volume, heat capacities and in some
cases even enthalpies. These relations are derived from fundamental property relations.
The derivations are based upon a mathematical relation applied to exact differential
equations.
 f   f 
If z = f(x,y) then df    dx    dy
 x  y  y  x
This equation is also written as
df = Mdx + Ndy
For this differential equation to be exact,
 M   N 
    
 y  x  x  y
Applying these conditions to all the property relations, we get,
 M   N 
df  Mdx  Ndy     
 y  x  x  y
 T   p 
dU  TdS  pdV     
 V  S  S V
 T   V 
dH  TdS  Vdp     
 p  S  S  p

 p   S 
dA   pdV  SdT    
 T V  V  T
 V   S 
dG  Vdp  SdT     
 T  p  p T
Generating function:
Consider
 G  RTdG  Gd( RT )
d 
 RT  R 2T 2
1 G
 dG  dT
RT RT 2
1  H  TS 
 ( Vdp  SdT )   2 
dT
RT  RT 
Vdp SdT HdT SdT
   
RT RT RT 2 RT
V H
 dp  dT
RT RT 2
 G  V H
d  dp  dT
 RT  RT RT 2
From this equation, at constant temperature and at constant pressure we can write,
 ( G / RT ) V
 p   RT ;
 T
 ( G / RT ) H
 T    RT
p 2
If we know G/RT in terms of p and T, it can be used to evaluate other

thermodynamic properties and hence it is called generating function.
Entropy changes:

 Q   Q 
We know that CP    ; CV   
 T  p  T V
Since dQ  TdS ,
 S 
CP  T  
 T  p
 S  C
   P
 T  p T
And
 S 
CV  T  
 T V
 S  C
   V
 T V T
Using these,
T 
T2
dT
ΔS p   CP  CP ln 2  and
T1
T  T1 
T 
T2
dT
ΔS V   CV  CV ln 2 
T1
T  T1 
If S is considered as
S = f (T,p) then
 S   S 
dS    dT    dp
 T  p  p T
In this equation, the first partial derivative is replaced by CP/T which is derived and
second by a Maxwell‘s relation, we get,
CP  V 
dS  dT    dp
T  T  p
Similarly by taking S as function of V and T, we get,

CV  p 
dS  dT    dV
T  T V
If there is any relation between three variables, from mathematics we have, a relation
between p, V and T as
 V   p   T 
       1
 p T  T V  V  p
Using these relations, we can get,
CV ( V / T )p
dS  dT  dV
T ( V / p )T
 ( V / T )p 
dU  CV dT  T  p  dV
 ( V / p )T 
Internal energy may also be written as

  V  
dU  CP dT  T   dp  pdV 
  T  p 
Using dH  TdS  Vdp , we get
  V  
dH  CP dT  V  T    dp
  T  p 
Internal energy changes:

The internal energy changes can be expressed in terms measurable quantities such as heat
capacities, pressure, volume and temperature. We can use Maxwell‘s relations to get
these expressions.
The following are fundamental property relations.

dU  TdS  pdV
dH  TdS  Vdp
dA   pdV  SdT
dG  Vdp  SdT
We have derived the following relations.
CP  V 
dS  dT    dp
T  T  p
CV  p 
dS  dT    dV
T  T V
CV ( V / T )p
dS  dT  dV
T ( V / p )T
 V   p   T 
       1
 p T  T V  V  p
Let us derive the expression for internal energy in terms CP and CV.
dU  TdS  pdV
Replace dS in terms of CV,
C ( V / T )p 
dU  T  V dT  dV   pdV
T ( V / p )T 
 ( V / T )p 
dU  CV dT  T  p dV
 ( V / p )T 
Internal energy change in terms of Cp:
dU  TdS  pdV
Replace dS in terms of Cp,

C  V  
dU  T  P dT    dp   pdV
 T  T  p 
  V  
  T  p 

Enthalpy changes:
Starting from
dH  TdS  Vdp
in the same way we can get,
  V  
dH  CP dT  V  T   dp
  T  p 
We can use these expressions and find the changes in enthalpy. These equations are
applicable for any gas. P-V-T relations used should be for the gas for which you are
determining the changes.
Use these relations and derive the expressions for dH and dU for ideal gas.
Effect of p, V and T on U, H and S:

 S   V 
    
 p T  T  p
This is one of the Maxwell‘s relations which gives the effect of pressure on entropy at
constant temperature.
 S  C
   P
 T  p T
This equation derived earlier gives the effect of temperature on entropy at constant
pressure.
 ( V / T )p 
dU  CV dT  Vdp  T dV
 ( V / p )T 
At constant volume, dU
 CV
dT
Or
 U 
   CV
 T  V
This gives the effect of temperature on internal energy at constant volume.

At constant temperature, since dT is zero,
 U   ( V / T )p 
    T  p
 V T  ( V / p )T 
This gives the effect of volume of internal energy at constant temperature.
Similarly from
  V  
dH  CP dT  V  T   dp
  T  p 
we can get,
At constant pressure,  H   CP
 T  p
At constant temperature,  H   V 
   V  T  
 p T  T  p
These expressions give the effect of temperature and pressure on enthalpy.
Relationship between the heat capacities:

The heat capacities are related by the following expression.
 V   p 
CP  CV  T    
 T  p  T V
which can also be written as
2
 V   p 
CP  CV  T    
 T  p  V T
using the cyclic relation of partial derivatives of p, V and T.
1  V  1  V 
    ;   
 p 

V  T  p V  T
are called Volume expansivity and isothermal Compressibility. The difference between
heat capacities is written in terms of these as
 2VT
CP  CV 


Effect of pressure and volume on heat capacities:
These are given by the following equations.
 CP    2V 
   T  
 T 2 
 p T  p
 CP    2V   p 
   T   
  V 
 V T  T
2
p T
 CV   2 p 
   T  
2 
 V T  T V
 CV    2 p   V 
   T    
 T 2   p
 p T  p  T
The equation of state of a gas

is given by
RT c
V  
p T3
and the specific heat is given by
Cp  a  bT
Derive the expressions for changes in internal energy, enthalpy and entropy for an
isobaric process.
  V  
  T  p 
As pressure is constant, dp = 0,
Internal energy: dU  CP dT  pdV
dU  ( a  bT )dT  pdV
b
U12  a( T2  T1 )  ( T2 2  T1 2 )  p( V2  V1 )
2
  V  
Enthalpy: dH  CP dT  V  T   dp
  T  p 
dH  CP dT

b
H12  a( T2  T1 )  ( T2 2  T12 )
2
CP  V 
Entropy: dS  dT    dp
T  T  p
CP
dS  dT
T
 a  bT 
dS   dT
 T 
T2
S1 2  a ln  b( T2  T1 )
T1
A perfect gas is heated from 60 to 300oC at a constant pressure of 4 bar. The gas is then
cooled to 60oC at constant volume. The mass of the gas is 5 kg. Determine total entropy
change. CP and CV are 1.0 and 0.72 kJ/kg.K
pressure
T1
2
1
T2
volume
T2
dQ
S1 2  
T1
T
T2
C p dT
 
T1
T

576
 ln  0.5479kJ / kg.K
333
T3 T3
dQ CV dT 333
 S2  3  
T2
T
 
T2
T
 0.72 ln
576
 0.3945kJ / kg.K
S13  S12  S2 3

S1 3  0.5479  0.3945
 0.2161kJ / kg.K
Total entropy change = 5(0.2161)=1.0805 kJ / K
Prove that
dU  ( Cp  pV )dT  V ( p  T )dp
1  V  1  V 
Where      ,    
V  p T V  T  p
U  U(T , p )
 U   U 
dU    dT    dp
 T p  p T
dU  TdS  pdV
 U   S   V 
   T   p 
 T  p  T  p  T  p
dQ C p dT  S  Cp
dS  dS    
T T  T p T
Equation (2) becomes
 U   Cp  V 
   T    p 
 T p T   T  p
 
dU  TdS  pdV
 U   S   V 
   T    p 
 p T  p T  p T

 V   S 
    
 T  p  p T
 U   V   V 
   T    p 
 p T  T  p  p T
  Cp  V     V   V  
dU  T    p   dT    T    p  dp
  T  p 
  T    T  p  p T 
  V     V   V  
 C p  p  dT  T    p  dp
  T  p    T  p  p T 
 ( Cp  pV )dT  ( TV  pV )dp
dU  ( Cp  pV )dT  V ( p  T )dp
For ideal gas show that
 U   U   U 
       0
 p T  V T  S T
dU  TdS  pdV
 U   V 
   T  p 
 S T  S T
 U   T 
   T  p 
 S T  p V
pV
T 
R
 T  V
  
 p  V R
 U  V
  T p 0
 S T R
dU  TdS  pdV
 U   S 
   T  p
 V T  V T
 p   S 
   
 T V  V T
 U   p 
   T  p
 V T  T V

H  U  pV
U  H  pV
 U   H    V  
       p   V 
 p T  p T   p T 
 H   V 
   V  T  
 p T  T  p
 U    V     V  
   V  T      p   V 
 p T   T  p    p T 
 U   V   V 
   T    p 
 p T  T  p  p T
 U  R RT
   T  p 2  0
 p T p p
And hence
 U   U   U 
       0
 p T  V T  S T
Fugacity
It is derived from Latin, expressed as fleetness or escaping tendency. It is used to study
extensively phase and chemical reaction equilibrium.
We know that
dG  VdP  SdT -(1)
For isothermal condition

dG  VdP
For ideal gases

RT
V 
P
RT
dG   .dP
P
dG  RTd ln P
To find Gibbs free energy for an real gases. True pressure is related by effective
pressure. Which we call fugacity(f).
dG  RTd ln f -------(2)
Applicable for all gases (ideal or real)
On differentiation
G  RT ln f  
 Is an constant depends on temperature and nature of gas.
fugacity has same units as pressure for an ideal gas.
For ideal Gases

dG  VdP  SdT
For Isothermal conditions
dG  VdP
from equation (2)
RTd ln f  VdP
V
d ln f  dP
RT
dp
d ln f 
p
d ln f  d ln p
f p Fugacity = Pressure for Ideal gases
Fugacity coefficient ( ) : Fugacity coefficient ids defined as the ratio of fugacity of a

component to its pressure.
f

P
 Is the measure of non ideal behavior of the gas.
Standard State: Pure gases, solids and liquids at temperature of 298k at 1 atmosphere are
said to exist at standard condition. The property at this condition are known as standard
state property and is denoted by subscript‘o‘.

