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Thermo PDF
Thermo PDF
Thermo PDF
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:
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.
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
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
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
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.
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.
pV nRT
n p
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
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.
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:
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.
2
p
1
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.
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
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 ) mu 2
2 2
2 2
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.
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
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.
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.
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.
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
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 )
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.
Fluid
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.
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.
1 fluid
pC C
L Gas
p
2 3 4
V
TC
L/V
T1
VC V
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:
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 )
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.
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
T2 V
ln ( 1) ln 2
T1 V1
1
T V
ln 2 ln 1
T1 V2
1
T2 V
1
T1 V2
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 )
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:
pV n const
Sl. No n Process
1. 0 Isobaric
2. 1 Isothermal
3. Isochoric
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.
Adiabatic curve
Isotherm
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.
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
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,
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.
RT a
p
V b V (V b) T
5/ 2
0.4278R 2TC 0.0867 RTC
a ;b
pC pC
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
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
U1 a CV dT
T1
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
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
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
No matter what is the process the internal energy and enthalpy are determined using the
following formulae.
dU CV dT
dH CP dT
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.
ΔU12 ΔU1a ΔU a 2
Since step 1 – a is a constant volume process, dU CV dT will have to be used. The step
ΔU12 CV dT 0
T1
Since Ta T2 ,
ΔU12 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 .
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
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.
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 .
1
C( s ) O2 ( g ) CO( g )
2
Then,
221.2 kJ
ΔH 0 298 110.6 kJ
2
A B C ΔH
Let A and B react to form C with heat of reaction H. Let there be one more method of
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
This idea is used to determine heat of reaction from heat of formation or heat of
combustion data.
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.
1
H2 O2 H 2 O ΔH 4 ----------(4)
2
2 H 2 O2 2 H 2 O 2 ΔH 4 ----------(4)
2 H 2 2 S 4O2 2 H 2 SO4
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
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?
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.
WS
Heat Exchanger
Q1
Condenser
Q2
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.
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 )
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
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.
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.
dQH dQC TH TC
dQH TH
dQC TC
dQH TH
dQC dQH
TC TH
Applying sign convention,
dQC dQH
0
TC TH
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
ΔSAB
A2 B
T
A1B
T
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
ΔSA1B
B2 A
T
0
dQ
ΔSB 2 A
B2 A
T
0
dQ
B2 A
T
ΔSB 2 A
LHS is dQ / T term and it is along an irreversible path and therefore it does not represent
entropy change.
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.
Wlost T0 ΔStotal
Where T0 refers to the temperature of the sink to which heat is rejected.
dQ dW pdV
pdV
dS
T
RdV
dS
V
V
ΔS R ln 2
V1
dU dQ dW
dU TdS pdV
H U pV
dH dU d(pV)
dU pdV Vdp
TdS pdV pdV Vdp
dH TdS Vdp
Differentiating,
dA = dU-d(TS)
= TdS – pdV – TdS – SdT
dA= - pdV – SdT
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
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
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
Entropy changes:
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,
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
V
dH CP dT V T dp
T p
dG Vdp SdT
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
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
dU TdS pdV
V
dU CP dT T dp pdV
T p
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.
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
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
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
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
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
Cp a bT
Derive the expressions for changes in internal energy, enthalpy and entropy for an
isobaric process.
V
dU CP dT T dp pdV
T p
As pressure is constant, dp = 0,
Internal energy: dU CP dT pdV
dU ( a bT )dT pdV
b
U12 a( T2 T1 ) ( T2 2 T1 2 ) p( V2 V1 )
2
V
Enthalpy: dH CP dT V T dp
T p
dH CP dT
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
T3 T3
dQ CV dT 333
S2 3
T2
T
T2
T
0.72 ln
576
0.3945kJ / kg.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
U Cp V
T p
T p T T p
dU TdS pdV
U S V
T p
p T p T 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
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
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)
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.
dp
d ln f
p
d ln f d ln p
f p Fugacity = Pressure for Ideal gases
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‘.
P
V
d ln f RT dP
1
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
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
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
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
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
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
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
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.
The term partial molar property is used to designate the component property when it is
admixture with one or more component solution.
It is defined as
nM
Mi ji
n i T , P ,n
j
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.
