Thermodynamics

GATE & ESE

Content Sheet

Thermodynamics 1
1. Thermodynamics 3

2.
 1 Thermodynamics

Chapter 1
Thermodynamics plays role in chemical engineering like let us take a Example
A reaction is occurring
N2 + 3H2 ⇋ 2NH3
1. Is this reaction feasible?
2. If reaction is feasible then what will be the conversion? Is it 100%?
3. If not 100 %, then what could be the maximum conversion.
4. If we change operating conclusions, can we change conversion?
In the case of microscopic Analysis pressure is the time average of the rate of momentum
change of the molecules or atom inside the container.
As in 22.4 liters there are 6.023 × 1023 molecules which mean molecules are present
everywhere (not gap) so we do macroscopic study of containers or we define pressure by
using pressure gauge without going at molecular level.
According to the Hagien Beng principle it is not possible to predict velocity & position
simultaneously, so microscopic study needs a large number of variables to get described.
Thermodynamics defines all fundamental laws which governs the occurrence of physical
process associated with transfer of energy O2 transformation of energy and also establishes
relationships between physical properties like density, temperature, pressure etc.
In other words, thermodynamics is Branch of science & Engineering that deals with the
energy & energy transfer & equilibrium.

As far as Chemical Engineer is concerned the following questions answers should be

known: -
1. Is the r x n is feasible at specified Temperature & pressure?
2. Does the reaction go for completion?
3. If it is not going for completion. What will be the extent for competition?
4. How many energies is required for the r x n to take place.
5. Is it possible to increase the conversion by changing the operating conditions?
6. How much energy is required to separate the desired product from byproduct & reactants?

Thermodynamics study can be studied by following too approach.

1. Macroscopic approach (Classical thermodynamics)
2. Microscopic approach (Statistical thermodynamics)

Macroscopic approach
1. The state (condition) of matter under consideration is described in terms of Macroscopically
measurable quantities. (Any quantities that can be sensed by human beings like
temperature, pressure, composition, volume) via thermometer, gauges, chromatograph
Thermodynamics

& dimensions of the vessel.

3.
 2. Only a small number of variables is used to describe the state of matter.
3. These variables can be estimated by humans.
4. The structure of matter under consideration is not taken into account or can say
knowledge of behavior of molecules is not required (Macroscopic).
5. It deals with the study of certain quantities of the matter without considering any event
occurring at molecular level.

Microscopic approach
1. This approach deals with the study of certain quantities of matter by considering events
occurring at molecular level.
2. Since every matter consists of large no of molecules or atoms and the velocity & position
of molecules are totally at random, hence large no of variables are required to describe
the state of the system.
3. These variables cannot be measured/ sensed by human operators.
4. Knowledge of structure or matter is essential to analyze the behavior of systems &
molecules.

Macroscopic approach is the time average of microscopic approaches.

Difference between Macroscopic approach and microscopic approach.

Macroscopic approach Microscopic approach

1. Attention is focused on a certain quantity 1. Matter comprising the system consists

of matter without taking into account
the events occurring at molecular level.
of a large number of molecules or
atoms, these molecules have different
velocity, different energy & position, &
these parameters constantly change
with the time.

2. Analysis is concerned with the overall 2. Knowledge of the structure of a matter

behavior of the system. (Overall study) is essential in analyzing the behavior of
and this approach is adapted in the a system.
classical thermodynamics study

3. Only a few variables are required to 3. Large number of variables is required to

define the state of matter. define the system.

4. The properties like temperature, 4. Momentum, kinetic energy, velocity

pressure, volume are needed to describe which describes the behavior of
the system (Microscopically quantities) molecules can neither be felt nor be
Thermodynamics

that can be easily measured/ sensed by measured by any instruments easily.

our senses

4.
 Macroscopic approach Microscopic approach

5. Properties (temperature, pressure, 5. Properties of each molecule are defined

volume) are the time average of individually.
properties at microscopic level.
For Example: Pressure is the time
average of rate of change of momentum
of molecules.
Temperature is the time average of rate
of change of kinetic energy of molecules

6. This approach requires simple 6. Advanced mathematical formulas are

mathematical formula to analyze the required to describe the system.
system

Note: - Since, macroscopic properties are the average properties of microscopic

characteristics then obviously when both methods are applied to a practical system both
will give the same result.
Hence, macroscopic approach is used (as required variable is less & easy).

Classical thermodynamics
System: - Small region in a spare on which we are going to focus our attention. Anything
beyond the system is called surrounding & the line which separates the system from
surrounding is called Boundary.
1. Types of SystemClosed System
2. Open System
3. Isolated System

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Control mass system: - Here, mass & Identity must be fixed.

We can fix Identity, when there is no mass interaction between the system & surrounding.
Also called a closed system. (m=0)
But energy can be exchanged.
Thermodynamics

y Energy interaction is allowed

y Mass interaction is not allowed
Example: - Piston cylinder assembly rigid vessel (nothing can be in or out)

5.
 Control Volume System: - It is also called an open system. The control volume is a small
volume in the system space or flow field through which mass can be in or out.
Example: - Nozzle

 

Purpose of nozzle is to Increase the K.E energy on the expansion of puss energy.

Boundary of control volume is control surface

Control Surface (CS)

IS  surface
Real


Imaginary surface

Real surface

In the open system mass as well as energy both can be interact with the surrounding.
Examples: - Nozzles, H.E, turbine compressors, pumps, all flow operations

A liquid is flowing in a pipe is also a example of control volume

CV


IS  IS

Isolated System: - No mass, No energy interaction.

Examples: - Well insulated thermo flask.
In the case of the Adiabatic System energy is not being transferred in the form of heat, but
there is Energy transfer in the form of work. (Energy in form of work or work interaction is
allowed).

Thermodynamics State & thermodynamics properties

Thermodynamics properties: - The properties which define the state of a matter/ a system
are called thermodynamics properties.
Thermodynamics

For example: - Pressure, temperature, volume, enthalpy, entropy.

6.
 Note: - Absolute value of Enthalpy, entropy, Internal energy cannot be measured easily,
always changes in ΔE, ΔS, ΔU is measured from reference point.
There are two types of thermodynamics properties.
1. Extensive property: Depends upon mass of the system.
2. Intensive property: Does not depend upon mass of the system.
For example: - Pressure (Extensive), Temperature (Intensive)
Example of Extensive property
Volume, mass, entropy, enthalpy, Gibbs free energy, Helmholtz Energy
Example of Intensive property
Temperature, pressure, density, conductivity, Specific heat (CP), Viscosity, molecular weight.
Note: - All specific Extensive properties are Intensive
For Example: - Volume is Extensive ( m3 ) but Specific volume is Intensive ( m3 / kg )
(J) enthalpy is extensive, but specific Enthalpy (h= J/kg) is Intensive.

Thermodynamic state
Condition of the system is called the State.
To define any system as a state, two criteria must be satisfied
y The properties within the system must be uniform.
y It must be invariant with the time, at least for those time intervals in which we are going to
define the system as state. Every state should be at thermodynamics equilibrium.

Thermodynamic equilibrium
If any system is in chemically, mechanically & thermally equilibrium that system is said to
be thermodynamic equilibrium.
Once the system reaches thermodynamic equilibrium, that system is called dead system,
the system is not in condition to do anything, there is no any interaction between the
system & surrounding. No process will be taking place within the system or from
the system.
Process: - takes place when there is driving force.
Dead State: - there is no driving force for anything to happen.
For thermal equilibrium: - dT = 0 (temperature)
For Chemical equilibrium: - dμ = 0 (Chemical potential)
For Mechanical equilibrium: - dP = 0

Thermodynamic process & thermodynamic Cycle

There is a huge difference between normal process & thermodynamic process. Process is
defined as taking place when there is a driving force.
Thermodynamics

Thermodynamic process is the sequence of the process via large no of states

7.
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sϭs;^ƉĞĐŝĮĐsŽůƵŵĞͿ

1. In the first condition, all the pressure applied by gas molecules is counterbalanced
by weight pressure (SD system is in thermodynamic stable equilibrium) so called
state.
2. If we remove weight from the piston, then a new equilibrium state will be achieved,
similarly, as we keep removing weights one by one new different states will be
achieved.

Hence, we can say that thermodynamic processes go through the no of states. (Process
should be quasi static)

Note: - If we remove weights suddenly then the process will be very fast and will not be a
thermodynamic process.

Note: - Our Objective

In the case of Expansion Our motive is to maximize the work obtained.

In the case of Compassion Our motive is to minimize the work required.
The change state is called a thermodynamic process, but the process should be gone
through via a large number of thermodynamic states.
Thermodynamics

8.
 Wϭ initial
 


W
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final

sϭ s;^ƉĞĐŝĮĐsŽůƵŵĞͿ

If we suddenly remove all the weights at one time, then piston suddenly strike on the stopper
& after some time system will reach to the final thermodynamic equilibrium state, but in
between the initial & final thermodynamic equilibrium state, there is a imbalance in the
process variables or can say properties (means in same location has pressure/temperature
is high or somewhere is low). We cannot define the state in between the initial and final
point which is shown in the figure as below: -

i

P

f

Quasistatic process: - Also called as Quasi equilibrium

Quasi is Greek word meaning as almost stop which process is carried out in a very slow
manner or the process is almost stop or static is called Quasi Static process. In other words,
very slow process is called as quasistatic process
Example: - Removal of weight from piston one by one is called quasi static process or can
Thermodynamics

say that a process which occurred via less no of states.

9.
 Reversible process: - for the system to be reversible, when the processor system undergoes
a change of state, it changes from one stable equilibrium state to another stable equilibrium
state.
In other words, a process is a path followed by a system in reaching the given final state
from the initial state. The process is said to be reversible where on reversing the direction of
the process, both the system & surroundings will restore or must be restored their original
state.
Note: - Removal of weight from piston leads to the change in volume as it was before the
addition of weight on piston is reversible process.
In other words, a process is said to be reversible if both the system & surrounding does not
suffer any change in reversing the direction of the process.

i

P

f

In real life, there is no any process which is perfectly reversible. But a process can be
assumed to be reversible in some limits.

If a process is perfectly reversible, this means that process does not exist. Some processes
can be said to be reversible in some certain limits. First there was no weight & the
volume was V1 & temperature is T. After Addition of weight temperature becomes T1. By
removing weight, we get some Volume V1 from V2 but temperature will never be the same
or close.
Example: - So, system returned to its initial state but surrounding has been charged T as
temperature has been increased due to friction &
Frictionless piston & cylinder assembly is the example of Reversible
Causes of Irreversibility
1. Lack of thermal equilibrium (ΔT≠0)
2. Lack of mechanical equilibrium(ΔP≠0)
3. Lack of chemical equilibrium (Δμ≠0)
4. Lack of Internal reversibility, or due to Internal irreversibility
Note: - If any system is in thermodynamic equilibrium, but it is not reversible, because of
Thermodynamics

its Internal Irreversibility.

Example: - friction, Viscous dissipation effect, elastic deformation.

10.
 Internal irreversibility are
1. Friction
2. Viscous dissipation effect
3. Elastic deformation
Hence, for a process to be reversible, the system must be in thermodynamic equilibrium &
there should be m internal irreversibility in the system.

A process is said to be reversible in some certain limit

1. dT≅0, dμ≅0, dP≅0
2. If there is no Internal irreversibility in the process
If the driving force is very very small, then the process is quasistatic. So, the reversible
process is quasistatic.
Note: - All reversible processes must be quasistatic, but all quasi static processes do not
need to be reversible.

Energy
There are two forms of energy
y Energy in transit Example: - Heat & work (Path function)
y Energy in stored formed (Internal Energy) (Point/ Stale function)
1. If Energy has been stored in the system, that can neither heat nor work.
2. Heat & work are said to be energy when they are going to transfer or can say in transit
mode
3. If the Energy gets transferred due to difference in temperature that energy is called heat
energy otherwise called work.

Heat & work both are boundary phenomena for the heat & work to be transferred they must
cross the boundary.
y Both are path functions
y Both heat & work has an exact differential.
Note:- Cyclic Integral of any point function is zero
Net heat transfer≠ 0 But ΔV is zero
As the path has been changed so heat energy has been changed.
(SD, here amount of heat & work transfer will be different

U1
b


Thermodynamics

a
U1


11.
 W1-a-2 ≠ W1-b-2
Q1-a-2 ≠ Q1-b-2
In between two points if paths are different than amount of heat energy & work energy will
be different
U2 − U1 =∆U
There is no meaning of Q2-Q1≠dQ. As heat is a path function, it cannot be described at any
particular point.
dQ & dW is incorrect
defined as dQ, dW inexact differential.

Note: -
∫ ðp = 0 Cyclic Integral of any point function will always be zero.
All energy is the point function except heat & work
Example: - enthalpy, Gibbs free energy, etc.
In between the same initial & final states the amount of heat transfer & work transfer will
be different for different paths.
W1-a-2≠W1-b-2≠W1-c-2
Q1-a-2≠Q1-b-2≠Q1-c-2

Energy in stored formed (point function)

y Macroscopic form of stored energy [Kinetic energy (KE) + Potential Energy (PE)]
y Microscopic form of stored energy (Internal energy)

Macroscopic: -
Potential Energy: - If an object is carried out from Z1 to Z2 then energy is being stored in
form of PEP.E= mg(Z2-Z1)

Z2

P.E= mg(Z2-Z1)
 (Z2 – Z1)

Z1

Kinetic Energy: - If we are going to drop any object before reaching the bottom, if we
calculate velocity
KE Energy is stored energy due to motion of object
Thermodynamics

Potential Energy
Let us assumed a mass (m) initially at elevation Z1 & it is desired to raise to elevation Z2, then
the work to be done on the body of mass (m) mg(Z2-Z1) or mgΔZ. If the body is allowed to

12.
fall from Z2 to Z1 it can do work on some other body & Y the amount of work it can perform
is mg(Z2-Z1) called as potential energy.

Kinetic Energy: - Energy stored by the system mgH

Initial velocity is zero.
u2 1
V2 = + 2gh= m v 2
0 2
To find the kinetic energy, the macroscopically observable quantity is V. Hence energy
possessed by due to its location as configuration is called potential energy while energy
possessed by a body by virtue in its motion is called as K.E.
V1→ Average velocity of every molecule (macroscopic)
V2→Average velocity of every molecule (at 2)

V2
V1

Ś

If system is stationary there is no change in K.E & P.E.

If the position of system is changed, then only the change in K.E & P.E

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V1

Z2
Z1 V2

Note: - Closed system is stationary generally

1
ΔKE = m [ V22 − V12 ]
2
Thermodynamics

ΔPE = mg (Z2-Z1)
Microscopic form of stored energy: - (Internal Energy)
(Here our motive to be attentive over molecular level)

13.
 Energy associated with the molecules due to its translation rotation, vibration, due to
electron motion.
Hence Internal Energy is the summation of the translational Energy molecules (every
molecule movement) rotational energy (Energy because of movement of molecules on the
mass center axis), Energy due to electrons motion, nucleus interaction energy, Vibrational
Energy.
=
Hence, E ∑ Macroscopic + Microscopic
E = KE + PE + U
∆Esystem = ∆KE + ∆PE + ∆U

If the system is stationary ∆K.E =

∆P.E =
0
∆Esystem =
∆U

Similarity between heat & work

y Both are path functions
y Both have inexact differential
y Both are boundary phenomena

Different form of work

Simple work
Work is defined as a product of applied force and the displacement in direction of applied
force. W= F × d
For Example: -
2 2
∫ða
1
= ∫ fdl
1

f
P= W1-2 = f(l2-l1)
A
W1-2= PA(l2-l1) W2-W1≠ can’t write as (Path function)
W1-2= P(V2-V1) This type of work is called displacement work.

Thermodynamic work
Work is said to be done by the system on its surroundings if the sole effect external to the
system could be reduced to raise the weight through a distance.

Example 1
Thermodynamics

This type of work is called displacement work.

14.
 System
  


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sϮ  tĞŝŐŚƚ

Expansion of gas will be work done by the system on surrounding.

If volume changes, mass will be raised.

Example 2:-

motor Shaft

 weight
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Battery

Current will start the motor & the shaft will move & weight will be raised so, work is said to
be done by the system on surrounding.
2
W1-2 = ∫ PdV
1
Displacement work also called as PdV work

Sign Convention for work

y Work done on the system (W<0)
y Work done on the system (W>0)
Work done on the system is given as 50 KJ
W= - 50KJ

Sign Convention for heat

Thermodynamics

y Heat into the system (Qin>0)

y Heat out from the system (Qout<0)
2
W1-2 = ∫ PdV
1

15.
 This is quasi static work

(1) =

P

(2)

v

If Volume increases, work is done by the system (positive)

If the process is irreversible.
W
=irreversible
P (
  external V2 − V1 )
As in case of irreversible, P cannot be defined at every state.
If the closed system (but rigid) then displacement work will be zero, but there may be
paddle work.Paddle Work: - Suppose there is a closed system

Here there is no change in volume, but still the work is then how?
As here only displacement work is zero.W≠0, dV=0
Consider the liquid contained in a rigid vessel as shown in the figure by loading the mass
from the distance (Z2-Z1). Work is done on the system by surrounding and dV=0, Since the
wall of the vessel are rigid but work is not zero (as paddle work will be there)

ϭ

Thermodynamics

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Ϯ

16.
Shaft work: -
(1)

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t

;ůŽǁƉƌĞƐƐƵƌĞƐƚĞĂŵͿ

Always take place in open system (Turbine producing device)

So, work done by the system (Weight raised)

(2)

 ŽŵƉƌĞƐƐŽƌ


t

So, work done on the system.

(Work consuming device)
(Weight falls)

There is no meaning of displacement work in open system (dV=0) because volume

is always fixed in the control volume system then in the control volume system (open
system), work can be paddle work, shaft work, electrical work, but never be displacement
work.
Example: - where dV≠0, w=0 (expansion)
Thermodynamics

If we remove stopper, then gas will expand, here PdV=0, through the volume is changing,
because it is not quasi static, (this process is very fast, does not pass through no of states),
so there is no any meaning of thermodynamic work (PdV).

17.
 ͘͘͘͘͘͘͘͘͘
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Here gas is expand against the no resistance, as here Pexternal=0 (perfectly vacuum)
W = Pexternal (V2 - V1) = 0
In case of piston cylinder, piston moves against the resistance (Pexternal)

When a gas is allowed to expand under vacuum that type of expansion is called free
expansion or unrestrained expansion. This is the situation where w=0, even though dV≠0 as
this is shown in the figure.

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͘͘͘͘͘͘͘͘͘͘ sĂĐƵƵŵ

As the barrier gets removed, the gas expands freely and occupies the whole volume.

In this case there is no resistance to oppose the notion of the piston, so here work is zero,
as work is always done against some resistive force
Can we calculate PdV work?
No, As PdV work is quasi static state, as here there is no intermediate states between the
initial and final (process is too fast)

Difference between the heat transfer and thermodynamics

Thermodynamics
1. Causes to be heat transfer
2. It is an equilibrium phenomena because it calculates the amount of heat transfer(Q)
when a system changes state from one equilibrium to another equilibrium.
3. Tells the extent of the heat transferred
4. Amount of HT is found by thermodynamics

Heat transfer
1. How the heat gets transferred (conduction, convection, radiation)
Thermodynamics

2. Non equilibrium phenomena

3. How fast the heat can be transferred (rate of heat transfer is find by the HT)
4. Temperature profile or distribution is found by the HT

18.
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Hot Plate Motor

Note:- Work is energy in transit & can be identified, while the process is being executed
Work does not exist before & after the interaction. It will be incorrect to say that work
is possessed or stored by the system. It is transferred energy that can be stored by the
system. Work is a path function δW/đW, where đw≠W2-W1
Whereas energy is a point function that enjoys the property of the system.
2 2
∫ 1
ðw = ∫ PdV 1
2
W1-2 = ∫ PdV
1
this equation is valid for quasistatic process

This equation valid for close & quasistatic process, it means frictionless & reversible process
There should be viscous effects & lack of irreversibility.

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Our motive to have <10°C temperature then process will be fast

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If the process is not quasi static, then there is no meaning of PdV work.

Different thermodynamic processes

Some, most common thermodynamics process are given below
a) Isothermal process
b) Adiabatic process
Thermodynamics

c) Isobaric process
d) Isochoric process
e) Polytropic process

19.
 Displacement work in different processes
Isothermal process
2
W1-2= ∫ PdV
1

For ideal gas PV= nRT

nRT
P =
V
Isothermal means temperature remained constant throughout the process
Expansion gives cooling effect (low in KE ↓ low temperature↓)
Compression gives heating effect (high in KE ↑ high temperature↑)

Difference between heat & work

Heat Work

Heat is highly disorganized form Organized form of energy

Low grade energy. High grade energy

If we supply the heat, all the molecules Work can be fully converted to
that composed the matter disorganized
randomness↑, KE↑, T↑. But heat cannot be
fully converted to work.

PV = nRT (Source used) During expansion T↑, Q is removed

During expansion T↓ so, Q is added

↓PV = nRT↓(To make it constant) P↑V↓=nRT↑ (removed to make it constant)

Constant heat supply

Isothermal (1)
C Expansion (at Qout Isothermal
Qin every point Compression
temperature is
P
P constant)
Qin = +ve
(2)
f
Thermodynamics


v
v

20.
 2
W= ∫ PdV
1

nRT
P=
V
2 nRT V
W1−2 = ∫ 1 V
dV = nRT ln ( 2 ) For reversible
V1
Work is done by the system (Positive) V2>V1 Expansion
Work is done on the system (Negative) V2<V1 Compression
When the gas has to be compressed from V1 to V2, then work had to be done on the system
(So we have to minimize that work)
(Reversible process set the limit that in case of expansion maximum work is done by the
system & minimum work done on the system in case of compression)
Since it is a reversible work hence it is a minimum amount of work required to compress
the gas from V1 to V2 (V2<V1) while in actual practice, work required to compress the same
gas from V1 to V2 is more than that.
Work done by the system calculated by this equation to change the volume V1 to V2 during
expansion is the maximum work & in actual practice the work obtained from the system in
case of expansion will be less than that work.
2 V2 p1
∫
W1−2 = PdV = nRT ln (
1 V1
) = nRT ln (
P2
)

Adiabatic process (R=0)

(Here heat transfer is absent, whereas there is work transfer)
If we remove the weight, then P↓, T↑, V↑

 
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(1) C WsƌсŽŶƐƚĂŶƚ
WsƌсŽŶƐƚĂŶƚ

džƉĂŶƐŝŽŶ
P ŽŵƉƌĞƐƐŝŽŶ P
Thermodynamics

(2) f

v     v

21.
 r = specific heat ratio
Cp
r =
Cv

Difference between Adiabatic & Isothermal

/ƐŽƚŚĞƌŵĂů Expansion
As P↓V↑T↓
Adiabatic Process, go through
the no of Isothermals
P ĚŝĂďĂƟĐ

v u  

Adiabatic is steeper/ vertical than the Isothermal line.

Means slope of adiabatic line is more than Isothermal line on PV plot
dP dP
Adiabatic > Isothermal
dV dV
Since PV= nRT PVr = nRT
vdP + PdV = 0 Vr dP + P[r Vr − 1 ]=0
dP −P
= Vr dP = -P[r Vr − 1 ]
dV V
dP −rP
=
dV V
So, r Slope of Isothermal = Slope of Adiabatic
 dP   dP 
  = r  
 dV Adiabatic  dV Isothermal

Compression
We are going to add the weight
P↑, V↓, T↓
Adiabatic is more vertical
Thermodynamics

22.
 /ƐŽƚŚĞƌŵĂů
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P

v ĚŝĂďĂƟĐ
ŽŵƉƌĞƐƐŝŽŶ

PVr = Constant = C
C
P= = CV −r
PVr
V2 V −r + 1
W1−2 = ∫ CV −r dV =C[
V1
]  V 1V
−r + 1 2 1
1
PVr C [PV ]
= [ V 1−r ]  V2 1 V1   = V2−r +1 − V11−r  1−r
1−r 1−r  
P1V1 − P2 V2
W1−2 =
r−1
nR[T1 − T2 ] nCv[T1 − T2 ]
W1−2 = OR W1−2 =
r−1 r−1
Cv → Specific heat capacity at volume
Expansion T2 > T1 (positive work) (by the system)
Compression T1 > T2 (negative work) (on the system)
P1V1 − P2 V2 P1V1 P2 V2 nRT1 P2 (V2 )
W1−2 = = [1- ]= [1- ]
r−1 r−1 r−1 r−1 P1 V1( )
r−1
nRT1 P2
W1−2 = [1-( ) r ]
r−1 P1
For Adiabatic process
PVr = Constant
P2 V2r = P1V1r
1
P2 V2
( )r = ( )
P1 V1
Thermodynamics

−1
P1 V2
( )r = ( )
P2 V1

23.
 Isobaric process (p=constant)
PV = nRT
During expansion
As T↓, P↓, V↑, here Q=Supplied
(Here we are not going to remove or add the weight, here we will maintain the by applying

YŝŶ džƉĂŶƐŝŽŶ
WĞdžƚĞƌŶĂů

 DV4VXSSOLHG7؆9؆

 
YŽƵƚ ŽŵƉƌĞƐƐŝŽŶ

sљ͕dљ
2
∫
W1−2 = PdV = P [ V2 − V1 ]
1

Isochoric process (here dV=0), so PdV work will be zero (as Volume=Constant)
ŽŵƉƌĞƐƐŝŽŶ
džƉĂŶƐŝŽŶ

YŝŶ YŽƵƚ

(Here expansion and compression defined for pressure)

Like to expansion P↓ in compression P↑

WsсŶZd

Ɛdљ͕Wљ
Thermodynamics

 ƚŽŵĂŬĞ
 ǀŽůƵŵĞ
ĐŽŶƐƚĂŶƚ

24.
Polytropic process (here PVk = Constant)
1<k <r Polytropic lies between Isothermal & adiabatic process
 k−1 
P1V1 − P2 V2 P1V1   P2  r  nR
W1−2 = = 1 −    = [ T1 − T2 ]
k−1 k − 1   P1   k − 1
 

/ƐŽďĂƌŝĐdžсϬ

P
/ƐŽƚŚĞƌŵĂůdžсϭ
/ƐŽĐŚŽƌŝĐ WŽůLJƚƌŽƉŝĐdžсŬ
džсཫ
ĚŝĂďĂƟĐdžсƌ
v 

ĚŝĂďĂƟĐdžсƌ

WŽůLJƚƌŽƉŝĐdžсŬ
P
/ƐŽĐŚŽƌŝĐdžсཫ/ƐŽƚŚĞƌŵĂů
džсϭ


P 

1 v

2
W1−2 = ∫ PdV
1

Area under the curve will give displacement work

Cyclic process
Thermodynamics

Note: - Straight light can never say like it is Adiabatic or Isothermal as (we have seen that
they use curve)
W1−2 =0

25.
 W2−3 = P2 [ V3 − V2 ]
W1−3 is given by the area under the curve

ϭ


Ɖ
 Ϯ ϯ

s


Anticlockwise is work consuming cycle as area under (2-3) curve< (1-3) curve
(2-3) expansion (1-3) compression
So, (1-3) (Negative)


Ɖ
 Ϯ ϯ

Clockwise cycle is work producing system as area under (2-3) curve < (1-3) curve
(1-3) is positive (expansion
(2-3) is negative (compression)

ϭ


Ɖ
 ϯ Ϯ

In case of cyclic process, total change in energy = 0 (Point function)But heat & work ≠0
(Path function)
Thermodynamics

26.
 ϭ


Ϯ ϯ

But heat & work ≠0 (Path function)

Since energy is point function or state function

Q A fluid at a pressure of 3 bar with specific volume of 0.18 sq m/kg is con-

tained in a cylinder behind the piston. The fluid expands reversibly to a
C
pressure of 0.6 bar according to the law P= 2 Calculate the work done by
V
the fluid on the system.

Sol: r=1
r−1
P1V1 − P2 V2 P1V1 P2
W1−2 = = [1-( ) r ]
r−1 r−1 P1
= 0.298
298580 Joule/kg OR 29.8 KJ/kg
9 kg of mass is there than 59.6 KJ

Q One kg of certain fluid is contained in piston cylinder assembly 10 bar, the

fluid is allowed to expand reversibly behind piston, until the volume be-
comes twice of that Initial volume & during this expansion process PV 2 =
Constant is constant, the fluid is than cooled reversibly at constant pressure
(PV↓=RT↑) until the piston gains its original position, finally the fluid is
supplied with the heat reversibly with the piston formally logged (constant
volume) in position & the fluid pursue rises to the initial value 10 bar. If the
fluid has an initial volume 0.05 m3 , then find net work done by the process.