G o = Standard Gibbs free energy
f o = Standard fugacity
Estimation of fugacity for gases

I method
dG  VdP  SdT
For Isothermal conditions
dG  VdP
from equation (2)
RTd ln f  VdP
V
d ln f  dP
RT
Integrating the above equation with the limits 0 to f and pressure 1 to P
P
V
 d ln f   RT dP
1
Lower limit is taken as P =1 atm

At 1 atm assuming the gases expected to behave ideally
P
1
RT 1
ln f  VdP
if PVT relations are known , we can find fugacity at any temperature and pressure
II method
Using compressibility factor
dG  VdP
RTd ln f  VdP --------------(2)
ZRT
V in terms of compressibility terms it is given as V 
P
Substitute V in equation 2
ZRT
RTd ln f  dP
p
d ln f  Zd ln p
subtracting both sides by dlnP
d ln f  d ln P  Zd ln P  d ln P

f
d ln  ( z  1)d ln P
P
d ln   (Z  1)d ln P
Integrating the equation from 1 to  and 0 to P
 P
 d ln    (Z  1)d ln P
1 0
P
dP
ln    ( Z  1)
0
P
Using generalized charts: using reduced properties a similar chart as compressibility chart
is predicted for fugacity.
f Z 1
ln   dPr
P Pr
Fugacity is plotted against various reduced pressure at various reduced temperature
Using Residual Volume(): The residual volume is the difference between actual
volume (V) and the volume occupied by one mole of gas under same temperature and
RT RT
pressure   V  , V  
P P
 RT 
dG    dP  RTd ln f
 P 
  dP 
RT  dP    RTd ln f
 RT P 

 f
dP  d ln  
RT P
f 
ln  dP
P RT
Problem
For isopropanol vapor at 200oC the following equation is available
Z=1- 9.86 x 10-3P-11.45 x 10-5P2
Where P is in bars. Estimate the fugacity at 50 bars and 200 oC
PV
Z  1  9.86  10 3 P  11.41  10 5 P 2
RT
ZRT RT
V  (1  9.86  10 3 P  11.41  10 5 P 2 )
p P
P
1
RT 1
ln f  VdP
P
1 RT
ln f 
RT 
1
P
(1  9.86  10 3 P  11.41  10 5 P 2 )dP
50 50 50
dp
1 p  1 9.86  10 dP  1 11.41 10 PdP
3 5
ln f 
 50  5 (50  1 )
2 2
ln f  ln    9.86  10 50  1  11.41  10
3
 1 2
f=26.744 bar
f 26.744
   0.5348
P 50
Fugacity for liquids and solids
General expression for fugacity is

P
1
RT 1
ln f  VdP

For solids and liquids at constant temperature the specific volume does not change
appreciably with pressure, therefore the above equation is integrated by taking volume
constant. Integrating the above equation from condition 1 to 2
f2 P
V 2
f ln f 
RT P dP
1 1
f2
ln 
V
P2  P1 
f1 RT
Problem:
Liquid chlorine at 25oC has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa and Molar
volume 5.1x 10-2 m3/kg mole. What is the fugacity at 10 Mpa and 25oC
P1  0.77  10 6 Pa
J
f1  0.7  10 6 Pa T  298K R  8314
Kgmole
P2  10  10 6 Pa
f2
ln 
V
P2  P1 
f1 RT
f=0.846Mpa
Activity(a):
It is defined as the fugacity of the existing condition to the standard state fugacity
f
a o
f
Effect of pressure on activity
The change in Gibbs free energy for a process accompanying change of state from
standard state at given condition at constant temperature can be predicted as
G  RT ln f G o  RT ln f o
 f 
G  G  G o  RT ln  o   RT ln a
f 
at constant temperature dG  VdP

G P
 dG  V  dP
GO Po
G  V ( P  P o ) RT ln a  V ( P  P o )
V
ln a  ( P  P o ) This equation predicts the effect of pressure on activity
RT
Effect of Temperature on Activity
G  G  G o  RT ln a
G Go
R ln a  
T T
Differentiating the above equation with T at constant P
 G   Go  
      
 d ln a    T    T  
R    
 dT  P  T   T 
 
  P  
P
 d ln a 
o
H H
R   
 dT  P
2
RT RT 2
 d ln a  Ho H
R   This equation predicts the effect of temperature on activity.
 dT  P RT 2
Properties of solutions
The relationships for pure component are not applicable to solutions. Which needs
modification because of the change in thermodynamic properties of solution. The
pressure temperature and amount of various constituents determines an extensive state.
The pressure, temperature and composition determine intensive state of a system.
Partial Molar properties:

The properties of a solution are not additive properties, it means volume of solution is not
the sum of pure components volume. When a substance becomes a part of a solution it
looses its identity but it still contributes to the property of the solution.
The term partial molar property is used to designate the component property when it is
admixture with one or more component solution.
A mole of component i is a particular solution at specified temperature and pressure has

got a set of properties associated with it like VP , S i etc . These properties are partially
responsible for the properties of solution and it is known as partial molar property
It is defined as
 nM 
Mi    ji
  n i  T , P ,n
j
M i = Partial molar property of component i.

M = Any thermodynamic property of the solution
n = Total number moles in a solution
ni=Number of moles of component I in the solution
This equation defines how the solution property is distributed among the components.
Thus the partial molar properties can be treated exactly as if they represented the molar
property of component in the solution.
The above expression is applicable only for an extensive property using
We can write
ni
nM   ni M i  xi
n
M   xi M i
xi=Mole fraction of component i in the solution.
Measuring of partial molar properties

To understand the meaning of physical molar properties consider a open beaker
containing huge volume of water in one mole of water is added to it, the volume increase
is 18x 10-6 m3 If the same amount of water is added to pure ethanol the volume increased
is approximately 14 x 10 -6m3 this is the partial molar volume of H2O in pure ethanol.
The difference in volume can explain the volume applied by water molecules depending
on water molecules surrounding to them. When water is added to large amount of
ethanol, ethanol molecules hence volume occupied surround all the water molecules will
be different in ethanol.

If same quantity of water is added to an equimolar mixture of H 2O and ethanol, the
volume change will be different. Therefore Partial molar property change with
composition. The intermolecular forces also changes with change in thermodynamic
property.
Let Vw = Partial molar volume of the water in ethanol water solution
V w = Molar volume of pure water at same temperature and pressure
V t =Total volume of solution when water added to ethanol water mixture and allowed
for sufficient time so that the temperature remains constant
V t  n w Vw
V t
Vw 
n w
In a process a finite quantity of water is added which causes finite change in composition.
Vw = property of solution for all infinitely small amount of water.
V t  V t 
Vw  lim v0  
nw  nw 
Temperature pressure an number of moles of ethanol remains constant during addition of

water.
 V t 
Vw    nE- no of moles of ethanol
 nw  T , P ,nE
The partial molar volume of component i

 V t 
Vi   
 ni  T , P ,n i
j
Partial molar properties and properties of the solution
Consider any thermodynamic extensive property (Vi, Gi etc) for homogenous system can
be determined by knowing the temperature, pressure and various amount of constituents.
Let total property of the solution

M t  nM
n  n1  n2  n3       
1,2,3 represents no of constituents
Thermodynamic property is a f T , P, n1 , n2 , n3      n j 

For small change in the pressure and temperature and amount of various constituents can
be written as
 M t   M t   M t   M t 
dM t    dP    dT    dn        dni   
 P  T ,n  P  p ,n  P  T , p ,n ,n   P  P ,T ,n i
1
2 3 j
At constant temperature and pressure dP and dT are equal to zero.

The above equation reduces to
 M t 
i n
dM   
t
 dni
i 1  ni  P.T , n
j i
dMt in terms of partial molar property

n
dM t   M i dni
i 1
M i is an extensive property depends on composition and relative amount of constituents.

All constituent properties at constant temperature and pressure are added to give the
property of the solution.
dM t  M 1dn1  M 2 dn2  M 3 dn3      

dM t  M 1 x1  M 2 x2  M 3 x3       dn 
 
M  M 1 x1  M 2 x2  M 3 x3       n  M 1n1  M 2 n 2  M 3 n 3
t
M t   ni M i
Problem
A 30% mole by methanol –water solution is to be prepared. How many m3 of pure
methanol (molar volume =40.7x10 -3 m3/mol) and pure water (molar volume =
18.068x10-6 m3/mol) are to be mixed to prepare 2m3 of desired solution. The partial molar
volume of methanol and water in 30% solution are 38.36x10 -6 m3/mol and 17.765x10 -6
m3/mol respectively.
Methanol =0.3 mole fraction
Water=0.7 mole fraction
Vt=0.3 x38.36x10-6+0.7x17.765x10-6
=24.025x10-6 m3/mol
For 2 m3soolution
2
 6
 83.246  10 3 mol
24.025  10
Number of moles of methanol in 2m3solution

=83.246x103x0.3= 24.97x103 mol
Number of moles of water in 2m3solution
=83.246x103x07= 58.272x103mol
Volume of pure methanol to be taken

= 24.97x103 x 40.7x10-3 =1.0717 m3
Volume of pure water to be taken

= 58.272x103 x 18.068x10-6 =1.0529 m3
Estimation of Partial molar properties for a binary mixture :

Two methods for estimation
Analytical Method and Graphical Method(Tangent Intercept method)
Analytical Method: The general relation between partial molar property and molar
property of the solution is given by
 M 
M i  M   x k   k  i x1
 x K  T , P ,n
k
For binary mixture

i  1, k  2
 M 
M 1  M  x 2   x2  x1  1, x2  1  x1 , x2  x1
 x 2  T , P
At constant Temperature and pressure
 M 
M 1  M  (1  x1 )  ------(a)
 x1 
 M 
M 2  M  x1  -----------(b)
 x1 
The partial molar property (extensive property) for a binary mixture can be estimated
from the property of solution using above equations (a) and (b).