We can write
ni
nM ni M i xi
n
M xi M i
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 v0
nw nw
Consider any thermodynamic extensive property (Vi, Gi etc) for homogenous system can
be determined by knowing the temperature, pressure and various amount of constituents.
M t
i n
dM
t
dni
i 1 ni P.T , n
j i
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
=83.246x103x07= 58.272x103mol
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
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).
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
dM I 1 M
and also (right hand side)
dx1 1 x1
dM
I 1 M 1 x1
dx1
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.
cal
Sol: G 100 x1 150 x2 x1 x2 (10 x1 x2 )
mol
G 9 x1 8x1 49 x1 150
3 2
G
G1 G (1 x1 )
x1
G
27 x1 16 x1 49
2
x1
G
G2 G x1
x1
cal
G1 102.944
mol
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
G1 G1atx1 1
cal
G1 100
mol
G2 G2 atx1 0
cal
G1 150
mol
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
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
dG
t
T ,P i dni
We know that
G t
i Gi -------------------(1)
ni T , P ,n j
i 2G
T Tdn ---------------------(2)
P ,n i
G
T S
P
differentiating again w r t ni
2G S t
Si
Tni ni P ,n j
i
T T i i
T
T T2
P ,n
G H TS
Gi H i T S i
i H i T S i
H i i T S i
i Hi
T
P ,n T2
Effect of Pressure:
We know that
G t
i Gi -------------------(4)
ni T , P ,n
j
i 2G
P Pdn ---------------------(5)
T ,n i
G
P V
T
2G V
Vi ,
Pni ni T ,n
j
i
P Vi
T ,n
Fugacity in solutions
dG RTd ln f
f
lim P0 1
P
d i RTd ln f i
f
limP 0 i
1
Pi
i is Chemical potential
PT – Total pressure.
We know that
G t
i Gi ------(1)
ni T , P ,n
j
i 2G
P -----(2)
T ,n Pdn i
G
P V
T
differentiating again w r t ni
2G V
Vi ,
Pni 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
d ln i
1
V i
RT
dP
RT P
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.
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
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
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 0.2975
0.7426
f
, f =44.558atm
P
n( M ) n( M )
(nM ) dT dP M i dni
T P ,n1 ,n2 P ----------(3)
T ,n1 ,n2
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)
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.
G
G1 G (1 x1 )
x1
G
G2 G x1
x1
G1 18x1 35x1 16 x1 101
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
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
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
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.
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
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
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
dG A V A dP S A dT
dG B VB dP S B dT
dPVB 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 TV
dP Q
----(4)
dT T V B V A
dP H V
dT TV g
RT
HV (Latent heat of vaporization), V g
P
dP P
dT TRT
dP dT
P RT2
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
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.
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.
At constant T and P
i i i for i=1,2,3--------C
Since i Gi RT ln f i
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.
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
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.
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
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
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
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
1x A 1
The above equation relates x and y
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
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.
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
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
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 2B Ax1
2
ln 2 x1 B 2A Bx2
2
When A=B
ln 1 Ax 2 , ln 2 Ax1
2 2
Wilson Equation:
Wilson proposed the following equation for activity coefficients in binary solution
12 21
ln 1 lnx1 12 x2 x2
x1 12 x2 21 x1 x2
12 21
ln 2 lnx2 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
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
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)
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
d ln f i d ln i d ln xi d ln f i
-------(8)
dx1 dx1 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
d ln Pi
x i
dx1
0 ------------(13)
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.
P1 y1 PT , P2 y 2 PT
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
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.
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 )
G e RT xi ln i
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
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.
And ΔH0298 be standard heat of reaction at 298 K and standard heat of reaction at any
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
Pr oducts
Re ac tan ts
Pr oducts
Re ac tan ts
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
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
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
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
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
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
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
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
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
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 x102 (0.038 x102 ) ( 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 x105 (0.193 x105 ) (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
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
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 yDD p
a A A y A A p
aB B yB B p
K= x x x
A y A A p B yBB 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
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
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
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
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)
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
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
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)
x = 0.8194
K x2 2 x
at 5.0 bar kY 0.26382 2
5 2 x 1 x
x = 0.5501