Sol: P1V12 = P2 V22

Thermodynamics

10bar × 12

22

27.
 P2 = 2.5 bar ϭ
P1V1 − P2 V2 ϭϬďĂƌ
W1−2 = 
r−1
20 × 0.05 − 2.5 × 0.05 × 2 Ϯ͘ϱďĂƌ Ϯ ϯ
W1−2 = = 0.25 bar
2−1
W1−2 = 25 KJ
W2−3 = P2 [ V3 − V2 ] = 2.5 ×105 (1x0.05-2x0.05)
= - 12.5KJ
W3− 1 = 0
Wtotal = 12.5 KJ

Q A cylinder with frictionless piston contains 0.1 m3 of gas at 200 KPa pres-
sure, the piston is connected to a coil spring which exerts proportional to
the displacement from its equilibrium position. The gas is heated until the
volume is doubled at which the pressure is 500 KPa. Find out the work done
by the gas takes atmospheric pressure as 100 KPa.

Sol: As volume ↑, then force (opposite) applied by the spring will be more
By applying force balance
pA= paA + Kx
Kx ͘͘͘͘͘͘͘͘͘
p = pa +
A ͘͘͘ŐĂƐ͘͘͘͘
 
KV ͘͘͘Wϭs͘͘͘͘
pA=pa +
A ͘ ͘ ͘ ͘ ͘͘ ͘ ͘ ͘
KV
p = pa + 2 džсϬdžϮ
A
y = C + mx
200 + 500
[ ]x[ V3 − V2 ]
2
(200-100)+200=300
35 KJ
Thermodynamics

28.
 Q 1 mole of gas which obeys PV=RT, R= 8.314 J/work, the gas is heated at con-
stant volume till the pressure rises to 0.5 mPa & then allowed to expand at
constant temperature till the pressure reduces to 0.1 mPa, finally the gas is
returned to its original by compressing at constant pressure, calculate the
work done by the gas in each of the process. The initial temperature & pres-
sure of the gas is 300 K & 0.1mPa.

Sol: ϭ
Ϭ͘ϱŵWĂ
W
Ϭ͘ϭŵWĂ Ϯ ϯ

W1−2 = 0 W1−3 = 0
P1
P[ V3 − V2 ] W1−2 = nRT ln
P2
W1−2 = nR [ T1 − T3 ] =20071.30J
= - 9976.3
P1V1 = P2 V2
nRT
P=
V
P ∝ T
P2 T2
=
P1 T1

0.5 T
= 2
0.1 300
T2 = 1500 K
W= 10095.0 J

Change in energy in the system due to work transfer

If the resistance wire replaces by motor pulley arrangement, then the current flowing in the
resistance wire will be utilized in raising the weight or falling of weight
Thermodynamics

PVT behavior on the fluids

Any equation that relates the pressure volume & temperature is called equation of state
(called as constitutive relationship)

29.
 For Ideal gas
PV = nRT
Size of the molecules is very small a negligible, 22.4 l→ 6.023x 1023 molecule
1 m3 = 2.68 x 1025 molecules
so whole volume is available for the motion of
gas or volume occupied by the gas molecules is
Volume occupied by 1 mole
1
very low. And this is high & low pressure = x 10−25
2.68
= 3.73 x 10−26 m3
π 3
d = 3.73 x 10−26
6
d = 4.4 x 10−4 = 2.2 nm = r
Assumptions: - In the Ideal equation of state
There is no molecular attraction or repulsion (intermolecular force) between the molecules
of gas, & they are in the state of continuous motion.
The volume occupied by the gas molecules is negligible as compared to volume occupied
by the gas.
For Example, at STP
1 m3 → 2.68 x 1025 molecules
& Hence volume occupied by 1 molecule is
1m3
25
= 3.73 x 10−26 m3 = 4 x 10−26 m3
2.68 × 10
Hence the diameter of the molecule is very small that is 4.4 mm & hence volume occupied
by molecules themselves is very very negligible.
Ideal gas equation of state can also be obtained from charle’s law & Boyle’s law
Boyle’s law: - The volume of gases varies inversely with the pressure when temperature is
held constant.
1
V ∝
P
Charle’s law: - volume of gas is proportional to the temperature when the pressure is kept
constant.
V ∝ T
By combining
PV= nRT
From experiment it is also found that pressure is directly proportional to temperature
P ∝ T
The behavior of Ideal gas can be assumed to be Ideal gas at sufficiently low pressure when
Thermodynamics

P → 0, At very very low pressure and at high temperature any gas said to be Ideal.
“from Ideal gas it is found that internal energy for Ideal gas is only a function of temperature.”

30.
Real gas: - There is no single equation of state, which will describe the behavior of Real gas,
throughout the operating range of temperature & pressure.
Hence no equations of states are available for the behavior of gases.

1. Van Der-waal equation of state

V → Molar volume
T → Absolute temperature
a, b → constant
a
(P+ ) (V-b) = RT
V2
Measure of inter
a → molecular attraction
b → size of molecules

2. Clausius equation of state

P(V-b) = RT
As in real practice, there is always attraction to the molecules.
Due to intermolecular force of attraction the molecules in the interior of gas, are attracted
equally in all directions by the surrounding molecules, but the molecules adjacent to the
container wall experience a net invert force & therefore a molecule adjacent to the container
wall exert the less force on the wall, their they observed pressure is less than the pressure
in the absence of attractive force & the production in the pressure is proportional to no
of molecules per unit volume in the layer adjacent to the wall and to the no of molecules
volume to the second layer of the wall which is attracting. If p is the pressure exerted by the
gas in the absence of attractive force.
2
 No 
p’ – p ∝  
 V 
2
 No 
Δp ∝  
 V 
2
 No 
Δp = a’  
 V 
a
Δp =
V2
a
P’ = (p + )
Thermodynamics

V2
Actual volume available for the molecular motion is (v-b) b indicates the molecule size.
It is also called the cubic equation of state.

31.
 RT a
P= - 2
V −b V
For a given P, & temperature then three molar volumes will be there on solving the given
equation of state for a given temperature & pressure three molar volume is obtained, all the
values are found to be real & positive.
At some certain set of temperature & pressure, all the roots will be equal.
When T>Tc, only one real value of volume is exit
When T<Tc, there real value of volume exists.
Vf→ Specific or molar volume of standard
Vg→ Specific or molar volume of standard vapor
At T=Tc, all these roots are real and equal.

dхdĐ

/ƐŽƚŚĞƌŵĂů
 dĐ ;ŽŶƐƚĂŶƚ
 ƚĞŵƉĞƌĂƚƵƌĞͿ

WĐ
  >нs 

W

Ă
> ^ĂƚƵƌĂƚĞĚ
;^ĂƚƵƌĂƚĞĚ
ůĂŐͿ sĂƉŽƵƌ

sĨsŝsŐ

Vander waal equation is valid for liquid & gases both.

Experiments say that a straight line should be followed.

limitation of Vander wall

Thermodynamics

Experiments show that curve should follow in (L+V)

Ace instead of abcde
The value of a and b can be found finding the slope and curvature.

32.
Slope → First derivative at critical point on Isotherms
→ Second derivative at critical point on Isotherms
∂P ∂ 2P
. = 0T = Tc  = 0T = Tc 
∂V ∂V2
Find the value of a & b
Redlich kowng equation of state
RT a
= -
V −b (
v v −b )
Peng- Robbinson of state

Virial equation of state

Compressibility Factor (z)
Molar volume of real gas to the molar volume of Ideal gas
V
z= Pvig = RT
Vig
VP ig RT
z= v =
RT P
Z = 1 for Ideal gas
Z > 1 For Real gas Z < 1
Most of the cases Z<1
When intermolecular repulsion is less than attraction then (z<1)
According to virial chacha
PV B C D
Z= =1+ + 2 + 3 + ………..
RT V V V
Constant B,C,D are the function of temperature & types of gas, If same gas is there then
B,C,D is function of temperature only where B,C,D are known as second third & fourth virial
coefficient & this coefficient express the deviation of the Real gas from Ideal gas behavior.
They depend upon gas species. Advantage of virial equation is that it can represent the
experimental result more accurately by increasing the coefficient.
PV R1 C1 D1
Z= = 1+ + 2 + 3
RT T T T
PV 
= Z = 1 + B1 P + C1P2 + D1P3
RT
Thermodynamics

Law of corresponding state

For every gas different behavior is there
Every gas has its own critical temperature & critical pressure

33.
 ϭ


 Ϯ

ϯ
ϰ
d

A T= 300 K P= 2atc

Tc=600 Pc=1atm

Tr=0.5 Pr=2

B T=600 P= 4atm

Tc=1200 Pc=2atm

Tr=0.5 Pr=2

Law of corresponding states that all fluids when compared at the same reduced
temperature & same reduced & pressure, will show the same value of reduced volume
or some value of compressibility factor. In other words, when all fluids compared, at the
same reduced temperature & pressure, they will show the same duration from the Ideality
(same value of Z)
Zr = f (Tr, Pr)
Vr = f (Tr, Pr)

ϭ͘ϭϭ
͘Ϭ
 dƌсϮϬϬ
 

 dƌсϭϴϬ
dƌсϭϱϬ

dƌсϭ͘Ϭ
Thermodynamics

a
Then, ( Pr Pr+  ) (Vr-b) = RT
V2r

34.
Corresponding state law involved two parameter reduced temperature & reduced pressure

temperature pressure Tc Pc

A 600k 2atn 1800 1atm

B 1200k 6atn 3600 3atm

This is also as law of two parameter corresponding state, when Z is a fn of Tr & Pr

Z = f(Tr, Pr) → two parameter model
Pitzer found that a group of fluids having identical intermolecular potential will follow
the two-parameter model corresponding state law & the fluid which have identical
intermolecular potential like Argon Krypton, Xenon they are called as simple fluid. So,
they found that we have to use one more parameter for different identical intermolecular
potentials.
Hence the pitzer defined the acentric factor ‘w’ in terms of reduced pressure.
As below
W= -1- log Prsat / 0.7 = Tr
W= log Prsat (SF)/ - log Prsat (CF ) / 0.7 = Tr
W measures the difference in intermolecular potential or deviation of complex fluid behavior
from simple fluid behavior and it is a characteristic of molecular structure.
If it is simple fluid w= -1-(-1) = 0
W = o for simple fluid
Vapor pressure & temperature will give the straight line in the log log plot. So, it is easy to
study.
Z = f(Tr, Pr, W) law of three parameter corresponding state
Generalized equation of state
Redlich Kowng Equation of State: - With some modification of RKE this can be changed into
a generalized equation of state.
Which can be valid for wide range of T & P
Find the PdV work done for the gas following Vander waal equation of state as below
a
( +  ) (V-b) = RT
V2
2
W= ∫ PdV
1

2 RT a 
w=
∫ 
1 V −b
−
v ( v − b )
 dV
Thermodynamics

 
a
= [RT ln(V-b) + ] V2 V1
V

35.
 [V2 − b] 1 1
W= RT ln +a[ −  ]
V1 − b Y2 Y1

P(V-b) = RT
V2 RT
∫
W= PdV = ∫ V1 V −b
dV

RT ln[V-b] V2 V1
[V2 − b]
W= RT ln
V1 − b

Zeroth law of thermodynamics

This law simply indicates the condition of thermal equilibrium.
If body A is in thermal equilibrium with body B & Body C is in thermal equilibrium with body
A, then Body B & C will always be in thermal equilibrium.
TA=TB and TA= TC →TB=TC
Then TA=TB=TC

First law of thermodynamics

Joule’s Experiment

For any cyclic process, net amount of heat transfer is equal to the amount of work
ΣQ =ΣW
Whatever amount of work done on the system equal amount of heat released
He did electrical work & displacement work, always the result was the same as the first law
of thermodynamics (only for close systems). In (1884-1946) joules done no of experiment,
one of them is described below: he placed a stirrer to churned the fluid in the Insulated
vessel, by performing the work on the system (By rotating the system) internal energy of
Thermodynamics

the fluid has increased & that increase in the internal energy has measured through in
temperature.

36.
In the Second step he has removed the insulation & allowed it to transfer the energy in form
of heat to the cold fluid surrounding the tank.
And he has found that the amount of heat transferred from the system is exactly equal to
the work done on the system.
Joules has performed different experiments by performing different forms of work in every
experiment he has found the same result.
In any cyclic process, net work transfer is equal to the net heat transfer.

∑ W 0Cyclic = ∑ Q 0Cyclic First law of thermodynamics for cyclic processes.

Work done by the system +ve W1-W2 = net work transfer to the system
Work done by the system -ve Q1-Q2 = net heat transfer from the system

∫ (ðQ − ðW ) =
0
Cyclic Integral of any property is zero

First law of thermodynamics process for cyclic process

First law of thermodynamics for cyclic process, we can see that if we are not going to
give any amount of heat then we are not able to have work. Perpetual machine of 1st kind
operates w≠0 or perform work without any heat (this is not possible) [Imaginary machine]
“Main role of TD is to obtain power from heat”
In a cyclic process there is no energy transfer in form of heat to a system, the system cannot
perform any network. The law of conservation will not be valid.
A cyclically working device which continuously delivers a network without receiving any
energy in form of heat surroundings is called a perpetual motion machine of the first kind
which is not possible.

Conclusion
It is impossible to construct a device whose sole purpose is to deliver the net amount of
work transfer, without receiving any net amount of heat transfer.

First law of thermodynamics for non-cyclic process

Since, energy should ever be conserved,
∆E = Q − W  (Energy stored in system)
ðQ – ðW = dE
2 2 2
∫ ðQ – ∫ ðW = ∫ dE
1 1 1

Q1−2 − W1−2 =
E2 − E1

Thermodynamics

Q1−2 − W1−2 =
∆E
ΔEsystem:- Energy can be stored in the system in two forms (Macroscopic, Microscopic)
∆Esystem =∆ [EK + EP + U]

37.
 For close system: - Ek & Ep = 0
∆Esystem =
∆U

ðQ − ðW =
dU
Q1−2 − W1−2 =
∆U
Stored Energy as a point fn or State fn
There are two cycle
1. 1-A-2-B-1
2. 1-A-2-C-1

For cyclic process

∫ (ðQ – ðW ) = 0
For 1 cycle (1-A-2-B-1)
st

2 2
A ∫
ðQ –( ðW
1 ∫
B ) + ðQ –( ðW
1
0) =

For 2nd cycle (1-A-2-C-1)

∫ (ðQ – ðW ) = AðQ∫ –( ðW 2

1
) – C ∫
2
ðQ –( ðW
1
) =0

2 2

∫1 (
ðQ – ðW
A ) = -C ∫ 1
(ðQ − ðW )
2 2
B ∫ 1 (ðQ − ðW ) =
C ∫ ( ðQ – ðW )
1

2 2
B ∫ dE1
=C ∫ dE
1

For Isolated system

Q1−2 - W1−2 = ∆U
U1 = U2 Energy is consumed
E 1 = E2

Application first law of thermodynamics in close system

Q1−2 − [ WPdV + WShaft + WElectrical + … ..] = ∆E
We can see that,
As ∆E is state fn, so it is valid for Irreversible and Reversible
ðQ − ðW =dU (For both irreversible and reversible)
Thermodynamics

ðQ – PdV = dU (Reversible only)

38.
Q consider a system taken from state 1 to state 2 as shown in the figure:
Along the path 1-a-2 100 KJ of heat flows into the system and the system
does 40 KJ of work.
i. Evaluate the heat that flows into the system along the path 1-b-2. If it is
accompanied by 20 KJ of work transfer from the system.
ii. Calculate the work done & heat exchanged if system returns to the initial
state along the straight path

Sol: i. 100 – 40 = ΔU = U2 - U1
ΔU = 60
Q1−b−2 - W1−2 = 60
Q1−b−2 = 80 KJ
ii. 100 + 80 =180
ΣQ – ΣW
Q1−a −2 - Q2− 1 = W1−a −2 - W2− 1
100 + Q2− 1 = 40 + W2− 1 -------------(1)
By applying 1st law for process 1
Q2− 1 - W2− 1 = - ΔU
Cycle total 1-a-2-b= 20 KJ
In Half cycle W1−a −2− 1 = 10 KJ
W1−a + Wa −2 + W2− 1 = 10
W2− 1 = - 30KJ
Q2− 1 = 40 – 30 – 100 = -90 KJ

Q When the system taken from a to b as shown along a & b 84 KJ of heat flows
into the system & system does 32 KJ of work. How much heat flows into the
system along the path a-d-b. If work done along this path is 10.5 KJ

Sol: Qa −c −b = 84 KJ
Wa −c −b = 32 KJ
Thermodynamics

Wadb = 10.5
84-32 = 52 KJ
Qa −d−b = 52 + 10.5 = 62.5

39.
 Q 90 KJ of heat is supplied to the system .System rejects 95 KJ of heat at con-
stant 18 KJ work done on its system is brought to the initial state via adia-
batic process, find work done during adiabatic process & also find change in
internal energy in all states of internal energy at state 105KJ.

Sol:

PV = nRT
P↑Cons T↓
P = Constant, T↓ V↓
90 – 95 + 0 = 0 – 18 + W1−2
-5 + 18 = W1−2
W1−2 = 13 KJ
U1 = 105 KJ
U2 - U1 = 90 - 0
U1 = 90 + 105 = 195 KJ
U3 - U2 = -95 + 18
U3 - 195 = -113
U3 = 118 KJ

Q 0.2 m3 of air at 4 bar and 130°C is contained in a system reversible Expan-

sion takes place till the pressure falls to 1.02 bar, gas is then treated at
constant pressure till enthalpy increases by 72.5 KJ. Find out work done
during whole process, assume Y = 1.4 & Cp =

Sol: Heat transfer in different thermodynamic process

Assume all process is quasistatic & reversible
Isobaric process (Constant pressure process)
From the 1st law of thermodynamics
dU = ðQ – ðW
dU = ðQ – PdV

∫ dU = ∫ ðQ - ∫ PdV 
Thermodynamics

ΔU = Q1−2 - P ( V2 − V1 )

40.
 Q1−2 = U2 − U1 - P ( V2 − V1 )
Q1−2 = U2 − U1 + P ( V2 − V1 )
Q1−2 = (U2 + PV2 ) − (U1 + PV1 )
Q1−2 = H2 - H1 = ΔH
Heat transfer to the system in constant pressure process results increase in
enthalpy
J H = U + PV
Or heat transfer from the system get constant pressure process results de-
crease in enthalpy
Isochoric (Constant Volume) process
dU = ðQ – ðW

∫ dU = ∫ ðQ - 0

Q1−2 = U2 − U1
Q1−2 = ΔU
Heat transfer to the system in constant volume process increase in the in-
ternal energy.

Specific heat capacity (C)

Amount energy (heat) transfer in form of heat to raise the temperature of unit mass of
substance by unit
dQ
C=
mdT
Heat can be supplied in any system by two ways
1) Either by making pressure constant
2) Either by making volume constant

Thermodynamics

Cp=  1 dQ  Cv=  1 dQ 
 m dT P  m dT V

41.
 Since at constant pressure process
dQ = dH

Cp =  dh 
 dT P

At constant volume process Cv=  dh  or dv = CvdT for constant volume process. It is more
 dT V
appropriate to write the specific heat capacity of a substance in terms of property change

called as U change or dU or Internal Energy Change hence Cv =  du 

 dT V
Same temperature change dT dU = CvdT either by work transfer process or heat transfer
process.
Note: dQ=CvdT valid only in case of constant volume process
dU=CvdT is valid everywhere either Adiabatic/Isochoric
As Internal Energy is point fn only depends upon two fixed points.
Here Insulated dQ=0
Still Internal energy is increasing and temperature is increasing, (as work is being transfer
via ***).
Here dR is being transferred. Internal Energy is increasing and temperature is increasing
Some can say that where temperature increasing, we can
dv = wdT
For Ideal gas Hf(T)
H = U + PV
= Uf(T) + RT(f)T Hf(T)
dh = CpdT can also be used anywhere
Whereas, dR = CpdT (can only be use when pressure is constant)
Change in temperature Cp =dK
Adiabatic process
dV = đQ - đW
dV = - đW
for reversible work done
du = - Pdv
R Cp − Cv
CvdT= -PdV = = r-1
Cv Cr
dV
CvdT= -RT
v
Thermodynamics

Cv dT dV
= -R
R T v

42.
 Cv T
lnT  2 = − ln [ V ]V2

R T1 V1

Cv T V
lnln 2 = − lnln 2  
R T1 V1

T2 R V
lnln  = − lnln 2  
T1 Cv V1
R
T2 V −
lnln   = 2 ) Cv
T1 V1
R
T2 V
lnln   = 1 )Cv
T1 V2
T2 V
lnln   = 1 )r −1
T1 V2
T1V1r − 1 = T2 V2r − 1 = Constant

TVr − 1 = Constant PV = nRT

V2 r −1 PV PV
) = lnln 2 2   =T
V1 P1V1 R

V2 r −1 PV T PV
) = 2 2 2 = 2 2
V1 P1V1 T1 P1V1
P2 V2 = P1V1 PV2 = constant For adiabatic
r −1
TP  T2
lnln  1 2  = lnln   PV = nRT
 T2P1  T1

nRT V2 T2P1
TrPr − 1 Constant V = =
P V1 T1P2
P1r − 1T1r = P2r − 1T2r
Heat transfer in Isothermal process
dU = dQ – dW dU = 0, as Uf(T) only
dQ = dW there is only two processes, when there is dQ =dW
Q1−2 = W1−2 1) Cyclic 2) Isothermal
HT in Polytropic process
PV = Constant
Thermodynamics

PVk Constant 1<K<r

W= ∫ PdV

43.
 P1V1 − P2 V2 nR ( T1 − T2 )
Wpoly = =
K−1 K−1
From the first law of thermodynamics
Q1−2 − W1−2 = U2 − U1
q1−2 − w1−2 = u2 − u1 n=1 per unit mole
P1V1 − P2 V2
q1−2 =
K−1
(
+ Cv T2 − T1 )
P1V1 − P2 V2 R
q1−2 =
K−1
+ ( )
T − T1 for adiabatic work
r−1 2
P1V1 − P2 V2 P V − P1V1
q1−2 = + 2 2
K−1 r−1

1 1  PV −P V  r −1−k + 1 
q1−2 = P1V1 − P2 V2  − = 1 1 2 2  
 K − 1 r − 1   (K − 1) (r − 1) 

r −k
q1−2 = w1−2 |polytrop
r−1
r −k
Here heat transfer is less than work transfer as >0
r−1
Only process, where internal energy decreased
In case of polytropic process
It is only the process in which on supply the heat the system stored energy will get ****
work transfer is more than HT.

Q A 3 kg of air is kept of an absolute pressure of 100 kPa and temperature of

300K is compressed polytropically until the pressure & temperature be-
comes 2500kPa & 500 K. Find out polytropic exponent, the final volume &
work of compression & heat interactions.

Sol: PVk = Constant

1−k r −k
Tp = Constant Q1−2 = Wpoly
k r−1
1−k
T2 P1
= ) k Q = 317.7 KJ
T1 P2
Thermodynamics

1−k
500 100
= ) k
300 1500

44.
 500 1−k
lnln = 0.510 = ln Y2k − 1T2 = P1k − 1T1
300 k
- 0.22184 k = 1-k V2 = 0.287 m3

k = 1.23 PV = nRT
P1V1 − P2 V2
w= v = 2.58 m3
K−1
nR ( T1 − T2 ) 3
w= n = × 1000 = 103.448 moles
K−1 29
103.44 × 8.314 × ( 300 − 500)
w=
0.23
(
Q-W = nCv T1 − T2 )
R
= 103.24 × (200) = -318 KJ
r−1

Q A 0.75 kW motor derives a paddle, which stirrers for an hour 50 kg of water

content in a thermally insulated rigid tank. Assuming the process at con-
stant volume, find out the rise in temperature & change in internal energy
KJ
of water. If Cp of water 4.186 .
KgK

Sol: Rigid tank = volume is constant (PdV=0)

2700
Q = mCvdT = =12.90
4.186 × 50
ΔU =dQ – dW = 0.75 × 3600 × 1000
ΔU = 2700 KJ Thermodynamics

45.
 Q A stationery mass of the gas is compressed without friction from an initial
state of 0.4 m3 & 0.1mPa to a find state of.0.2 m3 & 0.1 mPa, if there is a
transfer of 45 KJ of heat from the gas ** the process finds out the Internal
energy change.

Sol: 0.1 ×106 [0.2 – 0.4]

W= -20KJ
Q-W = ΔU
-45 + 20= ΔU
du= - 25 KJ

Q The relationship between pressure & volume in a close system is given by

 3 
P = + 2  during the process 1600 KJ of heat is added to the gas &
 V m3 
 1 
volume changes from 1.2 m3 to 4 m3 find out the change in internal energy.

Sol:

Q= 1600 KJ
W= PdV
W = [3lnln V + 2V ]4 × 105
1.2

W = 921.19 KJ
Q – W = ΔU
ΔU = 678.80 KJ

Q A close system consists of fluid inside the cylinder fitted with a frictionless
piston. When the fluid is stirred by a paddle 120 KJ mechanical work is sup-
plied along with 40 KJ of energy in the form of heat. At the same time the
piston moved in such a way that pressure remained constant at 200 kPa and
volume changed from 2 m3 to 4 m3. Find out the change in **

Sol: Q = 40 KJ
w 1−2 =P [ V2 − V1 ]
ΔQ = Δn only applicable when there is only PdV work

w 1−2 = 400 KJ Q – W = ΔU
Thermodynamics

wpadle = -120 KJ 40 – 280 = -240 KJ

H = U + PV
ΔH = dV + PdV = -240 + 400 = - 160

46.
Q 60 liters of an ideal gas at 290 K & 1 bar is compressed adiabatically to 10 bar
it is then cooled at constant volume and further expanded Isothermally so as
to reach the condition from where it is started.
Calculate
1. pressure at the end of constant volume cooling
2. Change in Internal Energy during constant volume process.
3. Net work done & HT during the process.