Tangent Intercept method:
This is the graphical method to estimate partial molar properties. If the partial molar
property (M) is plotted against the composition we get the curve as shown in the figure.
Suppose partial molar properties of components required at any composition, and then
draw a tangent to this point to the curve. The intercept of the tangent with two axis x 1=1
and x1=0 are I1 and I2.
dM M  I 2
Slope of the tangent 
dx1 x1
dM
M  I 2  x1
dx1
dM
I 2  M  x1
dx1
Comparing I2 with equation (b) I 2  M 2
dM I 1  M
and also (right hand side) 
dx1 1  x1
dM
I 1  M  1  x1
dx1

dM
I 1  M  1  x1 Comparing with equation(a) I 1  M 1
dx1
The intercept of the tangent gives the partial molar properties.
Limiting cases: For infinite dilution of component when at x1=0 a tangent is drawn at

x1=0 will give the partial molar property of component 1 at infinite dilution ( M 1 ) and

tangent is drawn at x2=0 or x1=1 will give infinite dilution ( M 2 ) of component 2

M2
Problem
The Gibbs free energy of a binary solution is given by
cal
G  100 x1  150 x2  x1 x2 (10 x1  x2 )
mol
(a) Finnd the partial molar free energies of the components at x2=0.8 and also at infinite
dilution.
(b) Find the pure component properties
cal
Sol: G  100 x1  150 x2  x1 x2 (10 x1  x2 )
mol
Substitute x2  1  x1 and simplifying
G  9 x1  8x1  49 x1  150
3 2
 G 
G1  G  (1  x1 ) 
 x1 
G
 27 x1  16 x1  49
2
x1
G1  18x1  35x1  16 x1  101

3 2
 G 
G2  G  x1  
 x1 

G2  18x1  8x1  150
3 2
To find the partial molar properties of components 1 and 2
x2=0.8, x1=1-0.8 = 0.2
G1  18x1  35x1  16 x1  101

3 2
cal
G1  102.944
mol
G2  18x1  8x1  150

3 2
cal
G2  149.824
mol
At infinite dilution

G1  G1atx1  0
 cal
G1  101
mol

G2  G2 atx1  1 or x2=0
 cal
G2  160
mol
To find the pure component property
G1  G1atx1  1
cal
G1  100
mol
G2  G2 atx1  0
cal
G1  150
mol

Chemical Potential:
It is widely used as a thermodynamic property. It is used as a index in chemical
equilibrium, same as pressure and temperature. The chemical potential  i of component i
in a solution is same as its partial molar free energy in the solution G i
The chemical potential of component i
 G t 
i  Gi   
 ni  T , P ,n j
G t  f P, T , n1 , n2     
 G t   G t  i n
 G t 
dG    dP    dT   
t
 dni
 P  T ,n  T  P ,n i  1  ni  T ,n
j
 G t   G t 
dG t    dP    dT    i dni
 P  T ,n  T  P ,n
For closed system there will be no exchange of constituents (n is constant)
dG t  V t dP  S t dT
at constant temperature
 G 
 P   V
t
at constant pressure
 G 
 T    S
t
dG t  V t dP  S t dT    i dni

At constant temperature and pressure
dG 
t
T ,P    i dni
For binary solution G  x1 1  x2  2
Effect of temperature and pressure on chemical potential

Effect of temperature:
We know that
 G t 
i  Gi    -------------------(1)
 ni  T , P ,n j
differentiating equation (1) with respect to T at constant P
  i   2G
 T   Tdn ---------------------(2)
  P ,n i
dG  VdP  SdT ---------(3)
 G 
 T    S
P
differentiating again w r t ni
 2G  S t 
     Si
Tni  ni  P ,n j
S i is partial molar entropy of component I
  i    
  T  T  i   i
      T 
 T  T2
 
  P ,n

 T Si  i

T2
G  H  TS
In terms of partial molar properties
Gi  H i  T S i
 i  H i  T S i
H i    i  T S i
  i   Hi
 T  
  P ,n T2
This equation represents the effect of temperature on chemical potential.
Effect of Pressure:
We know that
 G t 
i  Gi    -------------------(4)
 ni  T , P ,n
j
  i   2G
 P   Pdn ---------------------(5)
  T ,n i
dG  VdP  SdT ---------(3)
differentiating equation (3) with respect to P at constant T
 G 
 P   V
T

 2G  V 
   Vi ,
Pni  ni  T ,n
j
  i 
 P   Vi
  T ,n
This equation represents the effect of pressure on chemical potential
Fugacity in solutions
For pure fluids fugacity is explained as
dG  RTd ln f
f
lim P0 1
P
The fugacity of the component i in the solution is defined as analogously by
d i  RTd ln f i
f
limP 0 i
1
Pi
 i is Chemical potential
f i is partial molar fugacity
For ideal gases Pi  yi  PT
PT – Total pressure.
Fugacity in Gaseous solutions
We know that
 G t 
i  Gi    ------(1)
 ni  T , P ,n
j

  i   2G
 P   -----(2)
  T ,n Pdn i
dG  VdP  SdT -----(3)
differentiating equation (3) with respect to P at constant T
 G 
 P   V
T
 2G  V 
   Vi ,
Pni  ni  T ,n
j
  i 
 P   Vi
  T ,n
  i  Vi P
RTd ln f i  Vi dP
Vi
d ln f i  dP
RT
Subtracting both sides by d ln Pi
Vi
d ln f i  d ln P i  dP  d ln P i
RT
f  V
d ln  i   i dP  d ln P i
 Pi  RT
d ln Pi  d ln P  d ln yi
Composition is constant dln yi=0
The above equation can be written as

dP
d ln Pi  d ln P 
P
Modifying equation (a)
 
d ln i 
1 
V i 
RT 
dP
RT  P 
 i - Represents fugacity of the component i in the solution.
Ideal solutions
An ideal mixture is one, which there is no change in volume due to mixing. In other
words for an ideal gaseous mixture partial molar volume of each component will be equal
to its pure component volume at same temperature and pressure.
and V  Vi xi   xiVi --- Raoults law

Ideal solutins are formed when similar components or adjacent groups of group are
mixed
Eg: Benzene-Toluene
Methanol- Ethanol
Hexane- Heptane
Solutin undergo change in volume due to mixing are known as non ideal solutions
Vi  Vi
Eg: Methanol-Water
Ethanol-water.
Ideal solutions formed when the intermolecular force between like molecules and unlike
molecules are of the same magnitude.
Non-ideal solutions are formed when intermolecular forces between like molecules and
unlike molecules of different magnitude.
For ideal solutions
V t   niVi -------------------(1)
Vi is the molar volume of pure component I

 V t 
Vi   T , P , n j  Vi ----------------- (2)

 i 
n
The residual volume for the pure component is

RT
  Vi 
p

Therefore we know from reduced properties
1  RT 
P
f
ln i 
P RT 0   Vi  dP ----(3)
P 
For component i in terms of partial molar properties
1  RT 
P
f
ln i 
Pi RT 0   V i 
P 
dP ----(4)
Subtracting equation (3) from (4)
 V 
P
fi P 1
ln  i  Vi dP ----(5)
f i Pi RT 0
we know that Pi  yi P
equation (5) reduces to
 
P
fi 1
f i yi RT 0
ln  V i  Vi dP
comparing equation (2)

fi
1
f i yi
f i  f i yi --Lewis Randal rule

Lewis Randal rule is applicable for evaluating fugacity of components in gas mixture.
Lewis Randal rule is valid for
1. At low pressure when gas behaves ideally.
2. When Physical properties are nearly same.
3. At any pressure if component present in exess.
Henrys Law
This law is applicable for small concentration ranges. For ideal solution Henrys law is
given as
f i  xi k i
Pi  xi k i
ki- Henrys Constant, f i -Partial molar fugacity,

Pi -Partial pressure of component i.
Non Ideal solutions

For ideal solutions f i  xi k i ------------(a)

For non ideal solutions f i   i xi k i ----------(b)
Where  i is an activity coefficient of component i.

Comparing equation (a) and (b)
f
 i  i  Non ideal solution / Ideal solution
fi
For both ideal and Non ideal solutions the fugacity of solution is given by
equation
f
ln f   xi ln i
xi
ln    xi ln i
Problem:
A terinary gas mixture contains 20mole% A 35mole% B and 45mole% C at 60 atm and
75oC. The fugacity coefficients of A,B and C in this mixture are 0.7,, 0.6 and 0.9.
Calculate the fugacity of the mixture.
Solution:
ln   x A ln  A  x B ln  B  xc ln c
ln   0.2 ln(0.7)  0.35 ln(0.6)  0.45 ln(0.9)
ln   0.2975
  0.7426
f
 , f =44.558atm
P
Gibbs Duhem Equation

Consider a multi component solution having ni moles of component I the property of
solution be M in terms of partial molar properties
M t  nM   n M i -----------------------(1).
Where n is the total no of moles of solution

Differentiating eq (1) we get
d (nm)   ni d M i   M i dni ----------------------------(2)
We know that

nM  f T , P, n1 , n2     

 (nM )   (nM )   (nM )   (nM ) 
(nM )    dT    dP    dn1    dn2     
 T  P ,n1 ,n2   P  T ,n1 ,n2   n1  T , P1 ,n2.n3  n2  T , P ,n1 ,n3 
 n( M )   n( M )   (nM ) 

(nM )   
 T  P , n1 , n2  
dT   P  dP     dni
  T , n1 , n2    ni  T , P , n j
From the definition of partial molar properties
 n( M )   n( M ) 
(nM )   dT  dP   M i dni
 T  P ,n1 ,n2   P  ----------(3)
T ,n1 ,n2  
Subtracting equation (2) from equation (3)

 n( M )   n( M ) 
 T  dT   dP   ni d M i  0 ------------------(4)
P ,n1 , n2    P  T ,n1 ,n2 
Equatin (4) is the fundamental form of Gibbs Duhem equation
Special Case
At constant temperature and pressure dT and dP are equal to zero. The equation becomes
 xi d M i  0
For binary solution at constant temperature and pressure the equation becomes
x1d M 1  x2 d M 2  0
x1d M 1  (1  x1 )d M 2  0 ------------(5)
dividing equation(5) by dx1
d M1 dM2
x1  (1  x1 ) 0
dx1 dx1
The above equation is Gibbs Duhem equation for binary solution at constant temperature
and pressure in terms of Partial molar properties.
Any Data or equation on Partial molar properties must satisfy Gibbs Duhem
equation.

Problem:
Find weather the equation given below is thermodynamically consistent
G  100 x1  150 x2  x1 x2 (10 x1  x2 )
G
G1  G  (1  x1 )
x1
G
G2  G  x1
x1
G1  18x1  35x1  16 x1  101
3 2
G2  18x1  8x1  150

3 2
d G1
 54 x1  70 x1  16
2
dx1
d G2
 54 x1  16 x1
2
dx1
G D equation
d M1 dM2
x1  (1  x1 ) 0
dx1 dx1
x 1 ( 54 x 1  70 x 1  16 )  ( 1  x1 )( 54 x 1  16 x 1 )  0
2 2
It satisfies the GD equation, the above equation is consistent.
Phase Equilibrium
Criteria for phase equilibrium: If a system says to be in thermodynamic equilibrium,
Temperature, pressure must be constant and there should not be any mass transfer.
The different criteria for phase equilibrium are
At Constant U and V: An isolated system do not exchange mass or heat or work with
surroundings. Therefore dQ=0, dW=0 hence dU=0. A perfectly insulated vessel at
constant volume dU=0 and dV=0.
dSU ,V  0
At Constant T and V: Helmoltz free energy is given by the expression
A  U  TS
U  A  TS
on differentiating
dU  dA  TdS  SdT
we know that

dU  TdS  PdV
TdS  PdV  dA  TdS  SdT
dA  PdV  SdT
Under the restriction of constant temperature and volume the equation simplifies to
dAT ,V  0
At Constant P and T
The equation defines Gibbs free energy
G  H  TS
G  U  PV  TS
dG  dU  PdV  VdP  TdS  SdT
dU  dG  PdV  VdP  TdS  SdT

dU  dG  dG  PdV  TdS
Under the restriction of constant Pressure and Temperature the equation simplifies to
dGT , P  0
This means the Gibbs free energy decreases or remains un altered depending on the
reversibility and the irreversibility of the process. It implies that for a system at
equilibrium at given temperature and pressure the free energy must be minimum.
Phase Equilibrium in single component system
Consider a thermodynamic equilibrium system consisting of two or more phases of a

single substance. Though the individual phases can exchange mass with each other.
Consider equilibrium between vapor and liquid phases for a single substance at constant
temperature and pressure. Appling the criteria of equilibrium
dG  0
dG a  dG b  0
dG a and dG b are chane in free energies of the phases a and b respectively.
We know that
dG  VdP  SdT   Gi dni
For phase a
dG a  V a dP a  S a dT a  G a dn a
For phase b
dG b  V b dP b  S b dT b  G b dn b

At constant temperature and pressure
dG a  G a dn a , dG b  G b dn b
For a whole system to be at equilibrium
dn a  dn b  0
or
dn a  dn b
G a

 G b dn a  0
Ga  Gb
When two phases are in equilibrium at constant temperature and pressure, Gibbs free
energies must be same in each phase for equilibrium.
RT ln f a  C  RT ln f b  C
fa  fb
Clapeyron Clausius Equation

Clapeyron Clausius Equation are developed two phases when they are in equilibrium
(a) Solid- liquid

(b) Liquid-Vapor
(c) Solid Vapor
Consider any two phases are in equilibrium with each other at given temperature and
pressure. It is possible to transfer some amount of substance from one phase to other
in a thermodynamically reversible manner(infinitely slow).The equal amount of
substance will have same free energies at equilibrium .
Consider GA is Gibbs free energy in phase A and GB is Gibbs free energy in phase B
at equilibrium.
GA=GB ------(1)
G = GA -GB =0 ------(2)
At new temperature and pressure the free energy / mole of substance in phase A is
G A  dG A for Phase B G B  dG B
From basic equation

dG  VdP  SdT -----(3)
dG A  V A dP  S A dT
dG B  VB dP  S B dT

V A dP  S A dT  VB dP  S B dT
dPVB  V A   dT S B  S A 
dP S

dT V
V represents the change in volume when one mole of substance pases from
phase A to Phase B
Q
S 
T
dP Q

dT TV
dP Q
 ----(4)
dT T V B  V A 
This is a basic equation of Clapeyorn Clasius equation.

B—Vapor state A- Liquid state
Q=molar heat of vaporization = H V
VB is molar volume in vapor state, VA is molar volume in liquid state,
dP Q


dT T V g  Vl 
Vg>>>Vl (Gas volume is very high when compared to liquid volume)
dP H V

dT TV g
RT
HV   (Latent heat of vaporization), V g 
P
dP P

dT TRT
dP  dT

P RT2

Integrating the above equation from T1to T2 and pressure from P1 to P2.
dP  2 dT
P2 T
P P  R T T
1 1
P    1 1
ln 2     
 P1  R  T1 T2 
This equation is used to calculate the vapor pressure at any desired temperature.
Problem:
The vapor pressure of water at 100oC is 760mmHg. What will be the vapor pressure
at 95oC. The latent heat of vaporization of water at this temperature range is
41.27KJ/mole.
P1  760 mmHg T1  100  273  373 K
P2     T2  95  273  368 K
P    1 1
ln 2     
 P1  R  T1 T2 
 P  41.27  10 3  1 1 
ln 2    373  368 
760  8.314  
P2  634.3mmHg
Phase Equilibrium in Multi component system

An heterogeneous system contains two or more phases and each phase contains two or
more components in different proportions. Therefore it is necessary to develop phase
equilibrium for multi component system in terms of chemical potential.
The partial molar free energy or chemical potential is given as
 G 
 i  Gi   
 ni  T , P ,n
j
For a system to be in equilibrium with respect to mass transfer the driving force for
mass transfer( Chemical potential) must have uniform values for each component in
all phases.

Consider a heterogeneous system consists of phase  ,  ,          and
containing various components 1,2,3-------C , that constitutes the system.
The symbol  i represents chemical potential of component ―i‖in phase k.
k
At constant temperature and pressure, for the criterion for equilibrium is

dG=0 ----(1)
Free energy for multi component system given by the expression

dG  VdP  SdT    i dni ------(2)
At constant Temperature and pressure
dG  i dni ----(3)
Comparing equation 1 and 3

0    i dni
For multi component system
C 
  dni  0
k k
i
i 1 k 
Expanding the above equation
1 dn1  1  dn1   1 dn1             1 dn1 
 2  dn2    2  dn2    2  dn2               2  dn2  

-----(4)


 c  dnc    c  dnc    c  dnc               c  dnc   0
Since the whole system is closed it should satisfy the mass conservation equation
  
dn1  dn1      dn1 
  
dn2  dn2      dn2 
 ----(5)

  
dnC  dnC      dnC  0
The variation in number of moles dni is independent of each other. However the sum of
change in mole in all the phases must be zero. For the criterion of equilibrium is that the
chemical potential of each component must be equal in all phases.

1  1           1
 2   2            2


C   C           C 
At constant temperature and pressure the general criterion for thermodynamic
equilibrium in closed system for heterogeneous multi component system
At constant T and P
  
 i  i          i for i=1,2,3--------C
Since  i  Gi  RT ln f i  
The above equation is also satisfied in terms of fugacity

  
fi  fi        fi for i=1,2,3--------C
Phase Diagram for Binary solution
Constant pressure equilibrium

Consider a Binary system made up of component A and B. Where it is assumed to be
more volatile than B where vapour pressure ‗A‘ is more than ‗B‘. When the pressure is
fixed at the liquid composition can be changed the properities such as temperature and
vapour compositions get quickly determined VLE at constant pressure is represented on
T-xy diagram.
Boiling point diagrams
When temperature is plotted against liquid(x) and vapour(y) phase composition. The
upper curve gives and lower curve gives. The lower curve is called as bubble point
curve and upper curve is called as Dew point curve. The mixture below bubble point is
sub cooled liquid and above the Dew point is super heated vapour. The region between
bubble point and Dew point is called mixture of liquid and vapour phase.