Sol: (1) PV = nRT

PLV = Constant, as T↓ (work consuming)
KJ
Cp = 14.28
KgK
KJ
P1V1r = P2 V2r Cv = 10.15
KgK
V2 = 11.665 r = 1.406
T1V1r − 1 = T2 V2r − 1
290 × 500.406
T2 = = 560.53 K
11.6650.406
(2) dU = mCvdT PV = nRT
P T
1 = 1
P2 T2
P2 = 2.1711 bar
PV =nRT
105 × 60 × 10−3 = m = 5.046 ×10−3 kg
dU = mCv ( T3 − T2 ) = 13.958 KJ
P1V1 − P2 V2  
(3) = -12.282 or mCv ( T3 − T2 )
r−1
= 5.046 × 10−3 × 10.15 × 290 − 562.23
= −13.94 KJ
w2− 1 =0

V2
w3− 1 = nR lnln
V1
Thermodynamics

V1
= nR lnln
V3

47.
  60 
= 5.046 × 10−3 × 4.14  lnln   
 11.665 
= 9.92 KJ
Net work done = −  4.018 KJ

Free Expansion or (unrestrained)

When the gas is allowed to expand under vacuum it is called free expansion.
Consider a thermal insulated rigid tank which is initially divided into two compartments by a
membrane. One compartment contains an ideal gas and the other is completely evacuated.
When the compartment is removed or punctured the gas expands and rushes into the
evacuated compartment to occupy the entire volume of the container.
From the first law (as dt is closed system, we can apply)
dU= đQ - đw
Since, work done is zero during expansion Q=0 (insulated) of the gas, there volume is going
to increase but here, there is no resistance to be overcome and there is no meaning of PdV,
as PdV is defined for quasistatic process (whereas this expansion is very fast)
dU = 0
U1 = U2
T1 = T2
Properties of expansion process
1. Free expansion is highly irreversible
2. This is not isothermal (through T1=T2)
But the process is said to be isothermal, if the temperature between T1 & T2 at every state
should be the same, while in the free expansion process intermediate states are not able
to be defined.
Here in the starting of the process temperature starts to decrease, as it gets more area, but
after that increases strike on the boundary. So T↑
y It is a highly irreversible process. (As it is very fast)
y Work is always zero.
y Ti = T0 (does not mean that process is isothermal)
y ni = nf (initial and final mass will be same)
PiVi PfVf PfVf
y =  Pi =
RT RT Vi
PiVi = PfVf

For adiabatic process

Thermodynamics

TVr − 1 = Constant
lnln T + r − 1lnln V    = Constant
lnln T  = ( )
− r − 1 lnln V  

48.
First law of thermodynamics to the open system
(There is no meaning of PdV)
By applying law of conservation of mass
dmw
min − m  out = 
dt
n n dmCv
∑ i= 1
mi |Inlet - ∑ i= 1
me |Outlet =
dt
Appling the mass balance over small time interval Dt
min −  mout =
 ∆mCv

Law of conservation of energy

Flow work: work required to maintain in flow and out flow in the process.
Other fluid behind that element behaves as a piston.
w = F.l
= PA.l
w = PV

Type of energy
If e is the energy per unit mass or specific energy. Energy can be entered in a system by
following three ways
1. Energy transfer by mass flow
2. Energy by heat transfer
J K.E P.E U
e( )= + + + PV
Kg m m m
C2
emass =   + gz + u + Pv c→velocity As u + Pv = h
2
C2
emass =   + gz + h
2
for open or flow system h(enthalpy) is summation of Internal Energy or flow energy
C2
emass =   + gz + h
2
E = em
 Rate of energy in by mass flow
 C2  J
=E m    + gz + h 
 2  Sec
 
Thermodynamics

Energy transfer by heat transfer

(Q )= Q  −Q

net in 1 2

49.
 Energy transfer by work transfer
Net Energy out by the work transfer
w  w
 net =1− w
2 +w (
 3 System )
(Here w cannot be Pdv, It will over be shaft work)
By applying Energy balance
dEsystem
E in − E out =
dt
(By mass flow HT +work)
dEsystem
m
 inein − m
 out eout =
dt
ÿ 
Ci2  ÿ  ÿ  Ci2   dEsystem
mi  + gzi + hi + Qi− 0 − mi  + gzi + hi + 0 + Ws  =
 2    2   dt

n ÿ 
Ci2  n ÿ  Ci2  dE
∑ i
mi 
1=
 2 

+ gzi + hi + Q Net
−
i 1∑mi 
 2 
 ] =system .
+ gzi + hi − WNet
dt
Unsteady state flow Energy Balance equation
dEsystem d[esystemmsystem ]
=
dt dt
d
=
[E + Ep + U
  ]
dt k
For steady state flow process

m
 in =  m
 out
∑ m = ∑ m
in out

For single input & single output flow stream, S.S flow energy Balance
 ∆C2 
m
  
+ g∆z + ∆h − Q 
+W ] =0
Net Out
 2 
∆C2 Ce2 − Ci2
= , g∆z = ( z2 − z1 )g, ∆h = h2 − h1
2 2
 ∆C2 
 −  W
Q  = m
  + g∆z + ∆h
in out
 2 
ÿ   ÿ  
Ci2 Ci2
∑ mi 
 2
+ gzi + hi 2 e −

∑ mi 
 2
 −  W
+ gzi + hi 2I n =   Q

in

out
Thermodynamics

m
 1 +m m
2 =
3

m
 1e1 + m  −m
 2e2 + Q  =
 3e3 − W 0
in s

50.
 C 2  C 2  C 2 
 1  1 + gz1 + h1  − m
m 2  −W
 2 + gz2 + h2  + Q  − m
   3
+ gz3 + h3   =
0
in out 3
 2   2   2 
∆C2
If ≅ 0, g∆z ≅ 0
2
 −W
Q  = m
  ∆h
in out  
Applying the energy Balance for small time Interval Dt
mein − meout   + Qin − Wout =
 ∆Esystem

Applying of first law in flow system

In Heat Exchange
Always H.E work as on S.S
m =
1
m
 2m
  =
3
m=
4
 m
 =
H
  m
 C 
BY applying energy Balance
m  1e1 + m  −W
 3e3 + Q = m
 2e2 + m
 4e= 0 
4

As here m
1 =m
2 & m
4 =m
 3 at S.S

m
 H (e1 − e2 ) = m
  C (e4 − e3 )
m
 H (h1 − h2 ) = m
  C (h4 − h3 )
m
 HCPh (T1 −=
T2 ) m
  CCPc (T4 − T3 )
Energy given by hot fluid = Energy taken by cold fluid

Over the Compression

Work is done on the system to compress the gas
 ∆C2 
 −W
Q  = m
  + g∆z + ∆h
 2 
 2 
 +W
−Q  =  ∆C + g∆z + ∆h
 2 
For adiabatic
2
 = 0, ∆C & g∆z = 0
Q  −W
Q  = m
  ∆h
2  

−WShaft = m   ∆h
 
Thermodynamics

Over the turbine

ÿ  ∆C2 
 −W
Q = m
  + g∆z + ∆h
Shaft
 2 

51.
 ÿ
− WShaft = m
  ∆h
 
ÿ
WShaft = − m
  ∆h
 
ÿ
WShaft = − m
 h1 − h2 
 

Nozzle
 ∆C2 
 −W
Q  = m
  + g∆z + ∆h If R=0,Ws = 0
 2 
∆C2
∆h =−
2
∆C2
= h1 − h2 
2
We increase the kinetic energy at the expanse of decrease in enthalpy

Q A nozzle is a device for increasing the velocity of steadily flowing stream at

Inlet to a certain nozzle, the fluid parameter are

Inlet Exit

h1 = 2820 KJ/Kg h2 = 2650 KJ/Kg

C 1 = 50m/s Area
Area= 0.1 m 2
v= 0.49 m3 / kg
V= 0.18 m3 / kg

Make calculation for velocity of the at exit from the nozzle & the mass flow
rate of the fluid at the exit area of the nozzle, there is negligible heat lass
(nozzle is horizontal).

Sol: m
 ∆C2
 

+ g∆z + ∆h =0
 2 
502 Ci2
Thermodynamics

−  + 2650 − 2850 × 103

2 2
Ci = 630.47 m/s

52.
 A 1V1 = A2 V2 here we cannot use this
m
 = CAV As density has been changed
0.0079 1
m
 = x 630.47 m = 0.1x 50 x
0.49 0.18
m
 = 10.20Kg/s m = 27.778 Kg/s

A perfect gas (gas which having Ideal gas property but the Cp should not be
fn of temperature)
A perfect gas flows through a nozzle where it expands in reversible adiabatic
manner the inlet conditions are at 22 bar, 500°C & 38 m/s & at exit pressure
in two bar find out exit velocity, exit area, If the flow rate is in 4 Kg/s use
J
R = 190
KgK
r = 1.35
Cp
= 1.35
Cv
Cp = 1.35 Cv
 ∆C2 
hi  + g∆z + ∆h =0 ∆h =∆Cp∆J
 2 
∆C2
∆h = -   R= Cp - Cv
2
C22 − C12 R Cp
h1 − h2 = = – 1 = 0.35
2 Cv Cv
190
Adiabatic process = Cv
0.35
1−r J
TP = Constant C2 = 725.3 m/s Cv= 542.85
r KgK
−0.35 −0.35
J
500 x 22 1.35 = T2 × 2 1.35 Cp = 732.36
KgK
T2 = 268.521°C

T2 = 415.1

m
 = A 1 & C1 A 2 = 2.017 × 10−3 m2
m
Thermodynamics

A 1 =
R1C1
PV = nRT

53.
 PV = mRT
22 × 105
=e
(
190 × 500 + 273 )
e = 14.975 Kg/ m2
A 1 = 0.00703 m2

Q A perfect gas has a molar mass of 26 Kg/Kmol & Valve r= 1.25. Find the heat
rejected in the following two processes.
1. When 1 kg of mass of the gas is contained in the rigid in vessel at 2.5 bar
and 225°C, and is cooled until pressure falls to half of the initial value.
2. When 1 Kg/sec mass of the gas enters in pipeline at 300°C and flow
steadily to the end of pipe where T is 25°C, changes in the velocity of the
gas in the pipelines is negligible.

Sol: Cases Closed system r=

Cp
1.25Cv = Cp
Cv
J
Q – W= U R= 8.314
molK

8.314 J 1000 mol K mol

molK 1 Kmol 26 Kg

J
R = 319.76
KgK
J
Cv = 1.279 = 0.76
KgK
PV = nRT
P1 T1 498
= T1 =
225°C 498K T2 == 249K 
P2 T2 2
T1
2 =
T2
T2 = 249 K
Thermodynamics

Q = 1.279[249 - 498]
Q = - 318.471 KJ heat rejected= 318.47

54.
 II) m
 = 1Kg/s
Q= m  (Δh)
Q= m
 [Cp(ΔT)]

 (
= −1 ×  1.598 × 300 − 25 
)
R = - 439.659 Kw (heat rejected)

Q Air at 290 K temperature passes through a heat exchanger at 30 m/s velocity

& its temperature gets raised to 1100K. Subsequently the mated air enters a
turbine with the same velocity on its expansion and continues till the tem-
perature drops to 900 K. After exit from the turbine, velocity has increased
45 m/s. Further expansion occurs in a nozzle & temperature falls to 790 k. If
the mass flow rate of air is 2 Kg/s find out
1. Rate of heat transfer to the air in heat exchanger
2. Power output from the turbine
3. Velocity exit from the nozzle.
J
(Assume no heat loss and Cp= 1.005 of air)
KgK

Sol: (1) m
 Cp ( T2 − T1 )

= 2 × 1.005 ×  1110 − 290

KJ
= 1628.1 = Kw
S
 ∆C2 
(2) W − Qout = m
  + g∆z + ∆h
 2 
452 302
= 2[ − + 1.005 × b3 900 − 1100k  ]
2 2
Qout = 400.875 KJ/S

∆C2
(3) = ( h1 − h2 )
2
C22 − C12
= = 1.005 ×103 900 − 790
2
Thermodynamics

C2 = 472.36 m/s

55.
 Q During a steady state flow compression process of a gas with mass flow rate
KJ
2Kg/sec, there is increase in kinetic energy of 2 . and the heat rejection is
Kg
3 Kw. Find out the work done on compression.

Sol: Q−W = m
 ∆C2
 

+ g∆z + ∆h
 2 

−3 − W = 2  −2 + 15

−3 − W = 2  13
−W = 26 + 3
W = −29K J
Work done by compression is 29 KJ/sec

Throttling process
Throttling process is a process in which fluid is allowed to flow through restrictions.
Restriction may be in the form of valves/ porous plugs and small diameter tubes (capillary
tube).
In 1853, Joule & Thomson conducted a porous plug experience to measure the change in
temperature of a gas when it flows steadily through a porous plug.
In the Experiment, porous plug operates consist of long horizontal and insulated pipe at the
centre of which porous plug is inserted as shown in the figure.
Since pipe is insulated Q=0
Ws = 0 (no shaft work)
∆h = 0
h2 = h1
Change in enthalpy is zero. (Enthalpy is constant)
Or this process is also called the Isenthalpic process.
It means, whenever a fluid flows steadily from high pressure to low pressure through a
porous plug or partially opened valve, inserted in a long horizontal and insulated pipe,
enthalpy of the fluid remains constant. Such a process is called Throttling or Isenthalpic
process.
As T1 P
  1 is fixed as point 1, which means *** is fixed.
Thermodynamics

The point when uj=0 is called an inversion line or curved.

If the gas is allowed to cool via throttling, then its temperature, must be lower than the
inversion temperature cooling in takes place

56.
Maximum cooling will be obtained when the inlet temperature or pressure of the gas lies on
the inversion point.
If the operating temperature of the gas is more than maximum inversion temperature,
than that gas does not cool by the throttling than we would go for H.E upto inversion
temperature
Uj=0 for inversion pt
Tmax = 25°c (inversion)
And if any gas is at 45°c, we have to cool that gas via throttling, then we should take 45°c
to 25°c via H. E first, then leave for cooling.
For real gas h f(T)
For ideal gas h1 = h2 Note: we cannot cool ideal gas via throttling
T1 =T2
P2 <P1 in case of ideal gas
T1 = T2 In Isenthalpic process
1. In Air conditioning system
2. Refrigeration system
3. To measure the quality of steam

Second law of thermodynamics (directional law)

1. It imposed directional constraints for any process to happen hence called as directional
law.
2. Every process in the universe is not at random, they takes place in some certain directions,
and that direction constraints is given by second law of thermodynamics
3. It also states that, energy not only has quantity, it also has quality.
But Reverse is not true
W→ High grade energy Q≠W
Q→ Low grade energy Q>W
Work can be fully convertible to the heat during the process. 1-2 is ideal condition, but heat
cannot be fully converted into work when in the ideal condition, this indicates that energy
does not have quantity only even if it has quality also.

Statement of second law of thermodynamics

1. Kelvin &Planck’s statement: It is impossible by a cyclic process to convert heat absorbed
by a system completely into the work done by the system.
Or
In other words, it is impossible to construct a cyclic device whose sole purpose is to
convert all amount of heat absorbed into the work.
Not visible in real practise
Thermodynamics

Perpetual motion machine of second kind

57.
 Clausius statement
It is impossible for any cyclic device, whose only purpose is to transfer the heat
from low temperature to high temperature without any energy intersection to their
surroundings.
In real practice this type of device is not possible
To complete the cycle, always some amount of energy in the form of heat has to be wasted
in the sink, which can be recovered.

Heat engine and thermal reservoir

Thermal reservoir
It is an infinite source of energy, on removal of the heat and transferring of the heat
temperature off the thermal reservoir will not be changed.
There are following two types of thermal reservoir
y Heat source. on removal of the heat temperature plus source won’t change
y Heat sink. On transferring the heat to the sink temperature won’t change
It is only possible when Cp equals Infinity.
Heat engine
y It is a cyclic device that operates in a cyclic manner
y It absorbs the heat from source
y Some part of the absorbed heat will convert into the work by heat engine, remaining amount
of energy transfer to the sink in form of heat.

Efficiency of heat engine

Heat pump & Refrigerator
Revenue of heat engine is called heat pump/Refrigerator
For a heat pump, the objective is to maintain the source at high temperature, or to obtain
heat from sink & supply to source. (Maintain high temperature *** surrounding)
Refrigerator objective is to maintain the room cool.

Coefficient of performance
QH
QH QH QH 1
Cop| 2H
  P  = = = =
W QH − QC QC QC
1− 1−
QH QH

Qc Qc 1
Cop| 2R
  efri  = = =
W QH − QC QH
−1
Thermodynamics

Qc

Cop| 2H
  P  = 1 + Cop| 2R
  efri 

58.
 1 1
=1+
QC QH
1− −1
QH Qc
1
= 1−
Qc
Carnot cycle: - It is a reversible heat engine, which constitutes four reversible thermodynamic
processes.
Carnot reduces the effect of viscous dissipation or internal irreversibility using proper
lubrication, carried out in a quasi static manner. (DT ≅ 0, DP ≅ 0, DM ≅ 0)
There are four following thermodynamic processes in Carnot heat engine
P [1-2] → Isothermal Expansion
P [2-3] → Adiabatic Expansion
P [3-4] → Isothermal Compression
P [4-1] → Adiabatic Compression
From first law of thermodynamic
Net heat transfer = Net work transfer
PdQ = PdW .
QH − Qc = W1−2 + W2−3 + W3−4 + W4 − 1

( W )net QH − Qc 1 Q
ηc = = = = 1-   c
QH QH Qc QH
1−
QH
U=dQ – dW
Q3−4 = W3−4
V 
Q3−4 = nRTclnln  4   
 V3 
V 
Rc = nRTclnln  3   
 V4 
V 
Similar RH = nRTHlnln  2   
 V1 
V 
nRTclnln  3   
Q
1-   c = 1-  V4 
QH V 
Thermodynamics

nRTHlnln  2   
 V1 
For process 2-3 TVr − 1 =  constant

59.
 THV2r − 1 = TC V3r − 1
r−1
TH V 
= 3 
TC V 
 2
For 4-1 THV1r − 1 = TC V4r − 1
r−1
TH V 
=  4
TC V 
 1
By dividing these equation
r−1 r−1
 V4  V 
  =  3
V 
 V1   2
V3 V2
=
V4 V1
T
ηH.E  = 1 −   C
TH
QC TC
= Only for reversible process
QH TH

Carnot theorem: -
Theorem I: - There is no heat engine, which is more efficient than the Carnot engine operating
between the same reservoir.
First, we all going to assume 𝜂B > 𝜂A
For QA = QB

WB > WA WB Will be more (as we assumed)

Since A
If we reverse the heat Engine A the only direction will be changed with the same magnitude
and it will become a heat pump.
WNet
= WB − WA

Since WB > WA QB − WB < QA − WA QA = QB

By coupling the system, we get there is no use of sink; hence it violates the Kelvin Planck
Statement hence, whatever we assumed that was wrong.
From the Kelvin & Plank Statement, there is no device, which can produce a network out
Thermodynamics

with a single thermal reservoir.

Hence 𝜂A>𝜂B
No engine is more efficient than the Carnot engine

60.
 Second Carnot Theorem
T
ηc  =  1 −   C
TH
Efficiency of all reversible heat engines operating between the same thermal reservoirs is
the same.
Features of Carnot heat engine
y Efficiency of a heat engine does not depend upon the working fluid & types of process
that constitutes the cycle. All the processes that constitute the cycle must be
reversible.
y Efficiency of a heat engine only depends upon source & sink temperature.
Clausius inequality
Let us consider a reversible path ab, which is going to be replaced by path a-i-d-c-b. Area
of aid is the same as the area of d-c-b.
By first law of thermodynamics
dU = dQ – dW for path ab
Ub − Ua = Qab − Wab
For a-i-d-c-b
Ub –Ua = Qaidcb – Waidcb
Then, Qab − Wab =
Qaidcb – Waidcb
If Are under the curve ab = Area under the curve aidcb
Then work done will be same
Then
Qab = Qaidcb 
Conclusion: – We can replace any reversible path with two adiabatic lines & one Isotherm,
in such a way that Area under the reversible path & this conclusion should be the same.
Let us consider a reversible cyclic process.
(Whatever the process happening in the cycle is reversible.)
ðQH伭1 rev ðQC伭1 rev
= For first cycle
TH1 TC1

Conclusion by dia:- two adiabatic line can never intersect to each other as Qc = 0 ,It is going
to violate the Kelvin & Plank’s Statement.
(In a reversible cycle, there are no Carnot cycles.)
Similarly, for 2nd cycle
ðQH伭1r ev  ðQC
= 2

TH TC
Thermodynamics

2 2

Upto n
By adding left- & right-hand side

61.
 ðQrev ðQrev

∫ TH
= ∫ Tc
ðQrev ðQrev

∫ TH
− ∫ Tc
0
=

ðQrev

∫ Tc
=0

ðQrev
If ∫ T
= 0 , As we know ∫ ðP = 0 , cyclic integral of every property is equal to zero, hence
ðQrev
we can say that
T ∫
= 0 must be property or can say the term inside the Integral must

be changed in property & this property is called entropy. Hence entropy is a state fn or
point fn.
Since Entropy is a state function or point function, hence cyclic Integral of entropy change,
must always be zero either for Irreversible or reversible.
We have to choose a reversible arbitrary path to find the entropy within two points, as
entropy is a state fn. then for both the path entropy change will be the same.
2 dQ
∆S = a 
1 T ∫
2 dQ
∆S ≠ ∫ b  T
1

2 dR 2 dR 2 dR 2 dR
a ∫ 1 T
≠b ∫ 1 T
≠c ∫ 1 T
≠d ∫ 1 T
2 2 dQ
∫ ds = a ∫
1 1 T
2 dQ
S2 − S1 =
a ∫ 1 T
Them S2 − S1 will be the same in all the paths (though they are Irreversible).
If all Irreversible process
2 dR 2 dR 2 dR 2 dR
Then, a
1 T
≠b ∫
1 T
≠c
1 T
≠d
1 T ∫ ∫ ∫
Calculate the entropy change for an Irreversible path 1-a-2
Then we have to assume an artibitary reversible path between the same two points.
2 dQ 2 dQ
c
1 T ∫
= b
1 T
= S2 − S1 ∫
Thermodynamics

Once we have calculated the entropy change for c and b that will be the same as well.

62.
 dQ
Clausius inequality says that cyclic Integral of over a reversible cyclic process will be
T
zero.
dQ
∫ T
=0

dQ
But cyclic Integral of for Irreversible process is not zero (that trust be less than zero)
T
dQ
∫ T
<0

dQ
∫ T
≤ 0 Clasius inequality

Equality holds for reversibility.

Inequality holds for Irreversible.
Since, ηrev > ηIrr   operating in between same thermal reservoir
Wrev Wirr
>
QH rev QH irr

QH rev − QC rev QH irr − QC irr

>
QH rev QH irr

QC rev QC irr
1− > 1−
QH rev QH irr

QC rev QC irr
≥
QH rev QH irr

TC QC irr
<
TH QH irr

QH QC irr
− <0
TH TC
Q
∑ T
<0

dQ
∫ T
< 0 for Irreversible process

dQ
Thermodynamics

∫ T
≤ 0 Clausius inequality

63.
 Entropy change calculation for non-cyclic process
2 2 dQrev
∫ ds = ∫
1 1 T
2 dQ

1 T ∫
S2 − S1 = rev →entropy changes for a path

Consider two cycles as shown in the figure

1-a-2-b-1
1-a-2-c-1
dQrev
∫ T
=0

For first cycle

2 dQ 1 dQ
a ∫ 1 T
+ ∫b 2 T
0
= ……………………..(1)

For Second cycle

2 dQ 1 dQ
a ∫
1 T
+ c
2 T
0
= ∫ ……………………..(2)

From equation (1) find

2 dQ 1 dQ
a
1 T∫ = −b
2 T ∫
2 dQ 1 dQ
−b ∫ 1 T
+ ∫c 2 T
0
=

2 dQ 1dQ
b ∫ 1 T
=c ∫ 2 T

Principle of increase at entropy

Application of the second law of thermodynamics in an isolated system led to an important
consequence known as the principle of entropy increase and this principle is used to define
the second law of thermodynamics.
Let us consider two cycles
For reversible cyclic process
dQ
∫ T
=0

2 dQ 1dQ
a ∫ 1 T
+b ∫ 2 T
0
=
Thermodynamics

2 dQ 1 dQ
a ∫ 1 T
= −b ∫ 2 T

64.
For irreversible
dQ
∫ T
<0

2 dQ 1 dQ
a ∫ 1 T
+c ∫ 2 T
<0

1dQ 1 dQ
−b ∫ 2 T
+c ∫ 2 T
<0

1dQ 1dQ
c ∫ 2 T
<b ∫ 2 T

1dQ
c ∫ 2 T
< ∆S ( )
1 dQIrrev
∆S > c ∫ 2 T
1 dQIrreversible
It means ∫ 2 T
will not give entropy change.

2 dQ 2 dQ
∆S > ∫ b  T
1
∫
∆S = a 
1 T
2 dQrev 2 dQ
a ∫ 1 T
>b ∫ 1 T
dQ
Its meaning is that summation of an irreversible path will not give the entropy change.
T
dQ
While summation of . an over reversible path between two same states will give the
T
entropy change.
dQ
It means from above equation the summation of over irreversible path will be less than
T
dQ
the ∫ T
over reversible between the same states.

2 dQ
∆S > b ∫ 1 T
ÿ
Sg is entropy generation
ÿ
Sg > 0 Always (Irreversible)
| All Irreversible process is spontaneous
ÿ
Sg = 0 Always (reversible)
Thermodynamics

ÿ
Sg < 0 not feasible process

65.
 2 dQ
b ∫ 1 T
→ It is due to the External heat interaction

ÿ
Sg → due to Internal Irreversibility.
ÿ
2 dQ
=
∆S b ∫ 1 T
+ Sg

For irreversible adiabatic process

ÿ 2 dQ
Sg = 0 , ∫ 1 T
=0

S=0
Can conclude that all reversible adiabatic processes are isentropic, but it is not necessarily
all Isentropic will be reversible adiabatic.
For Example: - ∆S =−20 + 20 } not reversible adiabatic but Isentropic
Entropy change for isolated system
ÿ
ΔSU =ΔSsystem + ΔSsurrounding system =0+ Sg
ÿ
∆SU  =
Sg entropy generation
∆SU  ≥ 0 principle of increase of entropy
Every process in this universe takes place in the direction of increase in entropy except for
reversible processes.
System ki entropy decrease (System + surrounding) will ever be positive (If the process is
feasible).

Mathematical statement of second law

∆SU  ≥ 0 (System + Surrounding) = universe
System + surrounding = universe is always adiabatic
ÿ
Sg always more than zero for feasible
At some point, entropy of a system may decrease, but as a whole (system+surrounding) as
a whole must increase.

Statement: -
y In the universe all the processes take place in the direction of increasing entropy; there is no
process in the universe which takes place in direction of decrease in entropy, “only limiting
case is change in entropy is zero, when every process is reversible”.
Thermodynamics

ÿ
∆SU = Sg > 0 for Irreversible

∆SU < 0 not feasible

66.
 ∆SU =
0 reversible
Entropy generation is a path fn, whereas entropy is a point fn.

Entropy balance over a closed system

Energy can always be conserved, whereas entropy always generated (neither created nor
destroyed) (always gone to increase)
Entropy is only associated with the heat interaction; it has no meaning with the work
interaction (highly organized form of energy)
Even the system is adiabatic, no heat interaction but still the entropy can be increased due
to internal irreversibilities in the system.
By this process is feasible (as every feasible process is happen because of increase in
entropy)
[And here increase in entropy not because of mechanical work but whereas internal
irreversibility is responsible like thermal energy of molecules].
dQrev
Since, ds =
T
2 2
∫ dQrev =
1 ∫ Tds
1

2
Q1-2 = ∫ Tds
1
reversible heat transfer

Temperature versus entropy plot

(Area under the curve T & S will give the reversible heat transfer)
(this is basically Pdv work)
2
Q1−2 = ∫ Tds
1

Heat transfer in different thermodynamic processes

Carnet heat pump/Refrigerator
(here, Coefficient of performance is important)
1
(
COP =)
R TH
 −1
TC
1
(COP )P = T
1 −  C  
TH
Thermodynamics

Q1−2 − R3−4 =
QNet
QNet = Area under the curve

67.
 QNet > 0
Suppose, we have plot like that
W QH − QC
=
η =
QH QH

∫ dQ rev
= ∫ Tds
= (
Q1−2 TH S2 − S1 )
QC
= TC ( S4 − S3 )

TH ( S2 − S1 ) − TC ( S4 − S3 )
=
TH ( S2 − S1 )

TC
η= 1− As it is
TH

Area under the T − S plot
ηc =
Areau
  nder 1 − 2

For Reversible Isothermal process

∫ dQ rev
= ∫ Tds
(
Q1−2 T S2 − S1
= )

Reversible adiabatic process

= (
Q1−2 T S2 − S1 ) ∆S =0 for Reversible Adiabatic

So Q1−2 = 0
For Isochoric (Only Pdv work & here Volume is constant)
dU = đR – đW
dU = Tds
𝜂CvdT = Tds
dT
𝜂Cv   = dS
T
2 2 ds
lnln T    =   ∫
Thermodynamics

1 1 Cv

T S − S1
lnln  2  = 2
T1 Cv

68.
 T 
Cvlnln  2   
S2 − S1 =
 T1 

For Isobaric process

dU = đR – đW
dU = Tds – Pdv →valid for isobaric & reversible
dU + Pdv = Tds
dT T
d(U + Pv) = Tds =
dS Cp
dT
dH = Tds dS = Cp ∫ T
𝜂CpdT = Tds
T 
CpdT = Tds Cvlnln  2   
S2 − S1 =
 T1 
dT T
As for Isochoric = , as Cp > Cv
dS Cv
dT T dT dT
For Isobaric = then >
dS Cp Cv Cp
So slope of Isochoric process is always more than Isobaric

Q The following Pv has to be change in TS curve

Sol: Pv = nRT
v↓ = nRT↓, heat removed S↓
Since 3-1 Isothermal process
Expansion (Temperature↓)
To maintain temperature Q↑ (add) increase in entropy

Entropy change for polytropic process

For polytropic process
dU = dQ – dW
dU= Tds – Pdv
Tds = dU + Pdv
Thermodynamics

Tds = 𝜂CvdT + Pdv Since Pv = nRT

nRT
Tds = 𝜂CvdT +  dv
v

69.
 dT nRT
dS = ηCv +  dv
T Tv
dT dV
dS =
ηCv
T ∫
+ nR ∫ V
We are going to supply heat while the temperature is decreasing, because it is a polytropic
process, work is more, so that we can possibly decrease in internal energy hence temperature
decreases.