Consider a liquid mixture whose composition and temperature is represented by
point ‗A‘. When the mixture is heated slowly temperature rises and reach to point ‗B‘,
where the liquid starts boiling, temperature at that point is called boiling point of whether
heating mixture reaches to point ‗G‘ when all liquids converts to vapour the temperature
at that point is called as Dew point. Further heating results in super heated vapour. The
number of tic lies connects between vapour and liquid phase. For a solution the term
boiling point has no meaning because temperature varies from boiling point to Dew point
at constant pressure.
Effect of pressure on VLE

The boiling point diagram is drawn from composition x=0 to x=1, boiling point of pure
substances increases with increase in pressure. The variation of boiling point diagrams
with pressure is as shown in diagram. The high pressure diagrams are above low
pressure.

Equilibrium diagram
Vapor composition is drawn against liquid comp at constant pressure. Vapour is always
rich in more volatile component the curve lies above the diagonal line.
Constant temperature Equilibrium
VLE diagram is drawn against composition at constant temperature. The upper curve is
and lower curve is drawn at vapour comp(y). Consider a liquid at known pressure and
composition at point ‗A‘ as the pressure is decreases and reaches to point ‗B‘ where it
starts boiling further decreases in pressure reaches to point ‗C‘ when all the liquid
converts to vapour, further decreases in pressure leads to formation of super heated
vapour. In between B to C both liquid and vapour exists together

Non ideal solution
An ideal solution obeys Raoults law and p-x line will be straight. Non ideal solution do
not obey Raoults law. The total pressure for non ideal solutions may be greater or lower
than that for ideal solution. When total pressure is greater than pressure given by Raoults
law, the system shows positive deviation from Raoults law.
Eg: Ethanol-toluene
When the total pressure at equilibrium is less than the pressure given by Roults law the
system shows negative deviation from Raoults law.
Eg: Tetrahydrofuron-ccl4
Azeotropes
Azeotropes are constant boiling mixtures. When the deviation from Raoults law is very
large p-x and p-y curve meets at this point y1=x1 and y2=x2
A mixture of this composition is known as Azeotrope. Azeotrope is a vapour liquid
equilibrium mixture having the same composition in both the phases.

Types of Azeotropes
Azeotropes are classified into two types
1. Maximum curve pressure, minimum boiling azeotropes

2. Minimum pressure maximum boiling azeotrope
The azeotrope formed when negative deviation is very large will exhibit minimum
pressure or maximum boiling point, this is known as minimum pressure Azeotrope.
Eg : Ethanol –water, benzene-ethanol
The azeotrope formed when –ue deviation is very large will exhibit minimum pressure or
maximum boiling point, this is known as minimum pressure azeotrope.
Phase diagram for both types of Azeotropes
Minimum Temperature azeotropes

Maximum Tem – Min pressure Azeotropes
Calculation of VLE for ideal solution
Ideal solution: Ideal solution is one which obeys Raoults law. Raoults law states that the
partial pressure is equal to product of vapor pressure and mole fraction in liquid phase.
PA  PVA x A
PA- Partial pressure

PVA- Vapor pressure
xA- Mole fraction of component A
For binary solution (For component A and B)

We know that PT  PA  PB -------(1)
PA  PVA x A , PB  PVB x B
Substitute PA and PB in equation 1
PT  PVA x A  PVB x B
1  x A  xB , 1  x A  xB
PT  PVA x A  PVB (1  x A )
PT  PVA  PVB x A  PVB --------(2)
P  PVB
xA  T
PVA  PVB
Assuming the vapor phase is also ideal
PA PVA x A
yA  
PT PT
Substituting PT from equation (2)
PVA x A
yA 
PVA  PVB x A  PVB
Dividing numerator and denominator by PVB
PVA
xA
PVB
yA 
 PVA 
  1 x A  1
 PVB 
x A
yA 
  1x A  1
The above equation relates x and y
 is known as relative volatility of component A with respect to component B

Problem: The binary system acetone and acetone nitrile form an ideal solution. Using
the following data prepare
 P-x-y diagram at 50oC
 T-x-y diagram at 400mm Hg
 x-y diagram at 400 mm Hg
T PV1 PV2
38.45 400 159.4
42 458.3 184.6
46 532 216.8
50 615 253.5
54 707.9 295.2
58 811.8 342.3
62.3 937.4 400
PV 1 x1
Solution: PT  PV 1  PV 2 x1  PV 2 , y A  , PV1= 615, PV2 = 253.5
PT
x1 PT y1
0.0 253.5 0.0
0.2 325.8 0.377
0.4 398.1 0.6179
0.6 470.4 0.784
0.8 542.7 0.906
1.0 615 1
PT  PV 2 P x
T-x-y diagram at 400 mm Hg , PT=400mmHg x1  , y A  V1 1
PV 1  PV 2 PT
T PV1 PV2 x1 y1
38.45 400 159.4 1 1
42 458.3 184.6 0.7869 0.9015
46 532 216.8 0.5812 0.7729
50 615 253.5 0.405 0.6226
54 707.9 295.2 0.2539 0.449
58 811.8 342.3 0.122 0.2475
62.3 937.4 400 0 0
Calculation of VLE for non Ideal solution
For non ideal solution

Partial pressure is given by Pi   i xi PVi
 i - Activity coefficient

xi- Mole fraction
PVi – vapor pressure
For binary mixture
P1   1 x1 PV 1
P2   2 x2 PV 2
PT  P1  P2
PT   1 x1 PV 1   2 x2 PV 2
P1  1 x1 PV 1 1
y1   
 x P
PT  1 x1 PV 1   2 x 2 PV 2
1 2 2 V2
 1 x1 PV 1
The above equation relates x and y for non ideal solution
Activity coefficients are functions of liquid composition x, many equations are available
to estimate them. The important equations are
Vanlaar equation
Wilson equation
Margules Equation
Vanlaar Equation:
Estimation of activity coefficient
2
Ax 2
ln  1  2
A 
x
 B 1  x 2

2
Bx1
ln  2  2
 B 
 x1  A x 2 
Where A and b are known as vanlaar constants, if the constants are known the
activity coefficients can be estimated.
Estimation of Vanlaar constants

1st Method: If the activity coefficients are known at any one composition, then vanlaar
constants A and B can be estimated by rearranging the equation

2
 x ln  2 
A  ln  1 1  2 
 x1 ln  1 
2
 x ln  1 
B  ln  2 1  1 
 x 2 ln  2 
2nd Method
For a systems forming azeotrope, if the temperature and pressure s are known at
azeotropic composition then activity coefficients can be calculated as shown below.
P1  x1 1 PV 1
PT y1  x1 1 PV 1
At azeotrpic composition x1=y1

PT PT
 1, 2
PV 1 PV 2
Van laar constants A and B can calculated using the above equations.
Problem: The azeotope of ethanol and benzene has composition of 44.8mol% C2H5OH at
68oC and 760mmHg.At 68oC the vapor pressure of benzene and ethanol are 517 and 506
mmHg.
Calculate
 Vanlaar constants
 Prepare the graph of activity coefficients Vs composition
 Assuming the ratio of vapor pressure remains constant, prepare equilibrium
diagram at 760mmHg.
Solution:
At azeotropic composition x1=y1=0.448, x2=y2=0.552, PV1=506mmHg,
PV2 =517mmHg
PT PT
 1, 2
PV 1 PV 2
760 760
  1  1.501 ,   2  1.47
506 517
2
 x ln  2 
A  ln  1 1  2 
 x1 ln  1 

2
 (0.552) ln(1.47) 
A  ln(1.501) 1  
 (0.448) ln(1.501) 
A=0.829
2
 x ln  1 
B  ln  2 1  1 
 x 2 ln  2 
2
 (0.448) ln(1.501) 
B  ln(1.47) 1 
 (0.552) ln(1.47) 
B=0.576
Make use of the equations given below for plotting graph of activity coefficients Vs
composition.
2 2
Ax 2 Bx1
ln  1  2
, ln  2  2
A   B 
 B x1  x 2   x1  A x 2 
P1  1 x1 PV 1 1
y1   
PT  1 x1 PV 1   2 x 2 PV 2  x P
1 2 2 V2
 1 x1 PV 1
x1 x2 1 2 y1
0 1 6.745 1 0
0.2 0.8 2.4 1.095 0.384
0.4 0.6 1.644 1.374 0.4384
0.6 0.4 1.21 1.721 0.5077
0.8 0.2 1.0112 2.618 0.609
1.0 0 1 3.723 1
Margules equation
Eetimation of activity coefficients
ln  1  x2 A  2B  Ax1 
2
ln  2  x1 B  2A  Bx2 
2

The constant A in the above equation is terminal value of ln1 at x1=0 and constant B is
the terminal value of ln2 at x2=0
When A=B
ln  1  Ax 2 , ln  2  Ax1
2 2
The above equations are known as Margules suffix equation.
Wilson Equation:
Wilson proposed the following equation for activity coefficients in binary solution
 12  21 
ln  1   lnx1  12 x2   x2   
 x1  12 x2  21 x1  x2 
 12  21 
ln  2   lnx2   21 x1   x1   
 x1  12 x2  21 x1  x2 
Wilson equation have two adjustable parameters  12 and  21 . These are related to pure
component molar volumes.
V2    11  V2  a 
12  exp  12   exp  12 
V1  RT  V1  RT 
V1     22  V1  a 
21  exp   12   exp  21 
V2  RT  V2  RT 
V1 and V2 – molar volumes of pure liquids
 - Energies of interaction between molecule
Wilson equation suffers main disadvantages which is not suitable for maxima or minima
on ln  versus x curves.
Consistency of VLE data
Gibbs duhem equation in terms of thermal consistency
d ln  1 d ln  2
x1  (1  x1 ) 0
dx1 dx1
Plot of logarithmic activity coefficients Vs x1 of component in binary solution

According to Gibbs Duhem equation both slopes must have oppsite sign then only the
data is consistent, otherwise it is inconsistent.
For the data to be consistent it has satisfy the following condition.
1. If one of ln  curves has maximum at certain concentration and the other curve
should be minimum at same composition.
2. If there is no maximum or minimum point both must have + ue or –ue on entire
range.
Co-existence equation
The general form of Gibbs duhem equation at constant temperature and pressure
 xi d M i  0 ---(1)
In terms of partial molar free energies
 xi d Gi  0 ------(2)
dividing equation (2) by dx1

d Gi
x i
dx1
 0 -----(3)
Gi  RT ln f i  
at constant temperature
d Gi RT ln f i
 ----(4)
dx1 dx1
substituting equation (4) in equation (3)
RT ln f i
x i
dx1
0
d ln f i
x i
dx1
 0 ------(5)
For binary system

d ln f1 d ln f 2
x1  x2  0 ----(6)
dx1 dx1
x1d ln f1  x2 d ln f 2  0 -----(7)
Equation (5) (6) and (7) are Gibbs Duhem equation in terms of fugacites and thus
applicable for both liquid and vapor phase
For liquids
f i   i xi f i
ln f i  ln  i  ln xi  ln f i
differentiating with respect to x1 =0
d ln f i d ln  i d ln xi d ln f i
   -------(8)
dx1 dx1 dx1 dx1
fi is a pure component ffugacity it does not vary with x1
Substituting equation (8) in equation (5)

=0
d ln  d ln x
 xi dx i  xi dx i  0
1 1

d ln  i
x i
dx1
 0 ----------------(9)
For binary system

d ln  1 d ln  2
x1  x2  0 ---------(10)
dx1 dx1
x1d ln  1  x2 d ln  2  0 -----------(11)
Equation (9) (10) and (11) are Gibbs Duhem equation in terms of activity coefficients
For ideal vapor

f i  Pi
From equation 5
d ln Pi
x i
dx1
 0 ------------(13)
For binary system
d ln P1 d ln P2
x1  x2  0 ----------(14)
dx1 dx1
x1d ln P1  x2 d ln P2  0 ---------------(15)
Equation (13) (14) and (15) are Gibbs Duhem equation in terms Partial pressure.
For ideal vapor
P1  y1 PT , P2  y 2 PT
x1d ln( y1 PT )  x2 d ln( y2 PT )  0
x1d ln y1  x1d ln y2  ( x1  x2 )d ln PT  0
x1  x2  1
x1d ln y1  x1d ln y 2  d ln PT  0
dP
  x1 d ln y1  x2 d ln y 2
P

dP dy dy
  x1 1  x2 2
P y1 y2
y 2  y1  0 , dy 2  dy1
on simplification
dP   x (1  x1 ) 
 dy1  1  
P  y1 (1  y1 ) 
Further simplification
dP  y x 
 P 1 1 
dy1  y (1  y1 ) 
This is known as coexistence equation. It relates P,x,y for binary VLE system. This
equation is used to rest consistency of VLE data.
Consistency test for VLE data
x1d ln  1  x2 d ln  2  0
x1 d ln  1
d ln  2  
x2
x1 d ln  1
d ln  2  
(1  x1 )
x1 d ln  1
d ln  2   
(1  x1 )
Redlich Kister Test

The excess free energy of mixing for a solution is given as
G e  Gideal  GNonideal
G e  RT  xi ln  i
For binary system

G e  RT x1 ln  1  x2 ln  2 
differentiating with respect to x1

dG e  d ln  1 d ln  2 dx 
 RT  x1  ln  1  x2  ln  2 2 
dx1  dx1 dx1 dx1 
From Gibbs Duhem Equation

d ln  1 d ln  2
x1  x2 0
dx1 dx1
dG e  dx 
 RT ln  1  ln  2 2 
dx1  dx1 
dx2  dx1
dG e
 RT ln  1  ln  2 
dx1
dG e   
 RT ln 1 
dx1  2 
x1 1 x1 1
 1 
 dG  RT 
e
ln  dx1
x1 0 x1  0 
2 
The two limits indicates pure component for which G e  0 , where LHS is zero for both
limits.
We can write
x1 1
  
0   ln 1  dx1
x1  0 
2 
This can be checked graphically. Net area should be equal to zero for
consistency(Area=0).
Problem
Verify whether the following data is consistent

X1 1 2
0 0.576 1.00
0.2 0.655 0.985
0.4 0.748 0.930
0.6 0.856 0.814
0.8 0.950 0.626
1.0 1.00 0.379
Solution:
We know that the Redlich kister test is

x1 1
  
0   ln 1  dx1
x1  0 
2 
1 1
ln
2 2
0.576 -0.552
0.665 -0.408
0.804 -0.218
1.052 0.051
1.518 0.417
2.639 0.97
1
Plot ln Vs x1
2
\
Area under the curve is zero. Data is consistent.

CHEMICAL REACTION EQUILIBRIUM
Energy change accompanies all chemical reactions. Because of this energy
change the temperature of the products may increase or decrease depending on the
exothermic or endothermic nature of the reaction. The energy change may be
expressed in terms of heat of reaction, heat of combustion and heat of formation.
Heat of reaction is the change in enthalpy of a reaction under pressure of 1.0
atmosphere, starting & ending with all materials at a constant temperature T
Heat of combustion is the heat of reaction of a combustion reaction.
Heat of formation is the heat of reaction of a formation reaction. A formation
reaction is one which results in the formation of one mole of a compound from the
elements.
Eq. H2 + ½ O2  H2O
C +O2  CO2
C + ½ H2 + 1/2 Cl2  CHCl3
The standard heat of reaction, standard heat of formation, and standard heat of
formation are respectively the heat of reaction, heat of combustion and heat of formation
under 1 atmosphere starting and ending with all materials at constant temperature of
250C.
In chemical industries, processes are carried out under isothermal conditions
and this requires the addition or removal of heat from the reactor. Heat of reaction
values will give the amount of heat to be removed or added. Knowing of this heat
value helps to design the heat exchange equipment.
Standard heat of reaction
Calculation of ∆H298 form heats of formation data:
The standard heat of reaction accompanying any chemical change is equal to
the algebraic sum of the standard heats of formation of products minus the
algebraic sum of the standard heat of formation of reactants.
∆Hr = ∑∆Hf 298 products - ∑∆Hf 298 reactants

Heat of formation of any clement is zero

Heat effects of chemical Reaction:
For the reaction, aA + bB ↔ cC + dD
Let heat capacity be Cp = α + βT + γT2 then we have CpA = αA + βAT + γAT2
CpB = αB + βBT + γBT2
CpC = αC + βCT + γCT2
CpD = αD + βDT + γDT2
And ΔH0298 be standard heat of reaction at 298 K and standard heat of reaction at any
other temperature can be found by Kirchoff’s rule


d H o   C where
p
dT
Cp  
products
Cp  
reac tan ts
Cp
Cp  cCpC  dCpD   aCpA  bCpB  then substituting the values of C , C , and C , C
pC pD pA pB
= [c(αC + βCT + γCT2) + d( αD + βDT + γDT2 ) ] - [a (αA + βAT + γAT2 ) + b (αB + βBT +
γBT2 )]
= [(c αC +d αD ) – (a αA + b αB ) ]+ [ (c βC + d βDT) – (a βA + b βB)]T + [ c γC + dγD ) –
(a γA+ b γB )] T2
ΔCp = Δα + Δβ T + ΔγT2
or
  
Pr oducts
 
Re ac tan ts

   cCC  dCD    aCA  bCB 
  
Pr oducts
 
Re ac tan ts

  
Pr oducts
 
Re ac tan ts

Substituting in Kirchoff‘s rule

H 0  T   T   T 2
H 0 T
    T   T 
d
 H 0  2
H298
dT 298
 2  3
H o  T  T  T I
2 3
 2  3
H o  T  T  T I
2 3
H 0   CP dT      T   T dT

2
OR in general  2  3
=T  T  T I
2 3
A chemical reaction proceeds in the direction of decreasing free energy.The sum of the
free energies of the reactants should be more than the sum of energies of products. For a
reaction to take place
GRe action  
products
G 
reaction
G or GRe action  0
Therefore ΔG should be less than zero for a reaction to occur. When equilibrium is
reached free energies of the reactants equal free energies of products,. Therefore the
criterion for reaction equilibrium is ΔG = 0
ΔGReaction Calculation: Consider the reaction aA + bB ↔ cC + dD
Let GA , GB , GC , and GD be the partial molar free energies of A,B,C, and D in the
reaction mixture.
fA fA
GA  GA0  RT ln 0
but  aA the activity of A
f A fA0
GA  GA0  RT lnaA
GB  GB0  RT lnaB
GC  GC0  RT lnaC
GD  GD0  RT lnaD

GRe action  
products
G 
Re ac tan ts
G
  
 cGC  dG D  aGA  bG B 
 
= c GC0  RT lnaC  d GD0  RT lnaD
  

a GA0  RT lnaA  b GB0  RT lnaB
   

 cGC  dGD  aGA  bGB 
 RT lna C  lnaD  lnaA  lnaB 
 ac ad 
 G  RT ln C 
D
GRe action 0
 a ab
a 
 A B 
 ac ad 
At equilibrium ΔG = 0 and K   Ca Db  K is equilibrium constant of the reaction
a a 
 A B 
 ac ad 
0  G  RT ln C
0 D
  G0  RT ln K  at equilibrium
 a ab
a 
 A B 

EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT K
Gibb‘s - Helmoholtz equation at constant pressure is given
 G o 
d 
 T  H
 2 but G o  RT ln K
dT T
 RT ln K 
d 
 T  H d  R ln K  H
 2 or  2
dT T dT T
d  ln K  H
 Van't Hoff equation.
dT RT 2
This may be integrated to find the effect of temperature on K
K2 T2
H
When H is contant  d lnK    RT
K1 T1
2
dT
K2 H  1 1 
ln    
K1 R T2 T1 
if K1 is known at T1 , then K 2 can be calculated at other T2
d  ln K  H 0
When H varies with T 
dT RT 2
    T I 
d  ln K       2 
dT
 RT 2R 3R RT 
 ln T  T  T 2 I
ln K =    M
R 2R 6R RT
Where M is a consatnt of integration
G 0   RT ln K
  ln T  T  T 2 I 
G 0   RT     M
 R 2R 6R RT 
 T 2
 T 3
G 0  T  ln T    I  MRT
2 6
For the reasction C2H4 + ½ O2 ↔ C2H4O, develop equations for ΔH0, K, and ΔG0, find
ΔG0 at 550 K
Cp (Cal / mol K) Data: C2H4 = 3.68 + 0.0224 T
O2 = 6.39 + 0.0021 T

C2H4O = 1.59 + .00332 T
Standard heat of reaction ΔH0298
C2H4O = - 12 190 and C2H4 = - 12 500, Cal / mol
And ΔG0298 = -19070 Cal / mol
H Re action 298  
Pr oducts
H 
Re ac tan ts
H
= 1(-12190) – 1( -12500) = 310 Cal / mol
In this problem Cp     T
 1 
  
Pr oducts
 
Re ac tan ts
 = 1.59    3.68  6.39   5.285
2 
 1 
  
Pr oducts
 
Re ac tan ts
 =  0.0332    0.0224  0.0021  0.00975
 2 
Then the variation of standard heat of reaction with temperature is
 2  3 0.00975 2
H o  T  T  T  I   5.285 T   T I
2 3 2
0.00975 2
Given H298
0
=310 =  5.285 T   T I then I = 1452
2
0.00975 2
H o  5.285T  T  1452 This is variation of H298
0
with temparature
2
   I 5.285 0.00975 1452
lnK = ln T  T  T 2  M = ln T  T M
R 2R 6R RT 2 2(2) 2T
G0298 19070
but G  RT ln K 298
0
298 or lnK 298     32
RT 2(298)
5.285 0.00975 1452
32 = ln 298  298  M therefore M = 48.763
2 2(2) 2(298)
5.285 0.00975 1452
lnK = ln T  T  48.763
2 4 2T
G0  RT ln K  2T ln K
 5.285 0.00975 1452 
2T ln K  2T  ln T  T  48.763 
 2 4 2T 
3
G  5.285T ln T  4.875(10 )(T )  1452  97.526(T )
0 2
G0550  5.285(550)ln550  4.875(10 3 )(550)2  1452  97 .526(550)

G0550  35320.62 Cal / mol

50 mol% each of SO2 and O2 is fed to a converter to form SO3.
Show the variation of i) Standard heat of reaction with T ii) Equilibrium constant
with T. The ΔHf and ΔGf at 298 K are
ΔHf ΔGf
Component k Cal / k k Cal / k
mol mol
CP data:
SO2 -70960 -71680
Component a b(103)
O2 0 0
SO2 7.116 9.512
SO3 -94450 -88590
O2 6.148 3.102
SO3 6.0377 23.537
Feed contains 50 mole% SO2 and O2.This means for every one mole SO2 there will be
one mole O2 in the reactant side and ½ mole O2 in the product side, according to SO2 +
½ O2  SO3
Reactants: 1 mol SO2 + 1 mol O2 Products: 1 mol SO3 + ½ mol O2 (excess)
1
      = 6.0377 + 6.148  7.116  6.148  - 4.152
Pr oducts reac tan ts 2
1
  
Pr oducts

reac tan ts
 = 23.53(10-3 ) + 3.102(10 3 ) - 9.512 (10 -3 ) + 3.102 (10-3 ) =12.474 x10 -3
2
 2  3
H  T 
0
T  T I
2 3
12.474x10 -3 2
= -4.152T+ T I
2
But H 0 at 298 is given by H 298 0
  H 0   H 0  94450   70960   23490 k Cal / k mol
products Re ac tan ts
 -23490=-4.152 (298 ) + 6.237 x 10 (298)  I -3 2
 I = -22818.19
H 0  4.152 T  6.237 x10 3 T 2  22818.19
Next for K we have
   2 I
lnK= ln T  T T  M
R 2R 6R RT
4.152 12.474 x10 3 22818.19
lnK= ln T  T M
2 2 xR 2T

G0298
We have G0298 = -RT ln K 298 or lnK 298 =
2(298)
G0298 = 
Products
G - 
Reactants
G = - 88590 - (- 71680) = - 16910 k Cal / k mol
16910
lnK 298 =  28.372
2(298)
4.152 12474 x10 3 22818.19
28.372  ln 298  298  M
2 2x 2 2 x 298
 M  0.9842
11409.09
ln K  2.076lnT  3.1185 x10 3T   0.9842
T
Derive the general equation for the standard free energy formation for ½ N 2 + 3/2
H2  NH3
The absolute entropies in ideal gas state at 298 K and 1.0 atm are
NH3 = 46.01 g Cal / g mol K
N2 = 45.77
H2 = 31.21
0
ΔH 298 (g Cal / g mol) = - 11040
Heat capacity Data is given by Cp= a + bT + cT2 the values are

Component a bx102 cx105
NH3 6.505 0.613 0.236
N2 6.903 - 0.038 0.193
H2 6.952 - 0.46 0.096
Compute the free energy change at 1500K. Is reaction feasible?

We have G0  H o  S 0 and S298  
Pr oducts
S  
Re ac tan ts
S
1 3 
=46.01   (45.77) + (31.21) =  23.69 g Cal / g mol K
2 2 
G0298  11040  298( 23.69)  3980.38 g Cal / g mol K
1 3 
a  
Pr oducts
a
Re ac tan ts

 6.505   (6.903)  6.952   7.3745
 2
a
2 
1 3 
b   b   b  0.613 x102   (0.038 x102 )  ( 0.046 x10 2 )  7.01x10 3
Pr oducts Re ac tan ts  2 2 
1 3 
c  
Pr oducts
c 
Re ac tan ts
c  0.236 x105   (0.193 x105 )  (0.096 x10 5 )  0.045 x10 6
 2 2 
b 2 c 3
H298
0
 aT  T  T I
2 3
7.01X 10 3 0.045 X 10 6
11040  ( 7.3745)298  298 2  ( 298)3  I OR I = -9153.26
2 3
a b c 2 I
ln K  ln T  T T  M and R =2 gCal / g mol K
R 2R 6R RT
-3980.38
G298
0
 RT ln K 298 or ln K 298 = = 6.6784
-(2x298)
7.3745 7.01x10 3 0.045 x10 6 9153.26
6.6784  ln 298  298  (298)2  M
2 2x 2 6x2 2 x 298
M  11.7987
 The var iation of G with T is given by, G 0 = - RT lnK
 -7.3745 7.01x10 3 0.045 x10 6 2 9153.26 
G 0 = -2T  ln T  T T   11.7987 
 2 2x 2 6x2 2T 
 -7.3745 7.01x10 3
0.045 x10 6
9153.26 
G1500
0
= -2x1500  ln1500  1500  1500 2   11.7987 
 2 2x 2 6x2 2x1500 
g Cal
G1500
0
 
Pr oducts
G  
Re ac tan ts
G  28488.81
g mol
The reaction is not feasible ΔG is highly +ve: For feasibility it should equal to zero
The hydration of Ethylene to alcohol is given by C2H2 + H2O  C2H5OH
Temperature 0C 145 6.8 x 10-2

Equilibrium Constant 320 1.9 x 10-3

Component a bx103
C2H4 2.83 28.601
The heat capacity data for the component can be H2O 7.3 2.46
represented by Cp = a + bT where T is in kelvin C2H5OH
6.99 39.741
and Cp is in cal / g mol 0C
Develop general expression for the equilibrium constant and standard Gibb’s free
energy change as function of temperature.
a  
Pr oducts
a 
Re ac tan ts
a = 6.99  (2.83  7.3)  3.14
b  
Pr oducts
b 
Re ac tan ts
b  39.741x10 3  (28.6 x10 3  2.46 x10 3 )  8.68 x10 3
a b c 2 I
lnK = ln T  T T  M
R 2R 6R RT
3.14 8.68 x10 3 I

lnK = ln T  T M
2 2x 2 2T
3.14 8.68 x10 3 I 
At 418 K, ln 6.8x10 -2 = ln 418  418  M 
2 2x 2 2 x 418 
 Solving, I = -9655.807 & M = -5.667
3.14 8.68 x10 3
I 
At 593 K, ln 1.9x10 -3  ln 593  593   M
2 2x 2 2 x 593 
3.14 8.68 x10 3 -9655.807
 lnK = ln T  T  -5.667
2 2x 2 2T
 3.14 8.68 x10 3 -9655.807 
But G = -2T  ln T  T  -5.667 
 2 2 x 2 2T 
G = 3.14T ln T - 4.34x10 -3T 2  9655.807  11.334T
THERMODYNAMIC FEASIBILITY OF REACTIONS

The equilibrium constant K is a measure of the concentration of the products
formed at equilibrium. It is related by the equation ΔG 0 = - RT ln K. The more the value
of K, more will be the equilibrium conversion of products. When the value of ΔG < 0,
means the value of K should be very large. Hence ΔG is the measure of feasibility of a
chemical reaction.