Entropy Change Calculation for Ideal gas

TDs equation
dU = dQ – dW [for reversible or irreversible]
dU = Tds – Pdv [for reversible only]
Tds = dU –Pdv [Since, here all the terms are state fn, so we can use this for Irreversible/
reversible]
dU = Tds - Pdv
Although that equation is derived for reversible process, still this equation can be used for
reversible as well as irreversible because all the terms are state fn.
This equation can be used for closed systems, as well as open systems with no change in
composition(or no chemical reaction).
Tds
= dU + Pdv …………………………. (1)
2nd Tds equation
h = u + PV
u= h − PV
du dh – Pdv -Vdp
Tds
= dh − Vdp …………………………. (2)
du Pdv
From first Tds equation d s = +
T T
CvdT Rdv
d s = +
T T
dT dv
= ∫
ds Cv ∫ T
+R
  ∫ T
T  V 
s2 − s1 Cvlnln  2   +Rlnln  2   
=
 T1   V1 
From 2nd Tds equation
CpdT V
ds = −  dp
Thermodynamics

T T
dT V
= ∫
ds Cp ∫ −    dp
T T

70.
 dT dP
= ∫
ds Cp ∫ T
+R
  ∫ P
T  P 
S2 − S1 Cvlnln  2   +Rlnln  2   
=
 T1   P1 

Entropy change calculation for phase change operation

For Example: - Melting, sublimation, vaporization
(In all phase operation remain constant)
For melting O2 fusion
Δh = Change in enthalpy between saturated states
For melting Δhsf = hf – hs = λ [enthalpy of standard liquid = hf]
[enthalpy of standard solid = hs]
Q
Δhsf = λ =
m
For vaporization Δhfg = hg – hf
Latent heat of Ice = 570 Kcal/kg
For sublimation Δhgs = hg – hs
dQrev
∫ ds = ∫ T
Q mIrrev
S2 − S1 =rev =
Tsat Tsat

J Q
 s2 − s1 =rev
kgk Tsat

∆hαβ   J
s2 − s1 =  
Tsat kgk

m∆hαβ  J
S2 − S1 =  
Tsat k

Entropy change calculation for sensible heat transfer process for solid and liquid
Solid and liquid are assumed to be incompressible which means volume change and density
change is negligible.
Then Cp ≈ Cv} Liquid and solid
2 2 dQrev
Since, ∫ ds = ∫ T
Thermodynamics

1 1

mCpdT 2
S2 − S1 =
1 T∫

71.
 T
mCplnln  2  
S2 − S1 =
T1

Entropy Balance over a close system

T is the surrounding temperature
2 ðQ
= ds ∫
1 T
+ Sg Entropy Balance for close system

n Qi
∆S
= ∑ i= 1 Ti
+ Sg

Ti →temperature at which heat is going to enter in the system.

If T1 = T2 = T3 = …………….. Ti = To (Surrounding temperature maintain at constant temperature)

∆S
=
∑ Q + Sg for universe ∆S =Sg
T0
SSystem + SSurrounding =
Sgeneration

Entropy Balance for open/ flow system

Rate of entropy in by mass flow – Rate of entropy out by mass flow + rate of entropy
(due to H.T) + rate of entropy generated (due to Internal Irreversible) = Entropy
Accumulation.
For S.S process (Entropy does not accumulate)
Qi  J / S  
m
 isi − m
 ese +
∑  
Ti  K 
 + Sg =
0

Si→Specific Entropy (There is no entropy via work as not associated)

For multiple input & output

0 0 ∑Q i
∑ m s | Inlet − ∑ m s | outlet +
i i i i
Toi
 =
+ Sg 0

For Single stream

) ∑To
Qi
= m
Sg (
 Se − Si −
i

 =
Sg m
 ∆Sflowing  stream − ∑Q i
Thermodynamics

Toi

72.
 For multiple stream

0 0 ∑ Qi
 =
Sg ∑ misi |
outlet
− ∑ misi |
inlet
+
Toi
If process is adiabatic Q=0
Then= 
Sg m (
 Se − Si )
 > 0
If Sg (Process is feasible)
 < 0
Sg (not feasible)
 = 0 (reversible)
Sg

Entropy change calculation during mixing of two Ideal gas

Since If ideal gases, at the same temperature and pressure are allowed to mix, enthalpy
change of mixing must be zero, volume change of mixing should be zero, but ∆Smix ≠ 0 (as
mixing is a highly irreversible process) for every spontaneous (irreversible) process entropy
must be increased.
Let us assume n1 molecules of ideal gas (1) and n2 molecules of ideal gas (2), they are at the
same temperature and pressure is mixed or allowed to mix.
Since the mixing is a highly irreversible process, to find the entropy change that irreversible
process should be replaced by an arbitrary reversible path between the same initial state
and final state.
The irreversible process can be replaced by following two reversible processes: -
y Both gas (1) and gas (2) are allowed to expand isothermally from pressure P to corresponding
pressure P1 and P2 respectively.
y And then allow it to flow through a semipermeable membrane, which permits either the
flow of gas.

Isothermal process
ðQrev ðQrev
=∆S a ∫ T
+b ∫ T
a,b→reversible path

Entropy change for Isothermal process

dU = dQ – dW
dQ = dW
dQ = Pdv
dQ Pdv V 
=
ds ∫=
T
= nRlnln  2   
T  
 V1 
Thermodynamics

P 
∆S =nRlnln  1   
P 
 2

73.
 P P

= ∆S n1Rlnln   + n1Rlnln     
P  P 
 1  2
 1   1 

= ∆S n1Rlnln   + n1Rlnln     
y  y 
 1  2
∆S= n1R − n
  1Rln y 2  

∆Smix =
−R ∑ nln y
i i
for Ideal gas mixing

By dividing equation by n

∆Smix =
−R ∑ y ln y i i

∆Smix =
− nln 
i ∑
yi

∆Smix =−  −54.45 × R 

J
∆Smix =
+452.73 
K
J
∆Smix =
4.52 
K

Entropy change during the separation of Ideal gas

∆Sseperation = − ∆Smix( )
∆Sseperation =
nR yiln yi ∑
Negative hence separation of Ideal gas is not spontaneous (have to do work).

Work required to separate the gases

From first law of thermodynamics
dU = dQ – dW
dQ = dW
ʄdQ = ʄđW
Tds = Wsep

 
T nR ∑ y ln y  = W
Thermodynamics

i i sep


Wsep = nRT ∑ y ln y ] i i

74.
Q A reversible heat engine is supplied with 900 KJ of heat from a heat source
at 500 K, the engine develops 300 KJ of network and rejects heat to the two
sinks at 400K and 300K. find out thermal efficiency of the engine and the
magnitude of heat interaction with each of the sinks.

Sol: By applying balance over engine

900 - QC - QC = 300
1 2

600 = QC + QC …………..(1)
1 2

W 300
η= =
η = 0.333
QH 900
dQ
∫ T
=0

900 QC1 QC
− − 2
0
=
500 400 300
QC QC
1.8
= 1
+ 2

400 300
600 − QC =
QC
1 2

QC 600 − QC
1.8
= 1
− 1

400 300
QC QC
1.8
= 1
+2− 1

400 300
−8.33 × 10−1 QC + 2
1.8 =
1

QC = 249K
 J
1

QC = 360K
 J
2
Thermodynamics

75.
 Q A heat engine working on a carnot cycle absorbs heat from three thermal
reservoirs at 1000 K, 600 K, 800 K, the engine loses 10 KW of network and
rejects 400 KJ per minute of heat to the sink at 300 K. If the heat supplied
by reservoir at 1000 K is 60% of the heat supplied by the reservoir at 600K.
Find out the quantity of heat absorbed by each reservoir.

Sol: Q1 = 0.60 Q2
Q1 + Q2 + Q3 − Q4 =
W
0.60 Q2 + Q2 + Q3 − 6.667 =
10KW
1.60 Q2 + Q3 =
16.667
Q1 Q2 Q3 Q4
+ + − 0
=
1000 800 600 300
1.60 Q2 Q2 Q3
+ + 0.0223
=
1000 800 600
0.00185 Q2 + 0.001667Q3 =
0.0223
1.60 Q2 + Q=
3
16.667 × 0.001667
Q3 = 20.495
Q1 = 3.13 KW
Q2 = 8.39 KW
Q3 = 5.23 KW

Q A refrigerator operating on reserve carnot cycle consumes 150 KW power

in summer, when the ambient temperature is 310 K the heat leakage into
the refrigerator through the doors is estimated to be at a continuous rate of
15W/°C (temperature difference) between ambient space and cold space of
refrigerator for continuous operation of refrigerator. Find out the tempera-
ture at which the cold space is maintained.

Sol: 150 × 103

Thermodynamics

Qc (
15 310 − T )
(COP )=
'R =
W 150 × 103

76.
 W + Qc =
QH

150 × 103 + 4650 − 15 T = QH

QH
=
(
15 310 − T )
310 T
4650
0.00322 
= QH − 15
T
4650 15
150 × 4650
= − 15 −
0.00322 T 0.00322
1444099.37
= 159308.38 − 15T
T
2nd method
Qc 15 310 − T ( )
(COP=
)R =
W 150
Qc 1
= =
QH − Qc TH
−1
Tc

(
15 310 − T
= =
)
1 T
150 310 310 − T
−1
T
4650 − 15T T
=
150000 310 − T
( 4650 − 15T) 310 − T  =
150000 T

15T2 − 1441500 =
140700T
T = 10.25

Q It is proposed to design a refrigeration plant for a food store, which is to be

maintained at –5°C, the ambient temperature is 25°C and estimated heat
transfer from the store at the rate of 5 KW. If the system operates on reserve
carnot heat engine cycle. Find out performance index or ( COP ) and mini-
R
mum power required to operate the refrigeration plant.
Thermodynamics

Sol: W + Qc =
QH
5 Q
= H
268 298

77.
 QH = 5.559K
 W
W = 0.559K
 W
Qc TC
(
COP
= )
R
=
QH − Qc
= 8.933
298 − 2

Q A heat engine cycle is represented by a circle of 4 cm diameter on the T-S

plane, whose centre lies on the 500K temperature line. The temperature
KJ
scale is 1cm=100K and the Entropy scale is 1 cm= 0.1 . If the engine com-
K
pletes 10 such cycles/seconds. Find the power developed by the engine.
Calculate the heat supplied to the engine and efficiency of the engine.

Sol: Area = πr2

π
=  d2
4
π
= ×4×4
4
Qnet = 125.6KJ
W
=
η = 125.6
QH
Area under the Ts plot 125.6

= η = = 0.477
Area under the 1 − 2 62.8 + 200

Q Question. A system comprising of 5kgs of fluid changes reversibly changes

KJ
initial state of specific entropy 4 and temperature to 280K to final
KgK
KJ
state of specific entropy 4.25 and temperature 360K. Evaluate the heat
KgK
flow involved if the entropy varies linearly to the temperature.

Sol: Area of trapezium = Q
a +b ( )
1h a + b (
1 × 0.25 360 + 280 )
Thermodynamics

 h = =
 2  2 2
Q = 5 × 80 = 400 KJ

78.
Q Heat flows from reservoir at 800K to another reservoir at 250 k, if the entro-
KJ
py change of hot reservoir is –4 . If the entropy changes of the cold
K
reservoir.

Sol:
−Q
∆SHot =
T
KJ Q
∆SHot = 4 =
K 800
Q = 3200
KJ
∆SCold =
12.8
K

Q A steel casting made of mass 400 kg is quenched (sudden cooling) is 100 kg

of water at 30°C in an insulated container the temperature of the steel
KJ KJ
casting is 800°C, Cp of steel is 0.461 , Cp of water 4.23 , calculate
KgK KgK
the entropy generation entropy change.

Sol:  = ∆S
Sg System
+ ∆SSurrounding

 = T
Sg mCplnln  2  +11.43 = −5.704
T1

MCp (
T2 −=
T1 )
mCp
 (
T2 − T1 )

= Tf 38.3012°C
∆USteel = −∆UWater

MCp (
Tf − 800 =

)
− mCp (
Tf − 30 
 ) from first law of thermodynamics

∆USteel + ∆UWater =0

 = 5.7288 KJ
Sg
K
From the second law of thermodynamics this cooling is feasible or not we
will check
Thermodynamics

 = 5.7288 KJ
Sg
K
Entropy generation or totalE
  ntropy change.

79.
 Q A piston cylinder assembly contains 1 kg of saturated liquid water at 100 °C ,
Cylinder is brought into contact with the body at 500 °C . till all the water is
converted into saturated steam at the same pressure. Find out the entropy
change of the water. If λ (latent) heat of vaporization of water at 100 °C is
KJ
2257 .
Kg

Sol: ∆S =
mλ
Tsat
KJ
∆S =6.05093
K
 = ∆S
Sg + ∆SSurrounding
System

−1 × 2257
=
773
KJ
= −2.9197
kg

 = 3.1407 KJ
Sg
kg

Q M1 kg of water temperature at absolute T1, is Isobarically and adiabatically

mixed with M2 kg of water at temperature T2 where (T2>T1), show that for
equal masses of water the entropy change of the mixture is given by

Sol: T +T  
( ∆S ) =
U
2mCplnln 
2 T T
1 2  

 1 2 
CP = CP as water in M1& M2
1 2

T2 > T1
when they are going to mix
then, ΔU = dR – dω mCp
 T1 − =
Tf mCp
 (
Tf − T2 ) ( )
Thermodynamics

T1 + T2
Tf =
2

80.
 ΔS = Δ S1 + Δ S2
 Tf   Tf 
= mCplnln 
    +mCplnln 
   
 T2   T2 
 T1 + T2   T1 + T2 
= mCplnln 
    +mCplnln 
   
 2T1   2T2 
 T1 + T2 T1 + T2 
= mCplnln 
   × 
 2T1 2T2 

T + T 
 1
= mCplnln 
 2 
 
2 T T 
 1 2 

Q A heat engine operates between two simple thermal reservoirs, source is at

temperature T1 and sink is at temperature T2. If the source and sink are of
mass m and specific heat capacity C. Then set up the following expression
for maximum work output.

Sol: W + Qc =
QH
QH − Qc =
W
Wmax = QH
W
η=
QH
Entropy change for this system
dQ T
Δ S=
source ∫
= mCplnln 
T
   
 T1 
T
Δ Ssink = mCplnln 
   
 T2 
If the system is reversible then the process must be giving maximum work.
 =0
For reversible Sg
T T
Thermodynamics

mCplnln 
    = −mCplnln 
   
 T1   T2 
T= T1T2

81.
 Wmax
= QH − Qc
rev rev

= QH mCp
 T1 − T ( )
QC =
−mCp
 T − T2 ( )
W=
max
mCp
 T1 − T − mCp
 (
T − T2 ) ( )
Wmax = mCp
 (
T1 − T1T2 ) − mCp
 ( T1T2 − T2 )
( T− T)
2
=
Wmax mCp
 1 2

Q Heat pump operates between two identical systems, both being at temper-
ature T1 to start with, due to operation of the heat pump, one of the systems
cools down to temperature T2, showing that for this operation of the pump,
minimum work required by the heat pump is.

Sol: Work required will be minimum when process will be reversible.

 T2 
= C  1 + T2 − 2T1 
Wmax
 T2 
 
W + Qc =
QH

Wmin
= QH − Qc
For reversible cyclic process
dQ
∫ T
=0

 Tf   T2 
mCplnln 
    +mCplnln 
   
 T1   T1 
T12
Tf =
T2
mCp
 (
T − Tf )
mCp
 ( Tf − T ) − mCp
 ( T1 − T2 )
Thermodynamics

 T2 
mCp
  1 − T  − mCp
 T2 
 T1 − T2 ( )
 

82.
  T2 
Wmax mCp
=   1 + T2 − 2T1 
 T2 
 
1 kg of Ice at – 4°C is exposed to atmosphere at 20°C ( – 4°C)

Q The ice get melt and comes into the equilibrium (maximum temperature by
liquid can be 20°C) find the entropy generation or entropy change of ** for
KJ KJ KJ
ice 2.09 Cp and λ heat of fusion is 333 Cp of water 4.23 .
Kgk Kg Kg

Sol:  = ∆S
Sg System
+ ∆SSurrounding
For - 4°C - 0°C
 Tf 
mCplnln 
    = 0.0308
 T1 
mλ 333 KJ
S
∆= = = 1.219
Tsat 273 K
 Tf   293 
mCplnln 

=     4.23lnln 
=     0.29906
 T1   273 
KJ
∆SSystem =
1.5488
K
−Q
∆SSurrounding =
T
2.904 × 4 + 333 + 4.23 × 20
Q = 429.21
−429.21
= = −1.464
Thermodynamics

293
KJ
∆SU =
0.0956
K

83.
 Q Find the minimum work required to convert the water lag of 20°C to ice of
-4°C. 429.21 kg heat has to be absorbed to have - 4°C temperature

Sol:

429.21 kg heat has to be absorbed to have - 4°C temperature

∆SSystem + ∆SSurrounding + ∆SHP =0
1

KJ
∆SSystem =
−1.5488
1 K
Q=
H
QC + QW
424.9 + Wmin

= QH = 0
293
424.9 + Wmin
−1.5488 +
= 0
=
293
Wmin = 26.32 kg

Q Find the entropy change of 5kg of perfect gas whose temperature varies
from 150°C to 200°C, during a constant volume process, the specific heat
varies linearly with absolute temperature and given by
KJ
Cl = 0.45 + 0.009 T
Kgk

Sol: Constant volume process

du=dR – dw
dU = Tds
dT
Thermodynamics

dS ≅ mCv
T
T2 dT
S2 − S1 = ∫
m Cv
T1 T

84.
 T2 0.45 + 0.009T dt
S2 − S1 =
m ∫ T1 T
( )
S2 − S1 =5 × 0.45lnln T   473 473 +0.009lnln T   473 473 

KJ
S2 − S1 =
2.50137
Kgk

Q 11g water at 273 K is heated to 373 k by bringing it into contact with heat
source at 373 k, find the entropy change of water, entropy change of heat
source and entropy change of universe and entropy generator.
What will be the entropy change of the universe, if heating of water 273 to
373 by first bringing it in contact with a heat source at 323 K and then with
the heat source 373 K.

Sol: Entropy change of water

T 
∆S =mCplnln  2   
 T1 
 373  KJ
∆S = 1 × 4.18 × lnln    = 1.3046
 273  Kgk
Entropy change of heat source
∆SSource =
mCpD
 t
1 × 4.18 ×  100
=

KJ
= −1.1206
Kg
SU 1.3046 − 1.1206
∆=
KJ
∆SU =
0.1839
K
T 
mCplnln  2   
∆Swater =
 T1 
 323 
= 1 × 4.18lnln   
 273 
Thermodynamics

KJ
= 0.70299
K

85.
  373 
then               m
  Cplnln   
 323 
KJ
= 0.6016
K
∆System = 1.30459
−Q Q
∆System = 1 − 2
T1 T2

(
−mCp 323 − 273 ) − −mCp ( 373 − 323)
323 373
KJ
= −1.2073
K
 = 0.097 KJ
Sg
K

Q Question. A rigid and insulated tank of volume 2 m3 is divided into two equal
compartments by a partition. The first compartment contains an ideal gas at
400 K and at P reserves 3 mPa and the 2nd compartment contains the same
ideal gas at 600 K and 1 mPa. When the partition gets removed, then gases
are allowed to mix and find entropy change during mixing.

Sol: dU=dQ – dw
dU = Tds – Pdv
Tds
= dU + Pdv …………..(1)
H = U + PV
dH = dU + Pdv +VdP
Tds
= dh + VdP …………..(2)
T  P 

= ds Cplnln  2   −Rlnln  2   
 T1   P1 
First we have to find the common temperature & common pressure
∆Stotal = ∆Sgas1 + ∆Sgas2

Pressure should PF1 TF

Thermodynamics

mCp
 (
T1 − =
Tf )
mCp
 (
Tf − T2 )
902.06 ( 400=
− Tf ) 200.96 ( Tf − 600 )

86.
 Tf = 436.36K
 
PV = nRT
P × 2m3= 902.09 × 8.314 × 436.36
Pf = 2 mPa
T  P 
Cplnln  f   −Rlnln  f   
 T1   P1 
∆S1 =
5.17939 for 1st gas
∆S1 =
4672.27
∆S2 =−12.382
∆S =−2482.09
Joule KJ

= ∆SU 2190.17 
= 2.19 
K K

Q In steady state flow process 1 mol/sec of air at 600K and 1 atm is contin-
uously mixed with 2 mol/s of air at 450 K and 1 atm, the Pdt stream is at
400 k and 1 atm, a systematic representation of the process is shown in the
figure.
Find the rate of heat transfer and rate of entropy generation of process.
7
Assume air is an ideal gas Cp = R, that surrounding at 300 K, in case K.E &
2
P.E are negligible.

Sol: From mass balance

η A + η B = η C
1 + 2 = 3 mol/sec = η C
By energy balance
dm
∑ m e − m
in i
e =
out e
dt
η A eA + η BeB − η CeC + Q + W = 0
 ∆CA 2   ∆CB2   ∆CC2 
η A  hA + + g∆ZA  + η B  hB + + g∆ZB  − η C  hC +  −W=
+ g∆ZC  + Q 0
Thermodynamics

 2   2   2 
     
( ) ( ) ( )
η A Cp 600 − 300 + η BCp 450 − 300 − η CCp 400 − 300 + Q =
0

87.
  = −8729.7 J
Q
S

Heat removed Q = 8729.7
Applying entropy balance

η A SA + η BSB − η C SC + S g +
∑ Q =0
To
T 
mCplnln  2   
η A SA =
 T1 
 600 
SA =
η A SA =
1 × 3.5 × 8.314l nln    =
20.169
 300 
 450 
SB =2 × 3.5 × 8.314 lnln    =23.59
 300 
 400 
SC =3 × 3.5 × 8.314l nln    =25.1137
 300 
KJ
S g = 10.4537
K

(
S g = η C SC − η A SA + η BSB −
∑
) T

Q

= ( ) ( ∑
) T
η A + η B SC − η A SA + η BSB −

Q

( )
= η A SC − SA + η B SC − SB ( )− ∑ 
Q
T
 400   400  8729.7 KJ
1 × Cplnln 
=   +216lnln    + 10.44
=
 600   450  300 K
Thermodynamics

88.
Q An inventor claims to have a device which takes in steam at 150°C and deliv-
ers super heated steam at 0.2 mPa and 200°C. He also claims that 0.949 kg
superheated steam and 0.051 kg of saturated liquid at 100°C leaves devices/
kg of steam fed. He further claims that the device does not require any input
of energy; this process is feasible.Mass balance Mass is conserved

Sol: Mass balance

Mass is conserved

By applying energy balance

Following data is given for saturated steam at 150°C
KJ KJ
hgaseous hg
= 2745.4
=
kg
( )
                     Sg 6.8358 
kgk
 } Saturated steam

For saturated liquid (100°C)

KJ KJ
hf 419.06
= = , Sf 1.3069
kg kgk
For superheated steam 200°C
KJ KJ
= hs 2870.5
= ,S 7.5072
kg s kgk
m1e1 − m2e2 − m3e3 + Q − W =
0
η hA = η hB + η hC
1 × 2745.4 = 0.949 × 2870.5 + 0.051 × 419.06
Energy is conserved
For feasibility: - feasibility of process check by 2
Thermodynamics

 =
1 × 6.8358 − 0.949 × 7.5072 − 0.051 × 1.3069 + Sg 0
 > 0
Sg  = 0.355
Sg

89.
 Q Two basic type of steady flow heat exchanges are characterized by their
flow patterns (1) Co-current (2) Counter current and it is shown in the figure

Given that minimum temperature difference between the following steam is

10 K and the motor flow rate of hot steam 1 mol/sec assume, both steams
7
are Ideal gas Cp= R. find the entropy generation in both cases.
2

Sol:

 = ∆S + ∆S
∆Sg H C

By energy
mnCp
 h (
400 − 350
= mCp
 C
340 − 300 ) ( )
 350   340 
mCplnln 
    +mCplnln 
           m 1.25
C =
 400   300 
∆S =
g
0.6654K  J
IInd method

( η HS1 + η CS3 ) − ( η HS2 + η CS4 ) + S g +

∑ Q =0
T
Thermodynamics

( ) (
η H S1 − S2 + η C S3 − S4 + S g =0 )
( )
S g = η H S2 − S1 + η C S4 − S3( )

90.
 In mCp
 C (
400 − 350
= m )
 CCp 390 − 300 ( )
5  350   390 
m
C = mCplnln 
    +mCplnln 
   
9  400   300 
KJ
S g = 0.3558 
K

Calculation of ideal work

In any steady state flow process requiring work, there is an absolute minimum amount
which must be expanded to accomplish the desired change of state of a fluid flowing
through the control volume.

(Work consuming) (When process is reversible, then the work done on the system will be
minimum)
In a process producing work, there is an absolute maximum amount of work which may be
accompanied as a result of a given change of state of the fluid flowing through the control
volume.
In both cases, the limiting value obtained when the change of state associated with the
process must be completely reversible for such process entropy generation must be zero.
from entropy balance over the open system.

( )flowing  stream − ∑To

Q
m ∆S 
Sg
=

 =0
For process to be reversible Sg

m
 ∆S ∑
( )flowing  stream =
Qrev
To

∑ Q= rev
T0m ( )flowing  stream
 ∆S
Thermodynamics

From 1st law of thermodynamics for open system

 ∆C2 
m
  ∆h +  −W
+ g∆z  = Q 
 2 
 

91.
  =Q
For Q & ∆K.E & ∆PE ≅ 0
rev


Q −W  m 
=  =W
 ∆h W  in case of reversible
rev Ideal Ideal


Q
= rev
Tm 0 ( )flowing  stream
 ∆S

T0m ( )flowing  stream − m 

 ∆S  ∆h = W
Ideal

 T0 ( ∆S ) − ∆h = W
m 
 fs  Ideal

= m
W  T0 ( S2 − S1 ) − (h2 − h1 ) 
Ideal  

= m
 (T0S2 − h2 ) − (T0S1 − h1 )
 
Since gibbs free energy is define as h-TS
= m[ (
 −g 2 − −g 1 ] )
= m
W  g 1 − g 2 
Ideal  
Maximum work done decrease in Gibbs free energy ( g 1 > g 2 )
Minimum work on the system is obtained in the direction of increase in Gibbs energy.
( g2 > g 1 )

If W > 0 (work done by this system/maximum work) ‘The system is going to perform
Ideal
maximum work in direction of or with decrease in Gibbs free energy and increase in entropy’.
Where the surrounding temperature is equal to the system temperature then only we can
obtain the maximum work.
Gibbs free energy represents potential to do work by a fluid in a steady state flow processes
during which fluid exchange energy as a heat with surrounding such that the initial and final
temperature of the flowing stream must be equal to the surrounding temperature.

Lost work
=
Lost work Actual work − Ideal work
When work is done by the system
Ideal work > Actual work (or WIdeal > WActual )
Lost work = −ve
W = + ve When work is done on the system
Lost

as WActual > WIdeal

{Work that is wasted as a result of irreversibilities in a process is called lost work.}
And it is defined as the difference between actual work from the process and the ideal work
Thermodynamics

from the process.


W
= 
     W 
 −  W
LOST ACTUAL IDEAL

= WS - WIDEAL

92.
As by first law for open system
 – W  = m
ÿ
∆C2
Q   ( Δh + + ΔZ)
2
WS = Q – m (Δh)
Here, fs = Flowing system
m (Δs)fs - ƩQ/TD = Sg
Qrev = TD M(ΔS)
As we know , WIDEAL
WIDEAL = TD m(Δs)fs - m(Δn)
WIDEAL = TD m(Δs)fs - m(Δn) ……………..

Find lost work

Wlost work = actual work - ideal work
= Q - mΔn - TD m(Δs)fs + m(Δn)
WLOST WORK = Q - TD m(Δs)fs ……………..*
Here, ΔS = Entropy change of flowing stream
m (Δs)fs - ΣQ/TD = Sg
m (Δs)fs = Sg + ΣQrev/TD ……………….**
Replace the value ** in *
WLOST WORK = Q - TD Sg - ∑ Q
x TD
TD
WLOST = TDSg
WLOST = 0.667 X 300 = 200.01 J/S …………(1) Case

If the surrounding temperature is 300K then find the lost work

WLOST = 0.3558 x 300 = 106.74 J/S ………..(2) Case
That much energy is going to waste because of irreversibility in process

Third law of thermodynamics

Absolute entropy for every substance perfect Crystalline is always zero at absolute
temperature (0K)
Example:- Diamond (no randomness, so entropy is zero).

Properties of pure substances

Pure substances are those substance which are chemically, physically homogeneous
throughout the mass
Single component or pure element slash compound acts as a pure substance.
Thermodynamics

Example: -

O2 N2 H2O

93.
 More than one component in a mixture may also acts as pure substance unit they are
homogenous
Example: - Atmospheric air
(Every-where ratio or composition is same)
O2 / N2 = 79:21
More than one phase can also be acts as the pure substances
Acts as a pure substance
(As composition are same)

Gaseous air

Liquid air

Liquid air and gases do not act as a pure substance as condensation/vaporisation can be
different for different substances.Phases of pure substance
1. Solid
2. Liquid
3. Gases
If we consider H20 as pure substance

H20 has a unique property whose volume decrease by melting otherwise all substance
volume increase after melting.
Thermodynamics

(2), (3), (4), (5) are the saturated state points.