i) If ΔG0 < 0, there can be appreciable conversion of reactants in to products.
The more the –ve value, more will be the feasibility of the reaction
ii) If ΔG0 is +ve but less than 10 000 k Cal / mol, the reaction is not feasible,
at atmosphere , may be feasible at any other pressure
iii) If ΔG0 is greater than 10 000 kCal / mol the reaction is not at all feasible
under any condition.
Equilibrium Calculations ( Homogeneous gas Phase reactions):
aA (g) + bB (g) ↔ cC (g) + dD (g)

 ac ad 
We have K   Ca Db  for gases,
a a 
 A B 
f
Activity a  E as f 0 = p = 1 atmosphere: a = f
f0
fc =  c y c c but ac  fc x p =  c y c c p
aD   D yDD p
a A   A y A A p
aB   B yB B p
 c yc c p  D yDD p   c   D   y c   yD  c  D   p  p 

c d c d c d c d c d
K=  x x x
 A y A A p  B yBB p   A   B   y A   yB  A  B  p  p
a b a b a b a b a b
K  (k )(k y )( k )(Pc + d - (a + b) ) =( k )( k y )( k )(P n ) where  = activity co efficient for gas phase
y = mole fraction
 = Fugacity Co efficient for gas phase
P = Total pressure
Effect of variables on equilibrium :

Effect of temperature: G298
0
 RT ln K298 since ΔG depends only on temperature as the
pressure is fixed at 1.0 atmosphere, K value varies with temperature. It is not affected by
Pressure, Concentration, etc,. Variation of K with T is given by
d ln K  H
 Van't Hoff equation.
dT RT 2

For endothermic reactions ΔH0 is + ve as T increases K also increases. This
means that the equilibrium conversion is more at higher pressure.
For exothermic reactions ΔH0 is –ve. Therefore K increases with T. Hence the
equilibrium conversion decreases as T increases. Eg. SO 2 + 1/2 O2 ↔ SO3
Effect of pressure: Consider a reaction of ideal gases, then K = KyPΔn or Ky = K / PΔn
 When Δn > 0. An increase in pressure decreases Ky. Hence equilibrium product
yield is less at high pressures
 When Δn< 0. An increase in pressure increases Ky and equilibrium product
yield
C2H4 + H2O  C2H5OH Δn = 1 – (1+1) = -1, Δn < 0
N2 + 3H2  2NH3 Δn = 2 – 4 = – 2 Δn < 0 Here high
pressure is required
 When Δn = 0 Here pressure has no effect on reaction. For ideal gases the effect
of pressure depends on the variation of γ and Φ with pressure
Effect of Inert: Presence of inert has the opposite effect of increase of pressure.
Therefore when Δn > 0, addition of inert increases Ky and equilibrium
conversion
And Δn < 0, addition of inert decreases equilibrium conversion.
Effect of excess reactants: Presence of excess reactants increases equilibrium
conversion of the limiting reactant
Presence of products in feed: decreases the equilibrium conversion of reactants.
Eg. CH3COOH + C2H5OH CH3COOC2H5 + H2O
If water is added by 1.0 mole to the feed, equilibrium conversion of CH 3COOH
reduces from 30% to 15%
HCN is produced by the reaction N2 (g)+ C2H2 (g)  2HCN (g). The reactants are
taken in stoichiometric ratio at 1.0 atmosphere and 3000C. At this temperature ΔG0 = -
30100 k J / k mol. Calculate equilibrium composition of product stream and
maximum conversion of C2H2

 30100
Δn=2– (1+1) = 0 we have G0  RT ln K or lnK = or K = 1.8029x103
8.314(573)
Moles Moles Moles Mole

Component
in feed reacted present fraction
N2 1 X 1–X (1 – X) / 2
C2H2 1 X 1–X (1 – X) / 2
(2X) / X =
HCN -- 2X 2X
X
K  K  K y K P n Assume K   K  1 and P n  P 0  1
2
y HCN X2
K  1.8029(10)3  K y   Solving for X , X = 0.0207
y N1 2 yC1 2H2 1 X  1 X 
 2  2 
  
Equilibrium Composition:
1 X   1  0.0207 
N2    100    100  48.965%
 2   2 
1 X   1  0.0207 
C2 H2    100    100  48.965%
 2   2 
HCN  ( X )100  2.007%
Equilibrium Conversion of C2 H 2
Equilibrium conversion is max imum for reversible reaction
Moles of C2 H2 reacted X 0.0207
Max. Conversion of C2 H2  100  100  100  2.07%
Moles of C2 H2 in feed 1 1
Workout the problem, when the pressure is changed to 203 bar. Fugacity co efficients
of N2,,C2H2 and HCN are 1.1, 0.928, and 0.54 Assume KΦ= 1
 c    y Cc
K  K  K y K P n = (1)  a C b   a b
 203 where a,b, and c are stoichiometric co efficients
0
 A B   yA yB
 0.542  X2
and K is known already = 1.8029x10 -3 =   .(1)
 (1.1)(0928)   1-X   1-X 
 2  2 
  
solving X = 0.0382
then equilibrium Composion of C2H2 is ( Max reversible reaction)
moles C2 H2 reacted 0.0382
= x 100 = 3.82%
moles of C2 H2 in feed 1

Calculate the K at 673K & 1.0 bar for N2 (g) + 3 H2 (g)  2NH3 (g).
Assume heat of reaction remains constant. Take standard heat of formation and
standard free energy of formation of NH3 at 298 K to be - 46110 J / mol and – 16450 J
/ mol respectively.
G298
0
 2( 16450)  32900 J 
 G298
0
 RT ln K 298
H298  2 (-46110) = -92 220 J
0
G298
0
 RT ln K1
- 32900 = - 8.314 (298) ln K1
K1  564861.1
K2 H  10
1
we have ln    
K1 R  T2 T1 
K2 92220  1 1 
ln  
584861.1 8.314  673 298 
K 2  5.75 X 10 4
Acetic acid is esterified in the liquid phase with ethanol at 373 K and 1.0 bar according
to
CH3COOH (L) + C2H5OH (L)  CH3COOC2H5(L) + H2O (L)
The feed consists of 1.0 mol each of acetic acid & ethanol, estimate the mole fraction of
ethyl acetate in the reacting mixture at equilibrium. The standard heat of formation
and standard free energy of formation at 298 K are given below.
Assume that the heat of reaction is independent of T and liquid mixture behaves as
ideal solution.
CH3COOH C2H5OH
CH3COOC2H5(L) H2O (L)
(L) (L)
Δf0f
- 484500 - 277690 - 463250 - 285830
(J)
ΔG0f
- 389900 -174780 - 318218 - 237130
(J)

ΔG0298 = – 318218 – 237130 + 389900 + 174780 = 9332 J
ΔH0298 = – 463250 – 285830 + 277690 + 484500 = 13110 J
We have, ΔG0298 = – RT ln K
9332 = – 8.314 (298) ln K1 or K1 = 0.02313
K1 H  1 1
ln    
and for K2 at 373K we have K2 R T1 T2 
0.02313 12110  1 1 
ln     OR K 2  0.067
K2 8.314  298 373 
Moles Moles Moles Mole

Component
in feed reacted present fraction
CH3COOH 1 X 1–X (1 – X) / 2
C2H5OH 1 X 1–X (1 – X) / 2
CH3COOC2H5 -- X X X/2
H2O -- X X X/2
2
2
x
2
  x2
K2  K y P 0  0.067=  solving, x = 0.252
1 x 
2
(1  x )2
 2 
 
x 0.252
 mole fraction of CH3 COOC2 H5    0.126
2 2
The standard free energy change for the reaction C4H8 (g)  C4H6 (g) + H2 (g)
is given by ΔGT0 =1.03665 X 105 – 20.9759T ln T 12.9372 T, where range of ΔGT0 in J
/ mol and T in K
a) Over what range of T, is the reaction promising from thermodynamic view
point?
b) For a reaction of pure butene at 800K, calculate equilibrium conversion at 1.0
bar & 5.0 bar
c) Repeat part (b) for the feed with the 50 mol% butene and the rest inerts

a. For the reaction at ΔG = 0, T ≈ 812.4 K, above this temperature ΔG <
0, reaction is promising below 550 K, ΔG > 0, reaction is unfavorable,
b. At 800K, ΔG0 = 1842.16 J / mol

ΔG0 = - RT ln K, or 1842.16 = - 8.314 ( 800 ) ln K or
K = 1.3191
K = ky PΔn = ky P ( 2- 1 ) = ky P
Therefore at 1.0 bar K = kyP 1.3191 = ky ( 1 )

ky = 1.31910At 5 bar, 1.3191 = ky ( 5 )
ky = 0.26382
Moles in Moles in product stream

yi
feed
(1 – X ) / (1 +
C4H8 1 1-X
X)
C4H6 X X / (1 + X)
H2 X X / (1 + X)
1+X
 x  x 
' '   
Y Y 1  x  1  x 

x2
kY 
C4 H 6 H2
or 1.3191 = or x = 0.7541
YC' 4H8 1 x  1  x2
 
1 x 
Conversion of betene = 75.41%
x2
At 5.0 bar, k y = 0.26382 = , x = 0.4569, Conversion of betene = 45.69 %
1  x2
C.
Moles in Moles in product stream
yi
feed
C4H8 1 1-X (1 – X ) / (2 + X)
C4H6 X X / (2 + X)

H2 X X / (2 + X)
Inerts 1.0 1 1 / (2 + X)
2+x
x2  2x 
at 1.0 bar, k Y  K  1.3191   
2  x  1 x 
2
x = 0.8194
K x2  2  x 
at 5.0 bar kY   0.26382  2  
5 2  x  1 x 
x = 0.5501

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No two adiabatic curves will ever intersect.

Conditions for any equation to be equation of state:

1. The equation should reduce to

Van der Waals equation of state:

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Redlich – Kwong Equation:

Applying the partial derivative condition, we get

Note that the above equations reduce to the equation pV  RT , as p  0.

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Since pressure at a is same as that at 2,