94.
y As P increases, the volume of liquid (no change as much).
y As P increase, volume of gas Decreases
For H2O-

  

1. Compressed solid state

2. Standard solid state
3. Standard liquid corresponding to solidification
4. Standard liquid corresponding to vaporization
5. Standard vapor
6. Superheated vapor state
Before triple point pressure solid changes to vapor directly

Note:- All triple point all three phases coexist

2, 3, 4, 5 are the saturated points.
Lines joining the saturated point are called saturated lines.
Thermodynamics

95.
 y Line joining all 2 points 2, 2’, 2” → saturated solid lines
y Line joining all 3 point 3, 3’, 3” → saturated liquid line corresponding to solidification
y Line joining all 4 point 4, 4’, 4” → saturated liquid line corresponding to vaporization
y Line joining all 5 point 5, 5’, 5” → saturated vapour line
As for our application concern, we have to only concentrate on liquid and vapour state

ssume :

P = 1 Atm

25’ C

Liquid

WсϭĂƚŵ

WĂƌƟĂůǀĂƉŽƵƌ
d
Thermodynamics

WĂƌƟĂůůŝƋƵŝĚ

ƉƌĞƐƐƵƌĞ

96.
(P > PSat) → compressed liquid
V = specific volume

State 1

We have changed temperature sufficiently but the change in volume is very small
1 dV
β= With high pressure, TSat has been increasing.
T dT

TSat
Ϯ͟ ϯ͟ ϰ͟

TSat
Ϯ͛ ϯ͛ ϰ͛

TSat
Ϯ ϯ ϰ
ϭ͟ ϭ͛ ϭ

Effect of temperature in liquid is more as compared to the pressure.

As temperature increases, that will dominate which will increase the volume slightly.
Because of the increase in pressure, volume should be Decrease, But the temperature
effect is more dominating so an increase in volume will be there but in a trace amount.
But by increasing temperature as we reach the point 4 at high pressure, then vapor is more
compressible as compared to liquid, so the volume decreases sufficiently.
Since the liquid is incombustible, then the decrease in volume with the pressure is very less
or negligible but at the same time
Here, an increase in the pressure from P1 to P2 results in a smaller decrease in volume, but
an increase in the saturated temperature results in a large volume. (From T1Sat - T2Sat ) but
Thermodynamics

increase in volume ( due to increase in temperature) is more dominant over decrease in

volume due to increase in pressure from P1 → P2. Hence there is a very slight increase in the
volume for liquid state.

97.
 Hence the standard liquid curve is more stepper / more vertical and bends towards
the right.
Since gases are more compressible gases, hence decrease in volume more dominating due
to increase in pressure as compare to the increase in volume due to increase in temperature,
and hence there is sufficient decrease in the volume at high pressure, so the saturated
vapor curve sends towards the left and it is less stepper to that standard liquid.
A condition can occur when both curves can meet a point and that point is called critical
point (C)

L+V V

Below the critical point C saturated liquid state and saturated vapor state are distinguishable,
but beyond the critical point it is not possible to differentiate between liquid state and
vapor state.
Triple point: - minimum temperature pressure there all three phases will coexist.
Critical point: - maximum temperature pressure at which liquid /vapor Coexist with each
other.
Beyond the TC and PC, We are unable to differentiate the vapour and liquid
PT:-Triple point pressure of camphor/Naphthalene is more than the 1atm. 60 directly solid
converts to vapour.

Triple point.
Below triple point, solid directly changes to Vapour State, which means if operating pressure
is lower than the triple point pressure of that Substance, that substance can directly get
sublime.
Example :- camphor/ naphthalene
Thermodynamics

If pressure is more than first S-L-M

98.
 Degree of freedom at triple point
F=C–P+2
=1+2–3=0
Along the standard curve (fusion curve, sublimation, vaporization curve)
degree of freedom F=C–P+2
= 1 – 2 + 2 = 1 (One variable is required)
At critical point
F=C–P+2
=1–2+2=1
We are unable to condense a gas, but simply increase in the pressure but we can condense
a vapour by simple increase in pressure or decrease in temperature
y Gases having temperature T > TC condense by increasing pressure alone the thermodynamic
state of gas can only be defined, vapor has no thermodynamic state mixture or equilibrium
with liquid.
At critical point
F = C – P + 2 – r – S ……………….*
For any fixed gas TC and PC is same ( must be 0)
At CP : F = C – P + 2
= 1 – 2 + 2 = 1 (this definition is wrong)
By * :
F=C–P+2–r–S
=1–2+2–0–1=0
Where, r = reaction
S = constraints
And at critical point there is constraint which means for any gases, there is specific
temperature and pressure at critical point
dP
⇒ =0
dV
d2P
⇒ =0
d2 V

Saturation press & saturation temperature ( PSat and TSat)

Temperature at which phase is about to change at a given pressure is called saturation
temperature
For example:-
At 1atm, then the TSat of water is 100 degrees Celsius
At any given temperature, phase is about to change is called saturation pressure
Thermodynamics

For example:-
At 25’C, P = 0.2atm (PSat of water)

99.
 Compressed liquid or subcooled liquid (P > PSat) and (T < TSat)
At given temperature, pressure of liquid is more than PSat, that liquid is called compressed
liquid
T = 25’C, PSat = 0.2atm
Liquid at P = 0.5atm is the compressed liquid.
At a given temperature the pressure of liquid is equal to the saturation pressure that the
liquid state is called saturated liquid.
At a given pressure, (T < TSat) temperature of liquid is lower than the saturation temperature
of liquid, that liquid is called a subcooled liquid.
FOR SATURATION LIQUID : T = TSAT (AT GIVEN PRESSURE)
P = PSAT (AT GIVEN TEMP)

Superheated vapor or rarefied vapor (P < PSat) , (TSat < T)

Any vapour whose temperature is more than TSat (TSat < T) at a given pressure or specified
pressure that vapour is called as superheated vapour.
Any vapour whose pressure is lower than PSat (P < PSat) at a given /specified temperature is
called rarefied Vapour.
y Sat vap T = TSat at given pressure
P = PSat at given temp.
y Superheated / rarefied vapour (TSat < T) at given pressure
(P < PSat) at given temp.
y Supercooled/ compressed liquid vapour (TSat > T) at given pressure
(P > PSat) at given temp.

TEMPERATURE V/S ENTROPY PLOT

Sensible heat change
dQ
S= ∫ T
= m CP ln T2/T1 (Non linear)

For latent heat change

mλ
dS = ∫T
mλ
S=
TSat
Enthalpy v/s entropy (molier diag)
At P = Constant
At constant pressure
dQ = dH = mCPdt H↑, S↑ (by adding heat)
Thermodynamics

P↑ TSat↑
dU = dQ – dW
dU = TdS - PdV

100.
 and dH = dU + PdV + VdP
dH = TdS - PdV + PdV + VdP
dH = TdS + VdP
As P = Const , dP = 0
Hence, dH = TdS
dH
⇒ =T
dS
dh
⇒ =T
ds
Once the phase chase (TSat = T) temperature will be constant, so slope will be constant
increasing.
As P↑, TSat↑ (slope will be more vertical)

Quality of steam (x)

Quality of steam (x) is defined as mass of the poor to the total mass of (L + V)
mg
X= where, f → liq, g → gas
mf + mg
If V is the total volume of mixture or steam, then it is submission of V = Vf + Vg
If V, Vf, Vg are the specific volume of steam, saturated liquid and sat. vapour respectively
m3
⇒ =V
Kg
⇒ mv = V (Volume of mixture)
Where, mfvf = volume of standard liquid,
mgvg = volume of standard vapour
mv mv mg v g
⇒ = f f +
m m m
V = x v g + (1 – x) vf ……………….*

If x is known to us, then we can find the volume of steam.

Vfg = Vg - Vf
V = x (Vg - Vf) + Vf
V = Vfg x + Vf (specific volume)
In the similar way
y Specific enthalpy h = hf (1 – x) + x hg or a = af (1 – x) + x ag
y Specific interactives u = uf (1 – x) + x ug
y Specific entropy s = sf (1 – x) + x sg
Thermodynamics

Where, 0 ≤ x ≤ 1
y At x = 1, V = Vg
y At x = 0, V = Vf

101.
 y At x > 1, superheated vapour
y At x< 0, supercool liquid
We cannot define gf and gg as g = f (T, P)
As dG = - VdP – SdT gf = gg
During phase change operations (T and P) are constant. So there is no meaning of gg and gf

Q A tank contains 100Kg of liquid water and 5Kg of liquid vapour under satura-
tion condition, at 20 degrees Celsius. If the specific volume of saturated web
or at the temperature is taken as Vg @ 20’C = 57.78, calculate the volume of
tank, calculate the moisture content

Sol: x=
mg
= 0.0476
mf + mg
1 – x = 0.952 = 95.2%
Vf = 0.001002
V = x v g + (1 – x) vf
V = 2.752 m3 / kg
V = 289.002 m3

Q A closed container holds 1kg of water at 153.3 degrees Celsius with the fol-
lowing composition by volume 1/3 liquid 2/3 vapour. find out pressure quality
and enthalpy of the mixture if

Sol: From steam table, we would have PSat

At given temperature find the PSat first from the steam table of saturated
steam at this temperature and pressure
F=C–P+2
F=1+2–2
F = 1 (valid for gas only)
Only one variable is sufficient
By steam table we would have Sf, Sg, hf, hg, Vf, Vg for temperature and pres-
sure
Thermodynamics

Once we would have Vf, Vg we would have (x)

vg
X=
vf + vg

102.
DATA
Vf = 0.001094 m3 /kg
Vg = 0.361 m3/ kg

Find out quality-

V = x v g + (1 – x) vf
mfVf vf 1
= =
mgVg vg 2
mf
= 164.99
mg
mg
 x  =  
mf + mg
1
x=
mf
+1
mg
x = 0.00602
v = 0.00326 m3/ kg

Q A vessel of 0.3 cubic metre capacity contains 1.5 kg of mixture of water and
steam in equilibrium and the pressure of 5 bar. Calculate the volume and
mass of liquid and volume and mass of vapour from steam table at 5 bar

Sol: Vf = 0.001093 m3 /kg

Vg = 0.325 m3/ kg
V = 0.3m3
mTv = V
v = mT/V = 0.3/1.5
v = 0.2m3/ kg
we know, v = x v g + (1 – x) vf

0.2 = x v g + (1 – x) vf

0.2 = x (0.375) + (1 – x) 0.001093

0.2 = x (0.375) + 0.001093 – 0.001093x
X = 0.53197
Thermodynamics

mg
x =  
mf + mg
mg = 0.7979kg

103.
 ml = 0.70215 kg
hence, Vl = 7.67 x 10-4 m3
Vg = 0.299 m3

Q Find out the amount of heat required to generate 5 kg of steam at a pressure

of 10 bar and temperature of 250 degrees Celsius from the water at 25’C,
take specific heat of superheated steam as 2.1KJ/Kg from steam table, the
steam properties of 10 bar as given below

Sol: TSat = 1799’C

hf = 762.6 KJ/kg
hfg = 2013.6 KJ/Kg
hsuperheated = hg + CP [TSteam – TSat]
hsuperheated = hg + CP [250 – 179.9]
How can say that steam is saturated
As here, TSat = 1799’C
So here, T > TSat (at given pressure = 1 bar)
Hfg = hg - hf ……………….*
hfg = 2013.6 KJ/Kg
hf = 762.6 KJ/kg
so, hg = 2776.2 KJ/Kg
hsuperheated = 2923.41 KJ/kg

Since enthalpy or energy of liquid having T = 25’C have to be subtract

h = mCP (25 – 0)
CP = 4.18 KJ/Kg
h = 104.5 KJ/Kg
y Energy supplied for 1 kg = 2923.41 – 104.5 = 2818.91 KJ/Kg
y Energy supplied for 5 kg = 14094.55 KJ/Kg
Energy required to make steam at 10 bar end 179.9’C
Then, hg = 2776.2 – 104.5
hg = 26717.7 KJ/Kg

Specific heat (hf)

Thermodynamics

Quantity of heat or can say amount required to raise the temp. of 1 kg of water from 0’C to
the boiling point or (TSat) at given pressure.
Sensible heat increases as the pressure increases.

104.
Latent heat of evaporation (hfg) or λ
hg - hf = λ
It is the amount of heat required to convert 1kg of water at TSat for a given pressure into a
dry and saturated steam at that temp. and pressure.
As the P↑, Latent heat ↓ and becomes zero at critical pressure.
Depending upon the condition of steam, heat and enthalpy value are defined as-

1. Total heat of wet steam

It represents the quantity of heat required to convert 1kg of water at 0’C to wet steam.
h = hf + x hfg
xhfg = x fraction of latent heat.
X = quantity ka steam bnane k liye kitni heat chaiye.
Sensible heat increases with pressure.
As P↑, h↑, T↑, Sensible↑
2. Total heat of dry steam
X=1
h = hf + hfg
or, h = hf + hg - hf
h = hg
Enthalpy of dry saturated steam decreases with increase in pressure
3. Total heat of superheated steam
It represents the quantity of heat required to convert 1kg of water at 0’C into superheated
steam at constant pressure
hSup = hg + CP (TSUPERHEAT - TSAT ) at given pressure
Imp. If x > 0 and P < 30 bar, the specific volume of water is practically insignificant and
can be neglected for example, vf = 0
specific volume of steam (v ) = x v g + (1 – x) vf

hence, v = = x v g

4. Superheated steam:- At any given pressure, T > TSat, superheated steam is considered as
perfect gas or it behaves like a perfect gas, therefore its volume can be found by Charle’s
law
According to charley’s law
PV = nRT (by ideal gas law)
vg TSat
=
v sup TSup

v g TSup
Thermodynamics

Vsup =
TSat

105.
 5. Internal energy of steam
Enthalpy is defined as
H = U + PV
Internal energy of wet steam
U = ( hf + x hfg) - P [ x v g + (1 – x) vf ]
U = [(1 – x) hf + x hg ] - P [ x v g + (1 – x) vf ] (Internal energy of wet steam)

y Internal energy of dry steam (saturated vapour)

x=1
U = hg - Pvg
Ug = hg - Pvg
y Internal energy of superheated steam
USup = hg + CP (TSUPERHEAT - TSAT ) - PSup
U = H - PV
H = U + PV
HSUP = USUP + PVSUP
HSUP - PVSUP = USUP
hSup = hg + CP (TSUPERHEAT - TSAT )
hg + CP (TSUPERHEAT - TSAT ) - PVSup = USUP

6. Entropy of steam
y Saturated liquid
TSat
ΔS = CP(Water) ln
273.17
TSat
Sf – SO = CP(Water) ln
273.17
If SO = 0 , 0’C is taken as reference.
TSat
Sf = CP(Water) ln
273.17
y Entropy of phase change or evaporation
Since entropy of phase change operation is taken as
λ
S=
TSat
Then the entropy of wet steam can be written as entropy of water and entropy of phase
change.
xhfg
Thermodynamics

Swet steam = Sf +
TSat
Swet steam = Sf + x sfg

106.
 7. Entropy of dry steam
x=1
Sdry steam = Sf + Sfg
= Sf + Sg - Sf
= Sg

8. Entropy of superheated
Tsup
SSUP = Sg + CP(sup) ln
TSat
At given pressure from the steam table, we can find the following information
y TSAT
y hf
y hg
y vg
y vf
y Sf
y Sg

Q Steam at 10 bar and 200’C is cooled till it becomes dry saturated steam and
is then throttled to 1 bar pressure, finding out change in enthalpy and heat
transfer during each process. Also find out the quality of steam at the end
of the throttling process. Take CP(SUPERHEAT) = 2.25 KJ/ kgk, following data is
given-

Sol: a) 10bar, 200’C

F=C–P+2
=1–2+2
=1
Only one data is required to find the all variable/ property within (L – V)
But in case of superheated
F=C–P+2
=1–1+2
= 2 required (T, P)
hSup = 2827.9 KJ/Kg
hg = 2776.2 KJ/Kg
Thermodynamics

y At 1 bar (home steam table)

hf = 417.5 KJ/Kg
hf = 2257.9 KJ/Kg

107.
 Q Amount of heat to be removed? (During cooling)

Sol: Q = 2827.9 - 2776.2

= 51.7 KJ/Kg
hsup = hsat or hg + CP (TSUPERHEAT - TSAT )
51.7 = CP (TSUPERHEAT - TSAT )
TSat = 177.02’C
Throttling process Adiabatic, and Enthalpy remain constant
2776.2 = (1 – x)hf + x hg
2776.2 = hf + x hfg
X = 1.044
After exiting, our steam is superheated. (as x > 1)

Degree of superheated-
ΔT = TSUPERHEAT - TSAT
hg @ 1 bar = 1840.4
2776.2 at @ 10 bar = hg @ 1 bar + CP(sup) @ 1 bar (TSUPERHEAT - TSAT )
ΔT = 44.97’C

Q Determine enthalpy, volume and internal energy and entropy of superheated

steam at 15 bar pressure and temp. 220’C, the volume of water can be ne-
glected and take the specific heat of superheat 2.2KJ/Kg at 220’C

Sol: hsup = hg + CP (TSUPERHEAT - TSAT )

(a) P = 15 bar, TSat = ?, hg = ?
TSat @15 bar = 198.3’C
hfg = 1945.2 KJ/Kg
hf = 844.7 KJ/kg
vg = 0.132 m3/kg
hfg = hg - hf
hsup = 2837.48 KJ/Kg
vg TSat
=
v sup TSup
Thermodynamics

Vsup = 0.138 m3/kg

H = U + PV

108.
 hsup = 2337.64
hsup - PVSup = Usup (P should be in KPa)
2837.64 - 15 x 102 x 0.138 = USUP
USup = 2630.64 KJ/kg
@ 15 bar-
Sf = 2.314 KJ/ Kg K
Sfg = 4.1261 KJ/ Kg K
Sg = 6.4401 KJ/ kg k
493
SSUP = Sg + CP ln
471.3
SSUP = 6.539 KJ/ kg k

Q Steam generated boiler at 8.5bar and 0.95 dry is taken to a superheater

where it reserves 8.5 KJ/Kg of heat at a constant pressure. subsequently the
steam is knotted to the pressure of 8.5 bar. Find out the final state of the
steam.
a) Is steam is wet
b) It is dry
c) x > 1

Sol: At the pressure of 8.5 bar

hfg = 2037.9 KJ/Kg
hf = 732.05 KJ/kg
hwet steam = 732.05 + 0.95 x 2037.9
hwet steam = 2668.05 KJ/kg
hsuper heat or h2 = 2668.05 + 85
h2 = 2753.055 KJ/ Kg
h2 = h3
@3.5 bar it is found that dry saturated steam hg was an enthalpy of 2731.6
KJ/kg
2753.055 = hg + CP (TSUPERHEAT - TSAT )
CP (TSUPERHEAT - TSAT ) = 21.455
It is the energy required to make the steam superheat.
CP(sup) = 2.2 KJ/kg k
TSUPERHEAT - TSAT = 0.21’C
Thermodynamics

109.
 Q Steam from the boiler delivered at an absolute pressure of 15 bar and dry-
ness fraction of 0.95 into a steam superheater in which the steam values
additional heat at constant pressure and temp increases to upto 300’C. Find
out the amount of heat added and internal energy change per unit mass of
steam.

Sol: Data given : TSat, CP(SUP), hf, hg (required)

@15 bar data given- T = 300’C, vsup = 0.1669 m3/kg
hfg = 1945.2 KJ/Kg vg = 0.132
hf = 844.7 KJ/kg
h = 3037.6 kg (superheated)
hsup = hg + CP (TSUPERHEAT - TSAT )
Q = (hg – h) + (hsup – hg)
= hg – h + hsup – hg
Q = hsup – [hf + x hgf)
Q = 344.96 KJ/kg
2. USUP = hsup - PVSUP
= 3037.6 - 15 x 102 [ 0.166g]
= 2787.25 KJ/Kg
ΔU = USup - U
At 0.95 quality-
U = H – PV
= hf + x hfg - 15 x 102 x [ 0.95
= 2504.54
ΔU = 282.71
dU = dQ - dW
= Q2 - P (V2 – V1)
= 344.96 – 15 x 102 [0.169 – 0.132]
= 282.71
Thermodynamics

110.
Q Steam initially at the 10 bar pressure with 2% moisture, flows steadily
through jackets of reciprocating machine measurement indicating that 5 kg
of this wet steam condenses every minute and condensate leaves the jacket
of the temp. of steam . Calculate the heat that will be given up by the jacket
steam per min.

Sol: Applying the first law of thermodynamics-

(as it is flow system)
Q – W = m (Δh)
Q - W = m (h2 – h1)
Q = 5/60 (h2 – h1)
x = 0.98
at @ 10 bar (wet steam)
hfg = 2013.6 KJ/kg
hf = 762.6 KJ/kg
h1 = hf + x hfg
h1 = 2735.928
saturated steam can be condensed. So, we should know TSat
@ 10 bar TSat = 179.9
@ 10 bar x = 0 (during condensation)
h2 = 762.6 = hf
heat released Q = 9866.64 KJ/Minute
Q = 164.44 KJ/sec

Q A vessel of 1m3 capacity contains steam at 10bar and 0.9’. the steam is al-
lowed to blow off by opening the delay value and period of blowing is so
regulated that pressure drops to 5 bar, subsequently the value is closed, and
the vessel is cooled until the pressure becomes 4 bar. Make the calculation
of the mass of steam blown off and the dryness fraction of steam in the ves-
sel after cooling and heat transfer during cooling. Assume that total heat per
kg of steam in the vessel remains constant during the period of blown off.
(Enthalpy remain constant)

Sol: Following data is given-

pressure vg hf hfg
Thermodynamics

10 bar 0.194m3/kg 7626 KJ/Kg 2013.6 KJ/kg

5 bar 0.375 m3/kg 640.1 KJ/Kg 2107.4 KJ/Kg

4 bar 0.462 m3/kg 604.7KJ/Kg 2133.0 KJ/kg

111.
 mg
X=
mf + mg
5.514
0.9 =
mf + 5.514
Blown off –
h1 = h2
hf + hfgx (@10 bar) = hf + hfgx (@5bar)
x2 = 0.918
m = mf + mg v = m2g
v = vf + vg v = vf + xvfg
mv = mfvf + mgvg v = vf + 0.9 x 0.194
1 = mg x 0.1746 1m3 = mg x 0.375
mg = 5724 kg (initial mass)
mg
X=
mf + mg
Volume of mixture at 5 bar-
V = vf + x vg
V = 0.918 x 0.375
V = 0.34425 m3/kg
V = mg x 0.34425
Mg = 2.9048 kg
Mass released = 5.727 – 2.9048 = 2.822 kg mass blown off
2nd part :
Dryness fraction after cooling (at 4 bar)
In cooling process-
V = vf + x vfg
V = x (0.462)
0.3442 = x (0.462)
X = 0.74
H2 = 0.74 x 2133 + 604.7
H2 = 2183.12
H1 = 0.918 x 2107.4 + 690.1
H1 = 2574.69
dU = dQ + dW
U3 – U2 = Q2-3 – P(V3 – V2)
Q2-3 = (U3 – U2) + P (V3 – V2)
= U3 – U2 – P2V2 – P3V3
Thermodynamics

(in 2 -3 process rigid volume)

Q2-3 = (h3 – P3V3) – (h2 – p2V2)
= 2.9048 [2183.12 – 4 x 102 x 0.3442] – [ 2574.69 – 5 x 102 x 0.3]
= 1006.44 KJ

112.
 Q Consider a vessel containing steam at 180’C. The initial steam quality is 0.5
and the initial volume of the vessel is 1m3 the vessel loses heat at a const.
rate q = 950 basic so that quality of steam reduces to 0.1 after 10 hr. ther-
modynamic properties of water at 180’C are initially 0.5 then x = 0.5, which
means net steam so T and P is lost @ 180’C
Vg = 0.19405 m3/kg
Vf = 0.001127 m3/kg
Ug = 2583.7 KJ/kg
Uf = 762.08 KJ/kg
Hf = 763.21 KJ/Kg
Hg = 2778.2 KJ/kg
Find the rate of heat loss in KJ/hour

Sol: Calculate mass-

V = 1m3 (v initial)
V = vf + x vfg
1 = m x 0.0975
m = 10.247 (At const. pressure)
By * Q – W = ΔU H = U + PV
Q = m (U2 – U1)
Hence, pressure is the same, volume will change.
Q = h (At const. pressure)
V1 = 10.247
V2 = 48.7
H2 = hf + x hfg
= 763 + 0.1 (2778.2 – 763)
= 964.52
H1 = 1770.6
Q = 806.08 KJ/ Kg 10hr
m = 10.256
Q = 8267.48 KJ/ 10hr
Q = 826.748 KJ/ hr

HEATING AND EXPANSION OF VAPOUR

Constant volume process
Thermodynamics

Consider a unit mass of steam undergoing a const. volume heating process from initial wet
state (1) pressure P1 and dryness fraction x1, to final superheated state (2) P2.
At const. volume, pressure will be changed.

113.
 During heating S↑ (entropy increases)
For const. volume process v1 = v2
X vg + (1 – x)vf = v2

Q If V2 is given they will ask for x.

Sol: X, vg and vf given they will ask for v2

2
W1-2 = ∫ P dV
1
=0

Applying FLOT,
dQ – dW = dU
dW = 0
Q1-2 = U2 – U1 U = h – PV
Q1-2 = (h2 – P2V2) – (h1 – P1V1)

Heat at const. pressure process

P is const.
How to find v2
V1 = x vg + (1 – x) vf
By Charles law, v2 superheated
TSup
V2 = vg2
TSat
v2 TSup
= Sat
vg2 T
From FLOT,
dQ – dW = dU
dQ = dW + dU
dQ = dW + PdV
dQ = dH

Constant temp. process (isothermal process)

In wet region temp and pressure remain constant for 950 thermal processes, which means
P1 = Pa,
Thermodynamics

T1 = Ta
Once the steam enters in the superheated region it behaves like a perfect gas and obeys
the gas law.

114.
 W1 – x = P (Va – V1)
Ua – U1 = (ha – h1) – P (Va – V1)
Q1 – a = dW + dU
Q1 – a = ha – h1
y In superheated region a – 2
Pa Va = P2V2
V2 = Pa Va/P2 (v2 = superheated)
Then temp. of superheated can be found by Charles law.
PV = nRTSup
PaVa
= TSup
R
V2 Va
⇒ =
T2 Ta
Ta = saturation temp. corresponding to pressure Pa.
V2 = volume of superheated vapour
Va = volume of dry saturated steam at Pa

Q Wet steam at 1.5 bar and 0.8 dryness occupies a volume of 0.05 m3 in a cylin-
der where compression takes place, so that PV = const. until the volume has
fallen to three fifth of original volume. Find out work and heat transfer and
final condition of steam. Given that –
@ 1.5 bar, vg = 1.159 m3/kg
@7.5 bar, vg = 0.256 m3/ kg

Sol: y V at 1.5 bar

Uf = 467 KJ/kg
Ufg = 2052 KJ/Kg
y V @ 7.5 bar
696 + 720
Uf = KJ/Kg = 708 KJ/Kg
2
1877 + 1857
Ufg = KJ/kg = 1867.0 KJ/Kg
2
dU = dQ – dW
U2 – U1 = Q1-2 – W1-2
Q1-2 = m( u2 – u1) – 12.07
Thermodynamics

U1 = Ug1 x1 + Uf1 (1 – x1)

U1 = Uf + x Ufg
X = 2058.4
Q1-2 = - 14.78KJ/kg

115.
 Constant T ( 180 thermal)
T1 = Ta = T2 (Const. temp. line)
But we cannot say
P1V1 = PaVa (as ideal is not applicable)
But, PaVa = P2V2 (superheated)
P1 > P2
As p is constant. (k – 2)
We can apply Charles law-
v2 TSup
= Sat
vg2 T
TSup
V2 = Vg2
TSat
Const. pressure process-
As P is const.
We can apply Charles law
v2 TSup
= Sat
va T
TSup
V2 = Va
TSat

Q A piston cylinder simply contains 1 kg of wet steam of quality 0.8 and P =

0.1m Pa. energy transfer as heat takes place at const. pressure till the temp
of steam to 350’C, make calculations for work done and heat interaction.
Following data is given-
At 0.1 m Pa , Vg = 1.694 m3/kg, Vf = 0, hf = 417.5KJ/kg, hfg = 2257.9 KJ/Kg
At 1bar, T = 350’C, 0.1mPa, V = 2.871 m3/kg,(super) , hsup = 3176.25KJ/kg

Sol: At const. P
dQ = dH
H1 = 2223.82, hsup = 3176.25
dQ = 952.43 KJ/kg
W = P dV
W = -0.1 x 106 (1.3552 – 2.871)
Thermodynamics

W = 151.58 KJ/kg

116.
Q Wet steam at 20 bar pressure. and 0.9 dryness factor is heated reversibly
at low press. to a temp of 500’C. Calculate work done and heat applied and
changes in internal energy and entropy change.
Following data is given-
At 20 bar at 20 bar, 300’C (superheated)
Vg = 0.0995 m /kg
3
v = 0.125 m3 /kg
Vf = not given (assume 0) u = 2772.6 KJ/Kg
Ufg = 1693 KJ/kg h = 3023.5 KJ/kg
Uf = 907 KJ/kg S = 6.766 KJ/Kg
Hf = 908.6 KJ/Kg Sfg = 3.8898 KJ/Kg
Hfg = 1888.6 KJ/kg Sf = 2.447 KJ/kg

Sol: 1)

Work = P dV
= -20 x 105 (0.995 x 0.9 – 0.125)
= 709 KJ/kg
2) dQ = dH
H1 = 791.14
H2 = 3023.5
dQ = 415.6 KJ/kg
3) dQ - dW = dU
ΔU = U2 – U1
ΔU = 341.9 KJ/Kg

Q Steam at an absolute press. of 10 bar and 250’C expands is entropically in

a steam turbine. If pressed. drops to 1 bar, estimate the quality of steam,
leaving the turbine. Work develops per KJ of steam. If actual drop is 90% of
isentropic drop and steam flow rate through turbine 500 kg/min. find the
power developed by a turbine.

Sol: Q – W = m (h2 – h1)

Q=0
– W = m (h2 – h1)
P = mwater
500
P= x (h2 – h1) x 0.9
Thermodynamics

60
500
Power = 0.9 x x (h2 – h1) KW
60

117.
 Throttling process
Flow to calculate quality of steam by throttling process. Since, in the throttling process
enthalpy remains constant.
In the throttling process, P always ↓, as we passed any steam from throttled value.
Since h1 = h2
As part (1) saturated, we must know hf and hg
h1 = [(1 – x) hf + x hg ]
now, h2 @ P2, T2 (superheated)
h2 = [(1 – x) hf + x hg ]
find x –
h2 = [(hf1 – x hf1 + x hg1 ]
h2 − hf1
x=
hg 1 − h
  f1
P↓, T↓
Pa < P1, T2 < T1
As pressure has been ↓ after throttling and –
1 at superheated steam
2 at superheated
And volume will also change.
And temp. will ↓ (mainly)
H = U + PV
In fig (a)
h1 = Ha = h2
[(1 – x) hf + x hg ] @ P1 = hg @ Pa = [ hg + CP(SUP) (T2 – Tsat)] @ P2

Q Finding out the dryness fraction of a sample of steam at 14 bar. It was

passed through a throttling calorimeter attached to the steam main. The
pressure and temp after throttling process recording to the 1.2 bar and 120’C.
Calculate the dryness fraction before passing through the throttling unit.
Take CP(SUP) = 2.1 KJ/kg. What is the min value of dryness that can be found by
a calorimeter? If pressed. and vol. are assumed to be the same.

Sol: @ 14 bar @ 1.2 bar, TSAT = 104.8’C

Hf = 830.1 KJ/Kg Hf = 439.4 KJ/Kg
Hfg = 1957.7 KJ/kg Hfg = 2244.1 KJ/kg
Thermodynamics

The 2nd position is superheat.

Ha = H2
H2 = = [ hg + CP(SUP) (T2 – Tsat)]

118.
 H2 = 2715.42 h @1.2 bar = h2
Hg = 2683.5
830.01 + x 195.7 = 2715.42
X = 0.963
Minimum degree dryness that can be estimated for the situation, for which
steam must be saturated.
H1 = ha
H2 = ha
(1 – x) hf + x hg = 830.01 + x 195.7
2683.5 = 830.01 + x 195.7
X = 0.9467

Q A saturated liquid. at 1500 k Pa at 500k with an enthalpy of 750 KJ/Kg is

throttled to a liquid vapour mix at 150 k Pa and 300k, at the exit condition,
enthalpy of saturated liquid is 500 KJ/Kg and saturated vapour enthalpy is
2500 KJ/kg of original liquid that vaporizes.

Sol: 750 = 2500 x + (1 – x) 500

X = 12.5
Hfg = hg - hf

Q A steam undergoes isentropic expansion in turbine from 5000 kg and 400’C

and entropy is S = 6.65 KJ/kg to pressure of 150k Pa having entropy of satu-
rated liq. is 1.4336 KJ/Kg k and sat vap entropy 7.2234 KJ/kg k exit condition
of steam is superheated vapour.

Sol: 6.65 = 7.2234 x + (1 – x) 1.4336

X = 0.9
Partially condensed vapour with quality 0.9
Thermodynamics

119.
 Q A steam turbine operates with a sup. Heated steam flowing at 1 kg/s, this
steam is supplied at 41 bar and 500’C and discharges at 1.01325 bar at
T = 100’C

Sol: Data given-

At 41 bar, 500’C at 1.07325r, 100’C (superheated)
Enthalpy = 3443.9 KJ/kg hf = 908.6 KJ/Kg
Entropy = 7.0785 KJ/Kg /k hg = 2676 KJ/Kg
Sf = 1.3069 KJ/Kg k Sg = 7.3554 KJ/Kg
@ 41 bar, TSat = 251.8’C
Enthalpy of saturated steam = 2799.9 KJ/Kg
Entropy of std. steam = 6.053 KJ/kg
Q – W = m (ΔH)
7.0785 = 7.3554 x + (1 – x) 1.3069
X = 0.954
h1 − ha
ηeff =
h1 − h2
Wactual
η=
m ∆x
h1 = 419.1 (1 – x) + 2676 x
h1 = 2572.77
-w = (h2 - h1) x m
W = 871.13

Q Saturated water vapour at adiabatic turbine at 0.8 m Pa. and leaves at 0.1m
Pa, then mass flow rate of water vapour is 25 kg/s. use the following table-

pressure Temp Specific Specific

(‘C) enthalpy entropy

m Pa HL (KJ/Kg) HV (KJ/ Kg) SL = KJ/Kg k SV = KJ/

Kg k

0.8 170.43 722.11 2764.10 2.0462 6.6628

Thermodynamics

0.1 99.63 417.46 2675.55 1.3026 7.3594

120.
 1) The quality of steam at the exit of turbine after an isentropic expansion.
2) If the steam leaves the turbine as saturated vapour then find the power
produced by turbine in kw.

Sol: 1) At inlet –
6.628 x + (1 – x) 2.0462 = 7.35994x + (1 – x) 1.3026
x = 0.8853
2. w = m (oh)
W = 234.0 KJ

STEAM POWER PLANT CYCLE

Boiler
Turbine
Pump

H2 > h1,
P1 > P2,
T1 > T2

Network = Wshaft - Wphng

W QH − Qc
η= =
QH QH

QH = h2 – h1
Qc = h4 – h5

Q In a steam power plant, power output is 1 mw, while the boiler heat is at the
rate of 2.5 mw. The pump power input is negligible, in the condenser exhaust
steam of turbine rejects heat to the steady flow of cooling water, which
enters the condenser at 25’C and exits at 40’C. Ignore KE and PE for cooling
water. The specific heat of water is 4 Kg/k. Find the mass flow rate.

Sol: QH + WPUMP = QSHAFT + QC

Thermodynamics

2.5 x 103 = 1 x 103 + m x 4 x (40 – 25)

m = 25 kg/s

121.
 CARNOT CYCLE ON T/S for steam power plant
1 – 2, 3 – 4 (Isothermal expansion and reversible compression)
2 – 3, 4 – 1 (Reversible adiabatic expansion and compression)
In reversible adiabatic expansion T↓
Wactual TC
η= =1-
Qh TH

Quality is very high at exit of turbine, as (wet steam) So it can create severe conditional
corrosion, erosion in turbine.
If water more than (10%)
Special type of pump must be designed; (vapor + liquid) wet steam goes to the pump.
Generally, pump is designed to deal with liquid, but (has vapor + liquid)
So here we are facing these problems.
1. Corrosion
2. Erosion
3. Transportation problem via pump
In step 1-2, the Vaporisation process is taking place in the boiler where the saturated liquid
water absorbs the heat at a constant temperature TH. And produce saturated vapor.
In step 2-3, Is a reversible adiabatic expansion of saturated vapor into two phase
regions (wet region) to produce the mixture of saturated liquid and vapor at temperature
of Tc.
Step 3-4, It is a partial condensation process, where heat is rejected at temperature Tc.
Step 4-1, This step takes the cycle back to its origin, producing saturated liquid water at
point 1.

Rankine cycle
The thermal efficiency of Carnot heat engine can be written as
TC
ηC = 1 −
TH
Valid for Carnot only (as carnot is reversible)
As a reversible cycle it could act as a standard for comparison of actual steam power plants,
but there are severe practical difficulties for carrying out the steps 2-3 & 4-1.
Turbine that takes in saturated steam produces an exhaust with high liquid content which
causes severe erosion problems and even more difficulties in the design of the pump that
takes in the mixture of liquid and vapor at pt. 4. And has to produce saturated liquid at
points for this region, spiral design of pump required.
For this reason, an alternative modal cycle is taken as standard at least for fossil fuel
Thermodynamics

burning plants. It is called the Rankine cycle.

122.
 Rankine cycle
1-2 constant pressure heating process in a boiler, this step lies alone an isobar (constant
pressure) and this step consist of these sections
1. Heating of subcooled liquid water to its saturation temperature.
2. Vaporisation at constant temperature and pressure.
3. Superheating of vapor to a temperature, well above its Tsat

2-3
It is reversible adiabatic expansion of the vapor in a turbine to a turbine to a pressure of
condenser, this step normally crosses the saturation curve & producing a wet exhaust or wet
steam, but content of liquid not too large.

3-4
At constant pressure, constant temperature in a condenser to produce
Saturated liquid at point 4
Reversible adiabatic (isentropic) ramping of saturated liquid to the pressure of boiler is to
produce compressed or supercooled liquid.
The length of 4 – 1 is too short, because temp. The rise for the compression of liquid is very
small.
y Entropy increases in a reversible process.

Q The inlet and outlet condition of steam for an adiabatic steam turbine is
given in fig-
H1 = 3200 KJ/kg H2 = 2600 KJ/Kg
U1 = 160 m/s U2 = 100 m/s
Z1 = 10 m Z2 = 6m
P1 = 3m Pa P2 = 70k Pa
If the mass flow rate of steam through a turbine is 20 kg/sec. find the power
output of the turbine.

Sol: Q – W = m ( Δh +
∆C2
+ ΔZ)
2
∆C2
0 – W = m ( Δh + + ΔZ)
2
∆C2
Thermodynamics

-W = 20 x (Δh + + ΔZ)
2
W = 12.156 x 106 w

123.
 Q Assume the above turbine to be a part of a simple rankine cycle density of
water at inlet of pump is 1000 kg/m3 (at point 4). Ignore the KE and PE ef-
fect. Find the specific work in KJ/kg supplied to the pump.

Sol: Q – W = m ( Δh +
∆C2
+ ΔZ)
2
-W = m (h1 – h4)
Since work done in the open system is VdP
W KJ/Kg = -VdP
WPUMP = 293 KJ/Kg

WORK DONE IN AN OPEN SYSTEM

W = -VdP
y For adiabatic-
For closed system
For closed system-

W=
P1V1 − P2V2
=
(
nR  T1 − T2 )
= CV (T1 – T2)
r−1 r−1
Where, in open system-
PVr = constant (C) (for adiabatic process)

W= ∫ VdP
C
∫ (P )
1/r
W= dP

dP
W = -C1/r ∫ P1/r

∫P
−1/r
W = -C1/r dP

1
− +1
W = -C1/r [ r ] P1 → P2
1
− +1
r
(P1V1 ) = C
r 1/r
Thermodynamics

C = P11/r V1
−r
W= (P V – P1V1)
r−1 2 2

124.
 r
W= (P1V1 – P2V2)
r−1
rR
W= (T – T2)
r−1 1
W = r CV (T1 – T2)
y For isobaric process-

W=- ∫ VdP =0

y For isochoric process-

P2
W= − ∫ P1
VdP

W = -V (P2 – P1)
W = V (P1 – P2)
y For isothermal process-
PV = constant

W=- ∫ VdP
C
W=- ∫ P
dP

P2 dP
W = -C ∫ P1 P
P2
W = -P1V1 Ln ( )
P1
P1
W = P1V1 Ln ( )
P2
P1
W = RT1 Ln ( )
P2
It is the work done for open systems and closed systems for iso-thermal processes.

VAPOUR COMPRESSION CYCLE

1) Compressor
2) Evaporator
3) Condenser
4) Throttling valve/ expander

TWO TYPES OF REFRIGERATION CYCLE-

Thermodynamics

1) Non cycling (cooler and chiller)

2) Cycling (vapour compression and vapour absorption)

125.
 Two types of compression-
1) Mechanical means- compression in vapour by mechanical means.
2) Thermal means- vapour absorption

VAPOUR ABSORPTION (by thermal means)

Ammonia temperature is very low.
The main difference between the vapour compression and absorption refrigeration is means
for compression.
Qc
Cop =
Q + Wp
useful output Qc
Cop = =
useful input Q + Wp

Q A vapour compression refrigeration cycle using tetra-fluoro-ethane (R –

134a) is operating between the pressure limits of 0.17074 MPa to 1.13 MPa,
compression is isentropic with saturated vapour at the inlet and condenser
exit is saturated liq.
Following table gives saturation values of refrigerant at two pressure values.

Pressure Temp. Enthalpy Entropy

(m Pa) (‘C) (KJ/Kg) (KJ/Kg)

0.17074 -14’C 181.56 390.33 0.9311 1.7361

1.130 44’C 262.38 421.28 1.2091 1.710

1) Find the Cop of performance of refrigeration is expansion is happening

with isentropic expander (S1 = S2)
2) IF it is throttling value then h1 = h2

Sol: Compensation (S1 = S2)

1.7361 = 1.2091 (1 – x) + 1.710x
X = 1.052 quality
Qc
Cop =
W
h2 − h1
Cop =
h2 − h1 − h3 − h4
Thermodynamics

W = RH + RC
h2 − h1
Cop =
(h2 − h1) − (h3 − h4 )
126.
CPSUPERHEAT at 1.13 m Pa = 1.15 KJ/Kg
Condition to (1) isotropic expander
S4 = S1
1.2091 = 0.9311 (1 – x) + 1.7367 x
X = 0.345
At x = 0.1707
H1 = 181.56 (1 – x) + 390.33 x
H1 = 253.61 KJ/Kg
At x = 1
H2 = 390.33 KJ/Kg
H2 – h1 = 136.72 KJ/ Kg
At point between 2 and 3
S2 = S3
TSUP
1.7361 = Sg + CPSUP ln SAT
T
TSUP
1.7361 = 1.710 + 1.5 ln SAT
T
SUP
T
1.0229 = SAT
T
T = 51.276’C
SUP

H3 = hg + CP (TSUP – TSAT)
H3 = 421.28 + 1.15 (51.276 – 44)
H3 = 429.64 KJ/Kg
H4 = 262.38
QH − Qc
Cop =
QH

h2 − h1
Cop =
(h3 − h4 ) − (h2 − h1)
Cop = 4.476
Throttling value-
h4 = h1
262.38 = 181.56 (1 – x) + 390.33 x
X = 0.3871
H3 = 429.64 KJ/Kg
H4 = 262.38
H2 = 390.33
Thermodynamics

H1 = 262.38
Cop = 3.254

127.
 Q For expansion in the expansion valve, calculate and find the max flow rate of
refrigerant (2) power required for compression for a refrigerator capacity of
2 ton.

Sol: 1 ton of refrigeration = energy to vaporize to freeze 1 ton of liquid water at 0’C
into ice in 24 hr.
M = 1/24 x
Qc = mλ
1 ton of refrigeration = 50 kcal/min or 3200 w
Qc = 3200 w
Qc = 6400 J/S
mλ = 6400
6400
m=
h2 − h1
6400
m=
390.33 − 262.38
50
m= kg/sec
1000
m = 0.05 kg/sec
m = 3 kg/min
(2) Power required for compression
W = h3 – h2.
W = 118.08 KJ/Min
W = -1.968 Kw

Q Air enters an adiabatic nozzle in 300 k Pa and T = 5’k. with the velocity of
10m/s, it leaves the nozzle at 100 k Pa with the velocity of 180 m/s, the inlet
area is 80 cm2, CP(AIR) = 1.008 KJ/kg k. find out-
1) Exit temp. of air
2) Exit area of nozzle

Sol: Q – W = m (Δh +
C2
+ g Δx)
2
Thermodynamics

1802 −  102
-w = m [CP (T2 – 500) + ]
2
T2 = 483.97 K

128.
 (2) ρA1V1 = ρA2V2
A2 = 12.96 cm2
y P1V1 = RT
300 x v1 = 8.314 x 500
V1 = 13.85 x 103
y P2V2 = RT2
V2 = 40.23 x 10-3

UNSTEADY MASS BALANCE AND ENERGY BALANCE

dESystem
m1e1 - meee + Q – W =
dT
Ci2 Ce2 dESystem
mi [hi + + g Zi ] - me [he + + g Ze] + Q – WS =
2 2 dT
For small time interval
Miei - meee + Q – W = ΔU (control volume)
Q = amount of heat in that time interval
Ci2 Ce2
mi [hi + + g Zi ] - me [he + + g Ze] + Q – WS = U2 – U1
2 2
U2 and U1 are showing state before time interval and after interval (not inlet outlet)
m2u2 – m1u1 = u2 – u1
m2 = mass stored after the time interval
m1 = mass stored before the time interval
Ci2 Ce2
mi [hi + + g Zi ] - me [he + + g Ze] + Q – WS = m2u2 – m1u1
2 2
if K.E. and P.E. = 0
miei - meee + Q – W = m2u2 – m1u1 Thermodynamics

129.
 Q An insulated evaluated (mass = 0) container is connected to a supply line of
an ideal gas at pressure PS, Temp TS, and their specific volume VS, the con-
tainer is filled with the gas until the pressure in the container reaches PS.
There is no heat transfer between the supply line to the container and KE
and PE = 0 is CP and CV are the specific heat capacities at const. pressure and
volume, then final temp of the gas is -

Sol: 1) T2 = r Ts
2) Ts
r−1

Ts
r−1
3) Ts
r
mi = m2 – m1
Initially m1 = 0
As mass is going to accumulate as nothing is going out.
Energy balance-
dESystem
m1e1 - meee =
dT
For small time period-
mi hi - me he = U2 – U1
mi hi - me he = m2u2 – m1u1
mi hi = m2u2
CP TS = T2 CV
Cp
⇒ T = T2
Cv S
T2 = r Ts

Q An insulated rigid tank of volume 1m3 is initially empty. The tank is connect-
ed to a supply line of air at 2m Pa and 300k by a valve, the tank is allowed to
fill and process ends when the pressure in the tank reaches the supply line
pressure. Calculate the final temp of air in the tank and mass of the air that
entered. If the tank had initially air at 300k and 1 atm, find out final temp
and mass of air added.
Thermodynamics

Sol: For air r = 1.4

Mw = 29
T2 = r Ts

130.
 T2 = 420 k
P1V1 = nRT
2 x 106 = n (8.314 x 420)
n = 572.72 moles
m = 16.61 kg
(2) By applying mass balance
dM
mi + me =
dT
mi + me = m2 – m1
P1V1 = n RT
n = 40.09 mol
m1 = 1.1626 kg
dESystem
miei - meee + Q – W =
dT
miei = m2u2 – m1u1
P2V2 P1V1 Cp
mi = [ - ] x 29 =R
RT2 RT1 Cv
2 X  106  X  1 105  X  1
mi = [ - ] X 29 Cp – Cv = R
8.314 X  T2 8.314 X  300
mi hi = m2 [CV T2 – CV T1]
T2 = 411.65
m1 = 15.77 kg

THERMODYNAMICS PROPERTIES RELATION

H = U + PV
G = H – TS
A = U – TS
dH = dU + PdV + VdP ……………..(*)
From FLOT,
dU = dQ – dW
For closed system,
dwREVERSIBLE = ∫ PdV
dQRev = T dS
dU = TdS – PdV
TdS = dU + PdV
Thermodynamics

This equation is valid for irreversible/ reversible, open and closed systems but for constant
composition only.
dU = TdS – PdV ……………(1)

131.
 This eq. is combined eq. of first law and second law of thermodynamics.
Replace TdS, from (1) and (*)
dH = dU + PdV + VdP
dH = TdS + VdP ……………(2)
dG = dH - TdS – SdT
As, dH - TdS = VdP
dG = VdP – SdT …………..(3)
dA = dV - TdS – SdT
dA = -PdV – SdT ………….(4)
NOTE: all these eq. can be used as an irreversible/ reversible, open and closed system but
composition must be const.
NOTE: dG = VdP – SdT
dU = TdS – PdV
dH = TdS + VdP
dA = -PdV – SdT

During phase change operation-

dG = 0, dU ≠ 0, dH ≠ 0, dA ≠ 0
As T and P remain const. during phase change-
G = f(T,P) and dG = 0
Change in Gibbs free energy is zero.

SOME MATHEMATICAL THEOREMS

M = f (x, y)
∂M ∂M
dM = dx + = dy
∂x ∂y
dM = Pdx + Qdy
∂P ∂ 2M
|x = const. =
∂y ∂x∂y
∂Q ∂ 2M
|y = const. =
∂x ∂x∂y
∂P ∂Q
| = |
∂y x = const. ∂x y = const
If any eq. is given in this form-
dM = Pdx + Qdy
∂P ∂Q
Thermodynamics

Then, | = | this form is called Maxwell form.

∂y x ∂x y
Similarly,

132.
 ∂V ∂S
dG = VdP – SdT |P = − |
∂T ∂P T
∂T ∂P
dU = TdS – PdV | = − |
∂V S ∂S V
∂T ∂V
dH = TdS + VdP |S = − |
∂P ∂S P
∂P ∂S
dA = -PdV – SdT |V = − |
∂T ∂V T
y dG = VdP – SdT
y dU = TdS – PdV
y dH = TdS + VdP
y dA = -PdV – SdT

CYCLIC THEOREM
X = f (y, z)
∂x ∂y ∂Z
|Z. = |x = | = -1
∂y ∂z ∂x y
If S = f (T, V)
∂S ∂S
dS = |V dT + | dV
∂T ∂V T
Multiply the whole eq. by T
∂S ∂S
TdS = T | dT + T | dV
∂T V ∂V T
∂S ∂P
TdS = T( )V dT + T( ) dV
∂T ∂T V
1 dQ dS
CV = |V = T |
n dT dT V
∂P
TdS = nCV dT + T( ) dV
∂T V
When n = 1
∂P
TdS = CV dT + T( ) dV ……………(a)
∂T V
If S = f (T, P)
∂S ∂S
dS = |P dT + | dP
∂T ∂P T
Thermodynamics

Multiply the whole eq. by T

∂S ∂S
TdS = T |P dT + T | dP
∂T ∂P T

133.
 ∂S ∂V
TdS = T( )V dT + T(- ) dP
∂T ∂T P
∂V
TdS = nCP dT + T( − ) dP
∂T P
∂V
TdS = nCP dT - T( ) dP
∂T P
When n = 1
∂V
TdS = CP dT - T( ) dP ……………(b)
∂T P
From (a) and (b)
∂P ∂V
TdS – TdS = CV dT - CP dT + T( )V dV - T( ) dP
∂T ∂T P
∂P ∂V
0 = CV dT - CP dT + T( ) dV - T( ) dP
∂T V ∂T P
∂P ∂V
CV dT - CP dT = T( )V dV + T( ) dP
∂T ∂T P
∂P ∂V
(CP - CV ) dT = T [ ( )V dV + ( ) dP ]
∂T ∂T P
∂P ∂V
dT = T [ ( )V dV + ( ) dP ] / (CP - CV )
∂T ∂T P
If T = f (T, P)
∂T ∂T
dT = | dV + | Dp
∂V P ∂P V
∂P
|
∂T ∂T P ………….(1)
|P = T
∂V CP −  CV
∂V
|P
∂T
|V = T ∂T ………….(2)
∂P CP −  CV
∂V ∂P
(CP - CV ) = ( )P ( ) T
∂T ∂T V
∂V ∂P
(CP - CV) = T ( ) ( )
∂T P ∂T V
From cyclic theorem-
P = f (T, V)
Thermodynamics

∂P ∂T ∂V
)V ( )P ( ) = -1
∂T ∂V ∂P T

134.
 ∂P
By this find ( )
∂T V
∂P ∂V ∂V
(CP - CV) = -T ( ) ( ) ( )
∂V T ∂T P ∂T P
∂P ∂V
(CP - CV) = -T ( )T [( ) ]2
∂V ∂T P
1 ∂V
α= ( )
V ∂P T
1 ∂V
β= ( )
V ∂T P
β2 V
(CP - CV) = T (valid for any gas)
α
1 1
For ideal gases, α = ,β=
P T
2
1
  V
(CP - CV) = T T
1
 
T
PV
(CP - CV) =
T
PV = RT (for n = 1)
PV
⇒ =R
T
(CP - CV) = R (valid for ideal gas only)

JOULE THOMSON COEFFICIENT

It means change in temp with change in pressure.
In full expansion, Pressure always decreases.
∂T
Uj = |
∂P H
Uj > 0 (as P↓, T↓) cooling
Uj < 0 (as P↓, T↑) heating
Uj = 0 (for ideal gas, and at inversion point)
If ideal gas is allowed to throttled isentropic then Uj = 0
Since, dH = TdS + VdP ⇒ TdS = dH - VdP
Thermodynamics

∂V
TdS = CP dT - T ( ) dP
∂T P

135.
 ∂V
dH - VdP = CP dT - T ( ) dP
∂T P
∂V
dH = CP dT - T ( ) dP + VdP
∂T P
∂V
dH = CP dT + {V - T ( ) } dP
∂T P
For isentropic process dH = 0
∂V
0 = CP dT + {V - T ( ) } dP
∂T P
∂V
- CP dT = {V - T ( ) } dP
∂T P
∂T ∂V
| = {V - T ( ) } / CP ……………….(A)
∂P H ∂T P
For ideal gas-
PV = RT
∂V
| = R/P
∂T P
Putting value in (A)
∂T
| = {V - T (R/P)} / CP
∂P H
For ideal gas-
∂T
| = 0 = UJ
∂P H
There is no change in temp, when ideal gas is made to undergo a throttling process.
y If ideal gas is being throttled and pressure decrease upto 20%
P1V1 = P2V2
P1 = 1
P2 = 0.2

CLAUSIUS CLAPEYRON EQUATION

This eq. is used to find out the change in enthalpy during the phase change operation.
hαβ, hfg = hg – hf (enthalpy change during evaporation)
This eq. is used to find out the change in enthalpy during the phase change operation.
Since, during the phase change operation of the pure substance, Gibbs free energy
becomes zero.
Thermodynamics

dG = 0
gibbs free energy is constant.
dG = VdP – SdT

136.
There are two phases: α phase, β phase
at (1) gα = gβ @ (T1, P1)
as at point (2) @ (T2, P2)
gα + dgα = gβ + dgβ
dgα = dgβ
Vα dP - Sα dT = Vβ dP - Sβ dT
dP ( Vα – Vβ) = dT (Sα – Sβ)

⇒
dP
=
Sα − Sβ
=
∆S αβ ( )
dT Vα − Vβ ∆V αβ ( )
During phase change operation-

dS =
dQ
=
∆h αβ ( )
T T

⇒
dP
=
∆h αβ ( )
(clapeyron equation)
dT T ∆V αβ ( )
dP
At every point will be different.
dT
Hence, claperon eq. is frequently used to find the enthalpy change associated with phase
change from the knowledge pressure Kmp and volume data. This can be used for Vaporization,
Sublimation.

Clausius Claypan equation

By these assumptions, the Claypan equation can be changed into the Clausius Claypan
equation.
fg
v= vg − vf

If the volume v g  v f very more then

v fg = v g

Vapor behaves as Ideal gas

If latent heat of phase change is assumed to remain constant, small change in temperature
or can say for small temperature change λ is constant.
dP λvap
=
dT Tvg
dP λvapP  
=
dT
Thermodynamics

2
RT
dP λvap
=
PdT RT2

137.
 dlnlnP
    λvap
=
dT RT2
λvap  1 
lnlnP
=    − 
R  T

P λvap  1 1
lnln  2  
=  − 
P1 R  T1 T2 

P2sat λvap  1 1
lnln 
=    − 
P1sat R  T1 T2 

This equation is a combination of first law & second law.

According to the Clausius Clapeyron equation λvap is remained constant or hfg
= hg − hf is
almost constant.
Virtually it is independent of temperature. {This is not true because λvap or hfg decreases
monotonically with increase in temperature.}
At triple point it is maximum, & at critical point it is minimum, where it becomes zero. The
assumptions on which Clausius clapeyron equation is based have appropriate validity on
low pressure.

Antoine equation
Clausius clapeyron equation can be written in empirical form as
B
  sat=  A −
lnlnP
T
A satisfied relation is by Antoine
B
  sat  =
lnlnP A− → Antonie equation
T+C
As species change A, B & C changes.
This equation can be used for any pressure.

TROUTON’S RULE
It states that the entropy change of vaporisation is almost the same value from liquid to
vapour.
85 – 88 J/ mol/ k at this normal boiling point.
∆hfg λ Vap
ΔS = =
T T
We can also say, according to this rule the molar heat heat of evaporation at normal BP is
Thermodynamics

related to boiling temp as λ = 10R Tb

138.
Q The vapour pressure of water is given by –
500
Ln PSAT = A -
T
Where A = const., TSAT is vapour pressure (in atm), find out VP at 50’C.

Sol: At 1 atm, TSAT = 100’C = 373K

PSAT at 50’C = 0.1255

Q For a liq., the rate of change of VP with temp is 0.1 bar/k in the temp range
of 300 to 350k. if the BP of liquid at 2 bar is 320K then find the temp in k at
which it will boil at the pressure of 1 bar.

Sol: We know that,

dlnlnP  SAT  
=
λ vap
dT RT2
SAT
dP
As P↓, T↓ = 0.1 bar
dT
P2 – P1 = 0.2 (T2 – T1)
T = 310 K

Q At 100’C, water and methane-cyclohexane both at 100’C have pressure at 1

atm. Also, latent heat of evaporation of these compounds are 40.63 KJ/mol
for water and 31.55 KJ/mol for methane-cyclohexane. The VP of water at
150’C is 4.69 atm, then find the VP of methane-cyclohexane at 150’C.

Sol: dlnlnP  SAT  

=
λ vap
dT RT2
PSAT λ 1 1
Ln ( eSAT ) = ( - )
P1 R T1 T2
P = 3.32 atm (less than 4.69 atm)
dP λ vap ∆Hαβ
= =
dT RT2 T ∆V αβ
Thermodynamics

dP
0r ∝ Δn
dl nT
For the same temp diff, change in pressure will be zero, for a high value of
latent heat.

139.
 Q As ideal gas temp T1 and P1 is compressed iso-thermally to P2 in a closed
system. Which of the following is true for internal energy and GIBBS free
energy.
1) U1 = U2, G1 > G2 2) U1 = U2, G1 < G2
3) U1 < U2, G1 = G2 4) U1 > U2, G1 = G2

Sol: For Ideal gas,

U1 = U2, dU = 0
dG = VdP – SdT
P2 > P1
ΔG = RT ln P
G2 – G1 = RT ln P2/P1

Q For a superheated vapour that cannot be approximated as an ideal gas, de-

termine the small change in specific internal energy-
dU dU
1) dU = CP dT + ( )T dV 2) dU = CP dT + ( ) dP
dV dP T
dU
3) dU = CV dT + ( ) dV 4) dU = CV dT
dV T

Sol: Superheated vapour-

dU
U = f (T, V) ⇒ dU = CP Dt + ( ) dV
dV T
dU
U = f (T, P) ⇒ dU = CP Dt + ( ) dP
dP T

Q Which one of the following is correct for ideal gas in closed system-
dG dU dH dH
1) ( )S V = R ( )V 2) - ( )S P = R ( )
dV dS dP dS P
dG dH dH dV
3) ( ) V=R( ) 4) ( ) P=R( )
dV S dS P dP S dS V
Thermodynamics

140.
 Q Match the following-
dG
( ) = T ……..(4)
dV S
dG
( ) = P ……..(1)
dP T
dG
-( ) = V ……..(2)
dT P
dU
( ) = S ……..(3)
dS V

Q For water at 25’C,

dPSAT
= 0.189 K Pa/k, and the specific volume of saturated
dT SAT
vapour is 43.38 m3/kg. assume the specific volume of liq. is negligible, using
clausius- claypron eq. Find the enthalpy of evaporation.

Sol: We know that-

dPSAT ∆H
=
dT T ∆V
ΔH = 2443.24 KJ/kg

Solution thermodynamics
In chemical, petro chemical and pharma critical industries, the multicomponent gases and
liquid commonly undergo chemical changes, brought about by mixing, separation process
and transfer of species from one phase to other phase or by chemical reaction.
In this topic, we are able to study thermodynamics behaviour of multicomponent system
properties of a species in solution differ from its pure form properties.

Partial Molar property

To understand the partial molar properties, consider partial molar volume. Partial molar
volume is the contribution that a component in the solution makes to the total volume.
Consider an open beaker containing a huge volume of water. Assuming that one mole of
water is added to it. The volume increases by 18 × 10−6 m3 , which is the molar volume of pure
Thermodynamics

water. If the same amount of water is added to a large amount of pure ethanol taken in the
beaker, the increase in the volume will be approximately 14 × 10−6 m3 , which is the partial
molar volume water in pure ethanol. The difference in the increase in volumes can be

141.
 explained as the volume occupied by a given number of water molecules depends on the
molecules surrounding them. When water is mixed with a large volume of alcohol, there is
so much alcohol present that each water molecule is surrounded by pure ethanol.
Consequently. The packing of the molecules would be different from that in the pure water,
and the molecules occupy lesser volume.
Thus, it has been concluded that the partial molar properties of the components of a mixture
vary with the composition because the environment of each type of molecule changes as
the composition changes. In addition, the intermolecular forces get changed resulting in the
changes in the thermodynamics properties of solution with composition.
Consider any thermodynamic extensive property (such as volume, free energy , heat capacity,
etc) its value for a homogenous system being completely determined by the temperature,
pressure and the amounts of various constituents present.
Let M be the molar property of a solution and Mt be the total property.
Mt = nm = f T,P (
  , n1 ,n2 , ………… nn )
where
N is the total no of species in the mixture
n
n= ∑ n are the number of moles of the respective components 1,2,3,….. of the system
i= 1 i

If there is a small change in the pressure, temperature and the amounts of the various
constituents then,
∂ nm ∂ nm( ) ( ) N ( ) | dn                T,Pn j ≠ i 
∂ nm
dMt =
 d nm =
 
∂T
( )
dTP
  ,n +
∂P
dP T,n + ∑ i= 1 ∂ni i

mi . is the partial molar property of species i in the solution.

= mi
∂ nm ( ) dn
=                T,Pn
  j ≠ i 
∂M
dni                T,P nj ≠ i .
i
∂ni ∂ni
∂M
mi = | dni                T,P, n2 , n3  he partial molar property of species i is a measure of
∂ni
response of total solution property due to change in no of moles of that particular species
keeping T, P and all other species constant.
∂M
vi = | 0  T,P, n2  
∂ni
∆nw that much more of water is going to add (keeping T, P and n2 constant).

∂ nm ∂ nm( ) ( ) N ( ) | dn                T,Pn j ≠ i 
∂ nm
( )
Thermodynamics

dMt =
 d nm =
 
∂T
dTP
  ,n +
∂P
dP T,n + ∑ i= 1 ∂ni i

It can be written as

142.
 n ∂m ∂ nm ( ) ( )
dMt =
 d nm =
  ( )
∂T
dTP
  , x +
∂P
dP T,n + ∑ midn i

x = differentiation at constant composition

Since ni = xin
dni xidn + ndxi
=
( )
d nm
= ndm + mdn

n ∂m( ) dTP , x + ∂ (nm) dP T,n +

ndm =
+ mdn
∂T ∂P ∑ m ( x dn + ndx )
i i i

 ∂m ∂m   
n dm −
 ∂T
dTP
  , x +
∂P
dP T,n − ∑ m dx  + m − ∑ m x  dn =
i i
0 i i

Since n i.e no of moles and dn i.e change in no of moles cannot be zero for above equation,
Coefficient of n & dn must be zero.
By summation rule

m = ∑ xm i i

∂m ∂m
dm =
∂T
dTP
  , x +
∂P
dP T, x − ∑ m dx  
i i
……….. (1)

As differentiating summability relation

m = ∑ x mi i

= dm ∑ x dm + ∑ m dx
i i i i
……….. (2)

From equation (1) & (2)

∂m ∂m
∑ x dm + ∑ m dx
i i i i
=
∂T
dTP
  , x +
∂P
dP T, x − ∑ m dx i i

∑ x dm i i
= 0 This is Gibbs duhem equation valid for T & P

Important

m = ∑ x mi . i
Summation rule

∑ x dm = 0 | 0 T,P  Gibbs duhem equation

Thermodynamics

i i

For Binary mixture

>  xidmi =
= 0 (by Gibbs duhem equation)

143.
 Dividing this equationb
  y any constant quantity dn1
dm1 dm2
x1 = −x2
dn1 dn2

m =  ∑ xm i i

∑ n x mi
t
nm
= M
=   i

M =  ∑ n  m i i

If M =
=
dG  d=
nG G T,P ( ) (
  ,n1 ,n2 + …………… .  )
∂ (nG) ∂ (nG) ( ) | dn               T,P, n
∂ nG
( )
d nG =
∂T
dTP
  ,n +
∂P
dP T,n + ∑ ∂ni i j
≠ i 

It is valid for an open system (for changing no of moles).

dni Changes in no. of moles.

( ) (nv ) dP − (ns) dT
d nG
=

Valid for closed system or open system with constant composition

Internal Energy
( )
µf s, v for open/closed system for constant composition

µf ( s, v,n1 ,n2 + ……… nw )

=du Td (ns ) − Pd (nv ) Valid for closed system or open system with constant composition

∂ (nu) ∂ (nu) ∂ (nu)

du = d (nu) = ds   V,n + dv s,n + ∑ | dni               s, v, n j ≠ i 
∂s ∂v ∂n i

Enthalpy
( )
h = f s,P for closed system|open with constant composition.

h
= f ( s,P,n1 ,n2 …… .. ) open system

( ) ( ) ∑ ∂ (nh) | dn               s,P , n
Thermodynamics

∂ nh ∂ nh
dH = ( )
d nh = ds  P
∂s
     +
∂P
dv s,n +
∂n1 i j
≠ i 

144.
Helmoltz energy
( )
af v, T for closed/Open with no change in no of moles

af ( T, v,n1 ,n2 + ........ )

∂ (na ) ∂ (na ) N ∂ (na )

dA = d (na ) = dv   T, n   + dT v,n + ∑ | dni               T, v, n j ≠ i 
∂v ∂T i= 1 ∂n
1

Since, partial molar property is defined as

mi
( )  | 0              T,P , n
∂ nm
≠ i 
j
∂ni
Means we can define gibbs free energy as partial molar property

( ) | 0              T, v, n
∂ nG
≠ i =Gi
j
∂ni
Chemical potential ( mi ) – The chemical potential is a widely used thermodynamic property.
It is used as an index of chemical equilibrium in the same manner as the temperature and
pressure are used as indices of thermal and mechanical equilibrium. The chemical potential
mi of component i in a solution is the same as its partial molar free energy in the solution,
Gi .

The chemical potential of a component i in a solution can be defined as

 ∂Gt 
µ=i    Gi=    ...... (1)
 ∂n 
 i T,P,ni

mi −
( )=
∂ nG
0    T,P
  ,n
  ≠ i 
∂ (nu)
= 0   s, v,n
  ≠ i 
∂ (na )
= 0   T, V,n
  ≠ i 
∂ (nh)
0  P
  , s,n
  ≠ i 
j j j j
∂ni ∂ni ∂ni ∂ni

m= G=
( ) | 0              T, v,n 
∂ nG
≠ i 
i i j
∂ni
The total free energy Gt of a solution is a function of pressure, temperature and number of
moles of various components
Gt = f(P, T,n1 ,n2 ..........,ni

The total differential dGt is

 ∂Gt   ∂Gt   ∂Gt 

Thermodynamics

dGt = 

 ∂P
 dP +  

T,N

 ∂P
 dT +  

P,N
∑ 

 ∂ni


P,T,nj≠i

145.
 Using equation (1)
 ∂Gt   ∂Gt 
dGt  
=
 ∂P

 dP +  

T,N
 ∂P

 dT +  

P,N
∑ µ dn i i
(2)

We know that
dG  VdP − SdT
=
Considering the total properties of the system
t
dG
=  V t dP −  St dT
From which it follows
 ∂Gt   ∂Gt 
   =  −St ,    =  V t   ......(3)
 ∂T   ∂P 
 P,N  T,N
Equation (2) can be written as

Gt=   V t dP −St dT + ∑ µ dn

i i
......(4)

This is the fundamental relationship for changes in the free energy of a solution. At constant
temperature and pressure, the change in the free energy is due entirely to the changes in
the number of moles and is given by

dGtT,P = ∑ µ dn ...... (5)

i i

mi ≠ Gi ≠ vi ≠ hi

The partial molar property is defined only in case of constant Temperature & pressure.
mi = Gi

Short notes

m
= ∑
= xmM
 
i ∑ nm  
i t i i

∑
xidmi 0 
= = nidmi 0 |
= ∑
0 at T,P
  constant 

Summation rule

= mi
( ) | 0              T,P , n
∂ nm
≠ i 
j
∂ni

G
= m
=
( ) | 0              T,P ,n 
∂ nG
≠ i 
Thermodynamics

i i j
∂nc

146.
Relationship between partial molar property ( mi ) and molar solution property (m) for
Binary mixture.
m1 ,m
  2 given
m=?
m x 1m1 + x2 m2
=
(2) m given
m1 = ? m2 = ?

Since, from summation rule

m x 1m1 + x2 m2
=

dm = x 1dm1 + m1dx 1 + x2dm2 + m2dx2

From Gibbs duhem equation @ at constant and temperature & pressure.

∑ x dm
i i
=0

x 1dm1 + x2dm2 =
0

dm = x 1dm1 + m1dx 1 + m2dx2 + x2dm2

=
dm m1dx 1 + m2dx2

Since x 1 + x2 =
1
dx 1 = −dx2
dm
dm =
m1dx 1 − m2dx2 m1 − m2
=
dx 1
=
m x 1m1 + x2 m2

m − x 1m1
m2 =
x2

dm  m − x 1m1 
= m1 −  
dx 1  x2 

dm m1x2 − m + x 1m1 dm
=
− m1 =
m + x2
dx 1 x2 dx 1
x2 m2
Thermodynamics

Similarly, m=
1
m−
x1

147.
 dm m − x2 m2
=
− − m2
dx 1 x1

dm m − x2 m2 − m2 x 1
= −
dx 1 x1
dm
m=
2
m − x1
dx 1

( )   Infinite 
∞
mi =  mi ( Solution)

mi = m (
  i   pure species )
m =m (
  i pure species )

Q V = 500 x 1 +1000 x 2 + x 1 x 2 (50 x 1 +40 x 2 ) then find V1 & V2

Sol: ( ) ( )
= 500x 1 + 1000 1 − x 1 + x 1 1 − x 1 50x 1 + 40 1 − x 1 
V
  ( )
( )
= 500x 1 + 1000 − 1000x 1 + x 1 − x 12 50x 1 + 40 − 40x 1 
V

V = 500x 1 + 1000 − 1000x 1 + 50x 12 + 40x 1 − 40x 12 − 50x 13 − 40x 12 + 40x 13 ]

 −460x 1 + 1000 − 30x 12 − 10x 13
V=
dm
m
= m + x2  
dx 1

Vi =
 ( )
−460x 1 + 1000 − 30x 12 − 10x 13 + 1 − x 1  −460 − 60x 1 − 30x 12 

Vi =  20x 13 − 60x 1 + 540
∞
V1 =  V1
∞
Vi = 540

V1 =  V1

V1 = 500
For pure species
Thermodynamics

GR f  P vR P dP
= lnln =
RT    lnln 
P 
= φ  ∫ D RT
dP
= ∫ D
( z − 1)
P

148.
 For gaseous mixture
GR  ˆfi   ˆ 
= lnln  = ˆ   lnln  fi   
   lnln 
=φ i
RT  Pi   yiP 
ˆf
when ˆφi = i
yiP
ˆf
or ˆφi yiP = i

dG = vdP
dG = vig dP for Ideal gas
dG = vdP
R
dG=   ( v − v ) dPig

dGig  = viig dP
dGR  = vRdP
GR P vR

RT
= ∫ D RT
dP

Effect of temperature and pressure on chemical potential

Effect of temperature
Differentiating equation (1) with respect to T
T, we get
 ∂µi  ∂ 2Gt
   =   (6)
 ∂T P,N ∂T ∂ni

Differentiating equation (3) with respect to ni , we get

 ∂St  ∂ 2Gt
−   =
  (7)
 ∂ni P,T,n ∂ni∂T
j

Equation (6) and equation (7) implies that

 ∂µi   ∂St 
   =  −    −  Si   (8)
=
 ∂T P,N  ∂ni P,T,n
j

where Si is the partial molar entropy of the component i in the solution.

The variation of the chemical potential with temperature can be written in more useful form
Thermodynamics

as We know that
G= H − TS

149.
 G=i   H
  i  −  TSi
µi = H
  i −  TSi
We can write as
µ −H  i
 i
−Si = (9)
T
We know that
 ∂µ 
T  i   −µi

 ∂µi/T   ∂T 
   =  
 ∂T P,N T2

Substituting equation (8) and (9) in the above equation

 ∂µi/T  Hi
   = 2 (10)
 ∂T P,N T
Equation (10) predicts the effect of temperature on chemical potential.

Effect of pressure:
Equation (1) and (3) are differentiated to obtain the effect of pressure on chemical potential.
Differentiating the equation (1) w.r.t pressure,
 ∂µi  ∂ 2Gt
  =  (11)
 ∂P  T,N ∂P∂ni
Differentiating equation (3) with respect to ni ,

∂ 2Gt  ∂V t 

=  =  VI (12)
∂ni∂P  ∂ni 
P,T,n j≠i

Comparing equation (11) and (12)

 ∂µi 
  =  Vi (13)
 ∂P T,N
The rate of change of chemical potential with pressure is thus equal to the partial molar
volume of the constituent.
In case of an ideal gas,
 ∂µ  RT
 i   =  
 ∂P T P
Thermodynamics

Proof:
For a mixture of an ideal gas,

150.
 RT
( 1 + n2 + n3+............... )
V t =  n
P
where n1 ,n2 ,n3 .. are the moles of various constituents.
Differentiating this with respect to n1 , we get
 ∂V t  RT
   =   = Vi
 ∂n 
 1 P,T,nj≠i Pi

By equation (13) we know that

 ∂µi  RT
  =  V=
i
 ∂P T,N P

Fugacity in solution
The concept of fugacity is useful while dealing with mixtures. For pure fluids, the definition
of fugacity
dG =R
  T d ln f ( )
f
  =  1
P
The fugacity of a component i in a solution (gaseous, liquid or solid) is defined analogously
by
dµi =R
  T d ln fi( )
f
  =  1
pi
Here µi is the chemical potential, fi the fugacity and pi is the partial pressure of component
i in the solution. For an ideal gas mixture, the fugacity of a component is equal to tis partial
pressure. All gaseous mixtures behave ideally on approaching zero pressure. The partial
( )
pressure is defined as product of total pressure and mole fraction of i yi in the mixture.
pi  =  yi P

Fugacity in gaseous solutions

The fugacity of a component i in a gaseous solution is given by
dµi =R ( )
  T d ln fi , by equation (13)

 ∂µi 
Thermodynamics

  =  Vi
 ∂P T,N
where Vi is the partial molar volume of a component in the solution.

151.
 Rearranging the above equation
dµi =Vi  dP
Vi
( )
d ln fi  =
RT
  dP

( )
Subtracting d ln pi , where pi is the partial pressure of component i in the gas mixture, from
both sides
 f  1 
d
=  ln  i   
 p  RT  i
   VdP − RT d lnpi  (14)
 ( )
 i 

since, pi  =  yi P, where yi is the mole fraction

d=( ) ( )
ln pi    d lnP
  + d ln yi ( )
( )
At constant composition, d ln yi = 0 , so that the above equation reduces to

dP
d=( ) ( )
ln pi    d=
lnP
    
P
(15)

Substituting the equation (15) in equation (14),

 f  1  RT 
 ln  i   
d =   Vi −    dP
 
 pi  RT  P 

as P → 0 , fi  =
 pi , and the above equation can be readily integrated to give

 f  1 P RT 
 pi 
  RT 0 ∫
d  ln  i =   ln φ=i       Vi −    dP (16)
P 

where Ôi denotes the fugacity coefficient of a component in solution

f f
φi=    i =    i
pi yiP
For a mixture of ideal gas,
The equation of state is
RT
( 1 + n2 + n3+............... )
V t =  n
P
 ∂V t  RT

= Vi =  (17)
 ∂n  P
 i T,P.nj
Thermodynamics

Substituting equation (16) in equation (17)

fi    p=
= i
yiP

152.
which states that the fugacity of a component in a mixture of ideal gases is equal to the
partial pressure of that component in the mixture. However, this is not true for real gases.
Equation (16) provides the means for computing fugacities in the real gaseous solution. But
this requires the evaluation of Vi as a function of pressure, which in turn requires the
knowledge of how the solution volume varies with composition at each pressure.

Fugacity coefficient
The ratio of fugacity to pressure is referred to as fugacity coefficient and is denoted by f. It
is dimensionless and depends on the nature of the gas, the pressure, and the temperature.
We know that,
dG  =R ( )
  T d ln f

Integrating the above equation between the pressures P and P0

f
G −  G0  =
R
  Tl n  0 (1)
f
Since f0  =P
  0 and f = φP, we can write the above equation as

P
G=G0 + R   T ln φ (2)
  T ln  0  + R
P
For ideal gases ,
=  G0  +RT lnP
G   / P0 (3)
Combining equation (2) and (3)
The 
=free energy of a r eal gas   free energy of an ideal gas  +RTl n f
The quantity RTl n f , indicates the entire effect of intermolecular interaction

Effect of temperature and pressure on Fugacity

IN equation (1) , G0 and f0 refer to the molar free energy and fugacity respectively at a very
low pressure where the gas behaves ideally. This equation can be rearranged as
f G G0
R ln  =     −  
f0 T T
Differentiate the above equation with respect to temperature at constant pressure

 ∂ l n f   ∂ l n f0
R 
 
 
(
 ∂ l n G / T )   (
 ∂ l n G0 / T
) 
  −  =       −  
 
 ∂T P  ∂T    ∂T  ∂T
P   P  
P
Or
Thermodynamics

 ∂ l n f  H0 − H
  =  (4)
 ∂T P RT2

153.
 H is the molar enthalpy of the gas at the given pressure and H0 is the enthalpy at a low
  0 − H can be treated as the increase of enthalpy accompanying the expansion of
pressure. H
the gas from pressure P to zero pressure at constant temperature. Equation (4) indicates
the effect of temperature on the fugacity.
The effect of pressure on fugacity is evident from the defining equation for fugacity
dG    V=
= dP   R
  T  d ln f ( )
On rearranging,
 ∂ l n f  V
   =   (5)
 ∂P T RT

Lewis-Randall Rule
As the evaluation of fugacity in a mixture of gases through the general equation (16) is very
difficult, the model of mixture is devised known as the ideal solution model, the fugacity
of which can be easily evaluated. The fugacity in the actual solution is then determined by
taking into the account the deviation of the actual solution from this ideal behavior. As an
ideal gaseous solution, consider a gas mixture formed without any volume change on mixing
the components. A gas mixture that follows the Amagat’s law is an ideal gaseous solution.
For such solutions, the volume of the mixture is a linear function of the mole numbers at a
fixed temperature and pressure.
That is,
V t =  S niVi

where Vi is the molar volume of pure i at the same temperature and pressure.
For such ideal solution,
 ∂V t 

= Vi     =     Vi (18)
 ∂n 
 i T,P,nj

For pure component at a temperature T and the pressure P

f 1 P RT 
P RT  0 ∫
ln  i        Vi  −    dP (19)
=
P 
and for component i in a gas mixture at the same temperature and pressure,
f 1 P RT 
=
P RT 0  ∫
ln  i        Vi  −    dP (20)
P 

Subtracting equation (19) from equation (20)

Thermodynamics

fP 1 P
ln  i    
=
fp
i i
RT ∫ ( V  − V ) dP
0 i i

154.
we know that, pi  =  yiP , the above equation can be simplified as

f 1 P
ln  i    
=
yifi RT ∫ ( V  − V ) dP (21)
0 i i

Substituting equation (18) in equation (21)

fi
ln 
=    0=
  or fi   yifi  
yifi
This is known as Lewis fugacity. It states that the fugacity of a component in an
ideal solution is directly proportional to the mole fraction of the component in the
solution.
fi is the fugacity of the species i in an ideal gaseous solution, and fi is the fugacity of pure
i evaluated at the temperature and pressure of the mixture. Thus,
fi  =  yifi for the ideal gaseous solution
fi    y=
= i
P   pi for ideal (perfect) gases

For a gas mixture to behave as an ideal solution, it requires only that the molar volume in
the pure state and the partial molar volume in the solution be the same or Vi  =  Vi . For the
mixture to be an ideal gas it requires that V=i    V=i   R
  T / P , which means that the molar volumes
of all the components are the same whether in the mixture or in the pure state. For an ideal
solution, the volumes of components may differ from one another. In short, the concept of
an ideal gaseous solution is less restrictive than that of a mixture of ideal gases.
The Lewis- Randall rule is a simple equation and is therefore widely used for evaluating
fugacities of components in gas mixture. It allows the fugacity of a component in the
mixture to be calculated without any information about the solution except its composition.
Validity of the rule
1. At low pressure when the gas phase behaves ideally.
2. At any pressure if the component is present in excess.
3. If the physical properties of the component are nearly the same.
4. At moderate and high pressures, the Lewis-Randall rule will give incorrect results if the
molecular properties of the component are widely different and the component under
consideration is not present in excess.

Fugacities in liquid solution

For calculating fugacities in liquid solutions, the ideal solution fugacity can be easily
calculated knowing its composition and measure the departure from ideal behavior for
the real solution. A quantitative measure of the deviation from ideality is provided by the
Thermodynamics

function known as the activity coefficient.

155.
 Ideal solutions and Raoult’s Law
A solution in which the partial molar volume of the component is the same as their molar
volumes in the pure state is called an ideal solution. There is no volume change when the
components are mixed together to form an ideal solution. That is, for an ideal solution,
V =  Sxi Vi  =  SxiVi where, V is the molar volume of the solution, Vi and Vi are the molar
volume and partial molar volume respectively of the component i, and xi is the mole fraction
of component i in the solution. If the mixture of two liquids is to behave ideally, theoretical
consideration reveals that the two types of molecules must be similar. The environment of
any molecule and hence the force acting on it is then not appreciably different from the
existing in the pure state. Lewis-Randall rule is applicable which states that fugacity of each
constituent is directly proportional to the number of moles of the constituent in the solution.
The Lewis-Randall rule is applicable which states that fugacity of each constituent is directly
proportional to the number of moles of the constituents in the solution. The lewis -Randall
rule is applicable to ideal liquid solutions also.
fi  =   xifi

where fi is the fugacity of component i in the solution, fi is the fugacity of i in the pure
state, and xi is the mole fraction of component i in the solution.

Raoult’s Law
The criterion of phase equilibria allows to replace the liquid phase fugacities fi and fi with
fugacity in the gas phase with which the liquid is in equilibrium. Thus, fi L = fi V under
equilibrium.
where V and L refer to the vapour and liquid phase respectively.
If the vapour phase is assumed to be ideal gas, which is true if the pressure is not too high,
the vapour phase fugacity fi V is the same as partial pressure pi of component i in the
vapour. If the liquid phase is pure i, the fugacity of pure i in the vapour phase can be replaced
with the vapour pressure PiS . Under these conditions the Lewis-Randall rules,
pi =  xiPiS

The above expression is known as Raoult’s Law. This is a simplified form of the Lewis-
Randall rule , whereas the Lewis-Randall rule is obeyed by all ideal solutions, Raoult’s law
is applicable to ideal solutions if the vapour phase with which it is in equilibrium is an
ideal gas.
Raoult’s Law provides a very simple expression for calculating the fugacity of a component
in the liquid mixture which is the same as the partial pressure of the component in the
Thermodynamics

vapour. In this rule the partial pressure is directly proportional to the mole fraction in
the liquid solution. Ideal solutions which conform to Raoult’s law over the entire range of
concentration are rare.

156.
Henry’s Law and Dilute solutions
A solution, any of whose components does not obey Raoult’s law, is designated as a non-
ideal solution. Even non-ideal solutions exhibit a common form of ideal behaviour over a
limited concentration range, where the fugacity fi (or, the partial pressure pi ) is directly
proportional to the concentration in the liquid. This behaviour is exhibited by the constituents
as its mole fraction approaches zero, and is generalized by Henry’s law.
fi  =  xiKi
pi  =  xiKi

Often, the solute portion of the non-ideal liquid solutions can be assumed to follow Henry’s
Law.
pi is the partial pressure of the solute over the solution, xi is its mole fraction in the
solution and Ki is the proportionality constant known as Henry’s law constant. Ki may be
greater or less than PiS , the vapour pressure of the solute at the temperature and total
pressure.
Note : When Ki and PiS are equal, Henry’s law and Raoult’s law are identical.
Henry’s law may be thought of as a general rule of which Raoult’s law is a special case.
Henry’s law is obeyed in all solutions by the solute at extremely low concentrations.

Ideal behaviour of the real solutions

The ideal behaviour exhibited by non-ideal solutions
fi
  =  fi Lewis − Randall rule
xi

fi
  =K
  i Henry ' s law 
xi

Activity in the solutions

The activity of a component in a solution can be defined as the ratio of fugacity of a
component in the solution in a given condition to the fugacity of that component in the
standard state.
It is denoted as ai
fi
ai  =  
fi0
Since the fugacities are related to the chemical potential as
Thermodynamics

=µi   R
  T ln fi  +C

µi0 RT ln fi0 + C
=

157.
 It follows as

= f
∆µi   R
 =Tl n  0i   R
  T ln ai  
fi
The concept of activity plays an important role in the solution of thermodynamics because
activity can be related to compositions directly.
For example, let the standard state for a substance be the pure component at the temperature
and pressure of the solution. Then the activity of that component becomes equal to its mole
fractions in the case of ideal solutions and is a strong function of mole fraction in the case
of real solutions.
fi f
ai  =  = i 
fi0 fi

For ideal solutions as fi  =  xi fi ,

The activity ai  =  xi  . For real solutions, the activity can be shown to be equal to the product
of activity coefficient and mole fraction.

Activity coefficient
The calculation of fugacity of a component in a real solution should take into account the
degree of departure from ideal behaviour. Activity coefficients measure the extent to which
the real solutions depart from ideality. Activity coefficient of the component i in solution is
denoted by gi and is defined by the following relationship.
fi  =  γixifi0

where fi0 is the fugacity in the standard state. For ideal solutions gi  =  1 ,

fi  =  xifi0
which is the same as the Lewis-Randall rule.
Two types of ideal behavior are observed, the first conforms to Lewis-Randall rule (or
Raoult’s law) in which case fi0  =  fi , the fugacity of the pure species at the system pressure
and the second type conforms to an ideal solution behavior (the Henry’s Law), in which case
fi0  =K
  i , the Henry’s Law constant. Depending upon the standard states on which they are
based, the activity coefficients can take different numerical values. For the standard state
in the sense of Lewis- Randall rule or Raoult’s law.
fi  = γixifi0
Thermodynamics

where fi0 is the fugacity in the standard state. For ideal solutions gi  = 1 ,

fi  = xifi0

158.
Two types of ideal behavior are observed; the first conforms to Lewis-Randall rule in which
case fi0  = fi  , the fugacity of the pure species at the system pressure and the second type
conforms to an ideal dilute solution behavior (the Henry’s law), in which case fi0  = Ki  , the
Henry’s law constant. Depending upon the standard states on which they are based, the
activity coefficients can take different numerical values. For the standard state in the sense
of Lewis-Randall rule or Raoult’s law.
fi  = γixifi0 (1)
a
=γi  fi  /x
= f0     i
i i
xi
ai  = γixi   

Where ai is the activity of i in the solution.

Equation (1) is Lewis Fugacity rule is modified by the factor gi to correct for the deviation
from ideality. This equation is reduced to Raoult’s law as x approaches unity and to Henry’s
law as x approaches unity (Raoult’s law region) and Ki / fi as mole fraction approaches zero
(Henry’s ;aw region). In terms of partial pressures, this is may be written as
pi  =  γixipis

In the hypothetical state, where the pure component fugacity = Henry’s law constant, is
chosen as the standard state
fi  =  γ'ixiKi (2)

pi  =  γ'ixiKi (3)

Then the activity coefficient approaches unity as x approaches zero. In equation (2) and (3),
γ'i is the activity coefficient referred to infinite dilution

Effect of pressure on Activity Coefficients

The effect of pressure on fugacity
 ∂ l n fi  V
   =   i
 ∂P T RT

Here fi is the fugacity of pure i and Vi is its molar volume. In the similar way, fi , the fugacity
of i in solution varies with pressure according to
 ∂ l n fi  V
Thermodynamics

   =   i (4)
 ∂P T RT

159.
 Combining equation (4) and equation (5 previous equation)
 ∂  ln fi / fi  Vi −  Vi
   =     (5)
 ∂P T RT

We know that,
 fi  /fi0  =  γixi  
Equation (5) can be rearranged as
 ∂  ln γixi    Vi −  Vi
   =  
 ∂P T RT

( )
As the mole fraction xi  is independent of pressure ∂ l n xi  /∂P   =
 0 , and hence

 ∂  ln γi  Vi −  Vi
   =        
 ∂P  RT

The molar volume Vi and Vi correspond to the particular phase under consideration. For
liquid solutions, The effect of pressure on activity coefficient is negligible at pressure below
atmospheric. For gaseous mixtures, activity coefficients are nearly unity at reduced pressure
below 0.8.

Effect of Temperature on Activity Coefficients

The effect of temperature on fugacity of a pure substance
 ∂ l n fi  Hi0 −H i
   =  
 ∂  T P RT
2

For the substance in the solution

 ∂ l n fi  Hi0 −H i
   =  
 ∂  T P RT
2

Combining the above equation, and we know that fi / fi = γixi , where xi is independent of
temperature
 ∂ l n γi  Hi  −H 
   =   2 i  
 ∂T P RT
(
The above equation shows the effect of temperature on activity coefficient. The term Hi  −H
 i )
is the partial heat of mixing of component i from its pure state to the solution of given
Thermodynamics

composition both in the same state of aggregation and pressure. For gaseous mixtures, this
term is negligible at low pressure.

160.
Gibbs-Duhem Equations
In a mixture, the partial pressure molar properties of the components are related to one
another by one of the most useful equations in thermodynamics, the Gibbs- Duhem
equations.
We know that at constant temperature and pressure, the property Mt of the solution is the
sum of the partial molar properties of the constituents, each weighted according to the
number of moles of the respective constituents.

∑ nM
Mt   =   i i

The total derivative dMt gives the change in the property of the solution at constant T
and P
dMt  
= ∑ n dM  +  ∑ M  dn (1)
i i i i

where M is the molar value of the property of the solution Mt .

Mt =f(T,P, n1 ,n2 , .......) , at constant T and P

dMt  = ∑ M  dn   (2)

i i

Comparing equation (1) and (2)

∑ n dMi i
=  0

This result is the general form of the Gibbs -Duhem equation.

Let us take the property Gibbs free energy of the solution,
The above equation becomes

∑ n dµi i
= 0

Dividing throughout by n, the total number of moles in the solution, we get

Sxidmi  =  0 (3)

Here xi is the mole fraction of component i in the solution and mi is the chemical potential
of the component.

Other forms of Gibbs-Duhem equation

A binary solution composed of component 1 and 2 whose mole fraction in the solution are
x 1 and x2 respectively.
Equation (3) can be written as
Thermodynamics

x 1  dm1  +  x2dm2  =
 0 (4)

where m1 and m2 are the chemical potentials of components 1 and 2 respectively.

161.
 Equation (4) can be written as
x 1  dm1  =  −  x2dm2  

Dividing by dx 1 and noting that dx 1  =  −dx2 in binary mixture.

Therefore,
∂µ ∂µ
x 1   1  =  x2   2
∂x 1 ∂x2
The relationship between the chemical potential and fugacity,
∂f ∂f
x 1   1  =  x2   2 (5)
∂x 1 ∂x2
fi
We know that activity ai  = ,
fi0

(
∂  ln a 1 f10
x1  
) (
∂ln a2 f20
 =  x2  
)
∂x 1 ∂x2

Since fi0 , the fugacity in the standard state, is independent of the composition of the
solution

( )  = 0
∂  ln  f10
∂x 1
Thus the Gibbs -Duhem equation in terms of activity is

x1  
( )
∂ l n a 1 
 =  x2  
( )
∂ln a2 
(6)
∂x 1 ∂x2

We know that, ai  =  γixi . Substituting in equation (6), the equation formed is

( )
∂ l n  γ 1x 1  
x1  
( )
∂ln  γ 2 x2  
 =  x2  
∂x 1 ∂x2

x1  
( )
∂ l n  γ 1  
  +x 1  
( )
∂  ln  x 1  
 =  x2  
( )
∂ln  γ 2   ( )
∂ln  x2  
 +x2     
∂x 1 ∂x 1 ∂x2 ∂x2
The second terms on both sides of the above equation are equal to unity.
Therefore,
( )
∂  ln  γ 1   ( )
∂ln  γ 2  
Thermodynamics

x1      =  x2       (7)

∂x 1 ∂x2

As the activity coefficient directly measures the departure from the ideal solution behaviour.

162.
Equation (7) is the best form of the Gibbs-Duhem equation.
Gibbs- Duhem equation describes the partial molar properties of the mixture, that they
cannot change independently. In a binary mixture, if the partial molar property of one of the
components increases, the partial molar properties of the other should decrease.

Property changes of mixing

Molar volume of an ideal solution is simply the average of the molar volumes of the pure
components, each weighted according to its mole fraction.
V =  S xiMi

where M is the molar property of the solution, Mi and xi are the molar property of pure i
and its mole fraction respectively.
For non-ideal solutions, this equation cannot be used for the estimation of thermodynamics
properties unless we apply a correction term DM, known as the property change of mixing. In
general, when thermodynamics properties of a solution, whether ideal or real, are evaluated
from the pure component properties the equation should be
=
M  S xiMi  +DM
Where DM is the difference in the property of the solution M and sum of the properties of
the pure component that make it up, at the same temperature and pressure as the solution.
Thus,
DM 
= M  −  S xiMi
Replacing M by V
The equation becomes,
=
V  S xiVi  +DV
Where DV is the volume change on mixing. DV=0, for ideal solutions
The general definition of DM can be written as
  − S xiMi0 (1)
DM= M

Where Mi0 is the molar property of pure i in a specified standard state. If the component
exists in the pure form in the same state of aggregation as the solution and at the temperature
and pressure as the solution, then Mi0  =M
  i . For example, if all the components exists in the
pure state as stable liquids at the temperature and pressure of the solution,  Vi0  =  Vi and
DV=  V  −S xiVi0  . Here, DV is the volume change of mixing when one mole of the solution is
formed at constant temperature and pressure from the pure liquid constituents. Property
change of mixing is a function of temperature and pressure like any other thermodynamics’
Thermodynamics

property of solution and its value depends on the standard state specified for
the components.

163.
 We know that

M = ∑ xM i i

Therefore, transforming equation (1)

(
DM   S xi Mi − Mi0
= ) (2)
The quantity Mi − Mi0 can be treated as the change in the property of component i when one
mole of pure i in its standard state is brought to the solution of given composition at the
same temperature and pressure.
In view of equation (2), the volume change of mixing and free energy of mixing can be written
as
( ) (5)
DV   S xi Vi − Vi0
=

DG   S x ( G − G ) (4)

= i i
0
i

Activity and property change of mixing

Free energy change of mixing, DG
The change in the free energy of a substance when it is brought from its standard state to
the solution
f
Gi0   R
Gi − = =i   R
  T l n    Tl n ai (6)
fi
Substituting in equation (6)
∆G

RT 
 =   ∑ x l n a i i

Volume change of mixing, DV

The partial molar free energy ( the chemical potential) varies with pressure as
 ∂Gi 
   =  Vi (7)
 ∂P T,x

For pure substance,

 ∂G0 
 i   =  Vi0 (8)
 ∂P 
 T

Vi and Vi0 are the partial molar volume and molar volume of component i in the standard
Thermodynamics

state respectively. Replacing Vi and Vi0 in equation (5) in terms of Gi and Gi0 using equation
(7) and equation (8)

164.
  ∂ Gi  −  Gi0 ( ) 
∆V = ∑
  xi  
 ∂P 
(9)
  T,x
Using equation (6) in the above equation,

 ∂  ln ai 
∆V =RT  ∑ x   i
∂P  T,x
(10)

Equation (10) can be written as

P∆V  ∂ l n ai  

RT
 =   ∑ x   ∂  lnP  
i
T,x
(11)

Enthalpy change of mixing, DH

The Gibbs- Helmholtz equation can be related to the free energy of the substance in the
pure state or in the solution to the corresponding enthalpies of the substance as

 (
 ∂ G0 / T
i )   =  − H 0
i
(12)
 ∂T  T 2
 P


(
∂ G / T
i )  H
 =  −   2i (13)
 ∂T  T
 P,x
The enthalpy of mixing

=
∆H    ∑ x (H  −H  ) (14)
i i
0
i

Substituting equation (12) and (130 in equation (14)

 ∂ 
∆H =−T2R  ∑ x  ∂  T l n a 
i i
P,x

∆H  ∂ln ai 

RT
 =  ∑ x  i  
∂  T P,x
(15)

Entropy change of mixing, DS

The partial molar entropy Si and molar entropy of component i in the standard state Si0 are
related to the free energy of i in the solution and free energy of pure i
 ∂G 
    =  −Si
 ∂T P
Thermodynamics

 ∂G 
    =  −Si
 ∂T P,x

165.
 Entropy of mixing is defined as

=∆S    ∑ x ( S − S ) (16)
i i
0
i

Transforming equation (16)

(
 ∂ Gi − Gi0 ) 
∆S = − ∑ xi 
 ∂T 
(17)
 P,x
Using equation (6) in equation (17)

∆S   ∂ ( Tl n ai ) 

R
 −
= ∑
xi 
 ∂T
  −  
P,x
∑ x  ln a
i i

Excess properties
The difference between the property of a real solution and that of an ideal solution is
important in chemical thermodynamics, especially in the treatment of phase equilibria. The
excess property , ME , is defined as the difference an actual property and the property that
would be calculated for the same temperature, pressure and composition by the equations
for an ideal solution
ME=  M   id (1)
   −M

M is the molar property of the solution and Mid is the property of an ideal solution under the
same conditions.
The excess property change of mixing is defined in a similar manner
E
DM
=  D   Mid (2)
  M −D

DME is the excess property change of mixing, DM and DMid are the property change of
mixing for a real solution and an ideal solution respectively, both under the same conditions.
DM 
= M  −  S xiMi0 (3)
DMid 
= M   id  −S xiMi0    (4)
Equation (2) can be written as
DME=  M   id (5)
   −M
Comparing equation (1) and (5)
DME  =M
  E (6)
Equation (6) signifies that the excess property change of mixing and the excess property are
Thermodynamics

the same.
Let us consider the excess volume VE of a solution
E E
V=  D
  V= D   Vid
  V −D

166.
For ideal solution,
DVid  =  0
In this case, the excess volume of a solution and the volume change of mixing DV are the
same.
Excess functions indicate the deviation from ideal solutions behaviour and are easily
related to activity coefficients. Excess functions may be positive or negative; when the
excess Gibbs free energy of a solution is positive the solution is said to exhibit positive
deviation from ideality, whereas if it is less than zero, the deviation from ideality
is negative.
The definition of partial molar excess function is analogous to that of partial molar
thermodynamic properties
 ∂  nME 
MEi  =   
 ∂n 
 i T,P,ni
MEi is the partial molar excess property of component i.
Therefore,

∑ xM
ME  =   E
i i
(7)

Which indicates that the molar excess property ME of a solution is the average of the partial
molar excess property of each component weighted according to its mole fraction.

Excess Gibbs Free Energy

For phase equilibrium studies the most useful excess property is the partial molar excess
Gibbs free energy which can be directly related to the activity coefficient.
Excess Gibbs free energy is defined as
GE=   G −  Gid
Using equation (7)

GE     ∑ x  µ
E
= i i

where µEi is the excess chemical potential or excess partial molar free energy of
component i.
We know that
µEi  =  µi  −µ
  id id
i  =  ∆µi  −  ∆µi

∆µi the change in chemical potential for component i when it is transferred from its standard
Thermodynamics

state to the solution at the same temperature and pressure is related to its fugacity in the
solution

167.
 f
  T ln  0i (8)
∆µi  = R
fi

fi is the fugacity of component i in solution and fi0 is the fugacity in the standard state.
Similarly,if the component becomes part of an ideal solution at the same conditions

f id
∆µid   T ln  i 0 (9)
i  = R
fi

Since fugacity in an ideal solution is fi id  =  xi  fi0

Substituting in equation (9),
∆µid
i  = R
  Tl n xi
E
µ
=i
 R
  T ln γi (10)

Equation (10) indicates that activity coefficient is a function of composition.

The molar excess Gibbs free energy of a solution is

= GE   R
  T  ∑ x ln γi i

Since µEi  = GEi , the partial molar free energy of a component i in the solution, the above
equation can be expressed in the form

µE
ln γi =   i =   
(
 ∂ nGE / RT
) 
RT   ∂ni 
  T,P,n
i

CHEMICAL REACTION EQUILIBRIUM

Any reversible reaction can attain equilibrium constant at given temp and pressure is its
equilibrium conversion.
y At equilibrium conversion, Gibbs free energy reaches the minimum value.
A ↔ B
At constant temp and pressure-

d (ng) = ∑ ui dxi

∑ ui dxi = 0

(dG) T,P = 0 (at equilibrium)

ε = extent of reaction
Thermodynamics

Extent of reaction
aA + bB ↔ cC + dD

168.
Let us consider a reversible reaction-
−dnA −dnB dnC dnD
= = =
a b c d
For per mole of a

−dnA
=
−a dnB ( ) (mole will disappear)
1 b
dni −dnA −dnB dnC dnD
= = = =
vi a b c d
Vi > 0 (product)
Vi < 0 (reactant)
dni
Extent of reactant- = dE
vi
change inn
  o. of moles
⇒ = dE
stichiometric cofficient
dE does not depend upon species, it is the same for every species.
A + 2B ↔ 3C
A = 10 moles
B = 40 moles
If 50% of A is converted, then moles of A reacted 5 moles.

After reaction dn

nAo 10 5 5

nBo 40 30 10

nCo 0 15 15

5 10 15
dE = = =
1 2 3
dE = 5 (for every species is same)
dni
= dE
vi
ni E
∫ nio
dni = ∫ VdE
0 i
Thermodynamics

ni – nio = viE
ni − nio change inn
  o. of moles
E= =
vi stiochemistry cofficient

169.
 y Conversion will or may be different for every species, but the extent of reaction will be the
same for every species.
y Conversion is only the same for reactants when they are being fed in stoichiometric
proportion.
ni = nio + Evi
na = nAo – E vA

RELATIONSHIP BETWEEN EXTENT AND CONVERSION OF A REACTION

ni − nio
|ε| =
vi
−ni + n
  io
Conversion of any reactant species i = = Xi
nio
nio −ni
Xi =
nio
xi.  nio
|ε| =
vi
ε nio
=
xi vi

vi ε
Xi =
nio
Extent of reaction will be the same as of conversion when moles are being fed in stoichiometry
proportion.

Example:
A + 2B ↔ 3C
A = 10
B = 40
1
0.5 = ε ⇒ε=5
10
2
XA = x5
40
10
XB = = 0.25
40

EXAMPLE 2 :
Thermodynamics

A + 2B ↔ 3C
A=1

170.
 B=2
1
XA = xε=ε
1
2
XB = xε=ε
2
dni
dε =
vi
ni = nio + vi ε
n n
⇒ ∑ i= 1
ni = ∑ i= 1
nio + ∑ ( vi) ε
Total no. of moles = total no. of initial + vε
n = no + vε
ni
Mole fraction in pdt =
n
ni nio + viε
yi = =
n no + vε

EQUILIBRIUM CONSTANT (Ka)

Ka stands for activity.
We can find equilibrium constant by vant’s hoff equation.
Δg’ = -RT ln Ka (equilibrium const. based on activity)

Δg’ = ∑ vigi' (molar gibbs free energy of species is at std. state)

fi
ai =
fio
aA + bB → cC + dD
Δg’ = -a gA’ – b gB’ + c gC’ + d gD’
n
Ka = ∏ i= 1
aivi ai = activity, vi = stoichiometry coeff.
vi
 fi 
n
Ka = ∏
i= 1 fio



Ka = aA . aB . aC-c. aD-d
-a -b

acC .aDd
Ka =
aaA . aBb
Thermodynamics

n
Ka = ∏ i= 1
aivi

171.
 vi
n  fi 
Ka = ∏ 
i= 1 fio



vi
n  yiP
   Φi  fi
Ka = ∏ i= 1

 fio 
 as Φi =
yiP
 
For gases, fi = 1 bar
Std. the fugacity of species is 1 bar. Hence, yi P Φi → P must be in the bar.
n
∏ ( yiP  Φi)
vi
Ka =
i= 1

Since P is const, P x P x P = P3

P∑
n n
∏ ( Φi) ∏ ( yi)
vi vi vi
Ka = .
i= 1 i= 1

Ka = kΦ ky P∑
vi

n
∏ ( Φi)
vi
Where, kΦ =
i= 1
n
∏ ( yi)
vi
ka =
i= 1

For ideal gas mixture, Φi = 1, kΦ = 1

Ka = ky P∑
vi

P∑
n
∏ ( yi)
vi vi
Ka =
i= 1
vi
 ni 
P∑
n vi
Ka = ∏  
i= 1 n
 

P∑
vi
n
∏i=1 (ni)
vi
Ka = n = total no. of moles
n

P∑
vi
Ka = Kn
n
Ka is the only function of temp. Ka = f(T) only
There is no effect of P on equilibrium const.
If P changes, Kn will change accordingly. Hence, Ka will be same (at particular temp)

Effect of pressure on equilibrium conversion (or equilibrium const)

Thermodynamics

For ideal gas –

Ka = Ky P∑
vi

172.
 n
∏ ( yi)
vi
Ky =
i= 1

nio +  ε  vi
Yi =
no +  εv
A + B → 2C
yc2
Ky =
ya. yb
If Ky ↑, means more will be C, then reaction shifts in forward direction, then conversion will
increase.
If Ky↓, reaction shifts in backward direction and equilibrium conversion decreases.

At a given temp, Ka will be constant.

∑ vi > 0 → when moles are increasing

∑ vi < 0 → when moles are decreasing

∑ vi = 0 → when moles are neither increasing nor decreasing

Ka = Ky P∑
vi

> 0, P∑
vi
If ∑ vi ↑, Ky ↓ then reaction shifts in backward direction. Hence, equilibrium
conversion decreases.

< 0, P∑
vi
If ∑ vi ↓, Ky ↑ then reaction shifts in forward direction. Hence, equilibrium
conversion increases.
n
P= ∑ i= 1
Pi

P will be nowhere, moles will increase.

According to le-chattle’s principle, reaction shifts where the change is going to oppose.
As for vi = 0, as reaction proceeds P↑, then the reaction will shift where moles are less.
Hence, it is in backward direction.
For increasing no. of moles-

∑ vi > 0
On decreasing the pressure P∑ ↓, Ky ↑, the Ky should be increased. Reaction will shift in
vi
Thermodynamics

forward direction and reaction equilibrium conversion will be increased.

For ∑ vi < 0

173.
 On increasing the pressure ∑ Pi ↑ ∑ vi ↓, Ky ↑, the Ky should be increased. Reaction will
shift in forward direction and reaction equilibrium conversion will be increase (Xae ↑)
Effect of constant no. of moles-

∑ vi = 0
Equilibrium conversion is independent of pressure.

EFFECT OF INERT
1) Adding inert at const. pressure
P ∑ vi
Ka = Kn ( )
n
By addition of inert (n↑)
By adding inert at const. pressure, n goes on increasing then-

Case 1: For increasing no. of moles ∑ vi > 0

P
On adding the inert ( )∑ ↓ hence, Kn↑ hence, the reaction will shift in the forward direction.
vi

n
Hence, equilibrium conversion will increase.

Case 2: For decreasing no. of moles ∑ vi < 0

P
On removing the inert n↓, ( )∑ ↓ hence, Kn↑ hence, the reaction will shift to the forward
vi

n
direction. Hence, equilibrium conversion will increase.
Conclusion: Effect adding the inert is the same as decreasing the pressure effect.

Effect of ratio of food

A + 2B → C
n
Ratio of feed = AO
nBO

Ka = KΦ Ky P∑
vi

 1 ∑
vi

Ka = Ky   = Ky = KN
n
Ka = KN
Thermodynamics

A+B→C+D
n .n
Ka = C D
nA .nB

174.
 If A is the limiting reactant, then the conversion of A gets increased by increasing the moles
of B in the feed.
If nBO↑, nB↑
As A gets converted or conversion of A proceeds nA↓, nB should be ↑. So then Ka remains
constant. Hence, nBO should be high.
It means conversion of limiting reactant ↑, if all other reactants except limiting should be
in excess.
On the other hand, addition of PdT to the reaction mixture will decrease the degree of
conversion.
nAO
should be low.
nBO

EFFECT OF TEMPERATURE
Exothermic: Temp should be low
Endothermic: Temp should be high
dlnlnK
  a  ∆HR
We know, =
dT RT2
y For exo- ΔHR = -ve
On T↑, XA↓ Ka↓
y For endo- ΔHR = +ve
On T↑, XA↑ Ka↑
∆HR
Ln Ka = [−  ]T2
T1
RT2
∆HR 1 1
Ln Ka = [ - ]
R T1 T2

Q For a gas phase cracking reacting-

A → B + C at 300’C
Gibbs free for the reaction – ΔG’ = -2750 J/mol.
The pressure is 1 bar, gas can be assumed to be ideal.
R = 8.314 J/ mol K
Find the fractional molar conversion of A at equilibrium.

Sol: Δg’ = -RT ln K eq

Thermodynamics

KEq = KΦ Ky P∑
vi

= 1. Ky. 1∑
1

175.
 Ka = Ky
ya. yb
1.781 =
ya
Let us assume 1 mole of A
nA = 1, nB = 1, nC = 1
nio + viε
yi = n=1+ε
no + vε
1−E
yA =
1+E
+E
yB =
1+E
E
yC =
1+E
E2
(1 + E)2 E2
1.781 = =
1−E ( )(
1 + E .  1 − E )
1+E
E2
1.781 =
12 −E
 2
1.781 ( 12 −E
  2 ) = E2
E = 0.8 (stoichiometric ratio hence same)

XA =
( vi) E =
1 X  0.8
= 0.8
nio 1

Q The reaction of water and ethanol tertiary butyl ether.

TBA + Et OH → ETBE + H2O
A+B→C+D
Equilibrium const. for this reaction is KC = 1
Initially 74 gm of TBA is mixed with 100 gm of aqueous solution containing
46% by ethanol and 54% by water, the mw of 74 g/mol TBA, 46g/mol EtOH
and 102 g/mol for ETBE, 18 g/mol water. Find out the mass of ETBE at equi-
librium.

Sol: n
Thermodynamics

KC = ∏ i= 1
CiVi

CC.CD
KC =
CA CB

176.
 CC.CD
1=
CA CB
Liquid is independent of pressure.
Ka = Kb
wA 74
Also, = = 1 mole
mA 74
Assume 1 litre of solution-
ETBE (C) =

feed nio no

TBA 1 mole 1-x

ETOH 1 mole 1-x

Water 3 mole 3+x

ETBE 0 x

1=
( 3 + x )( x )
( 1 − x )( 1 − x )
(1 – x) (1 – x) = 3x + x2
1 – x – x + x2 = 3x + x2
1 – 2x + x2 = 3x + x2
X = 1/5
X = 20%
m = 20.4 kg

Q The std. Gibbs free energy change and enthalpy change at 25’C. For Gibbs
reaction-
CH3COOH (l) + C2H5OH (l) → CH3COOC2H3 (l) + H2O (l)
Δg’at 298 = -4650 J/ mol
ΔHat 298 = -3640 J /mol
If the solution is ideal and enthalpy change is assumed to be const. Find the
eq. constant at 95’C

Sol: Δg’ = -RT ln Ka

Thermodynamics

Ka = 6.5228
dlnlnK
  a  ∆HR
=
dT RT2

177.
 Ka2 ∆HR 1 1
Ln ( )= [ - ]
Ka1 R T1 T2
Ka @ 95’C = 4.932

Q Compute the equilibrium mole fraction of each of the species in gas phase
reaction-
CO2 + H2 → CO + H2O (at 1000K)
1) At pressure of 1 atm
2) At 500 atm
The reaction equilibrium constant is 0.693 at 1000 K, standard state is pure
gas at 1000K and 1atm pressure. Initially there is an equal amount of CO2 and
H2O. figacity coefficient at 5’atm. For species are-

Sol: CO2 0.99

H2 1.15

CO 1.08

H2O 0.86

0.693 = kΦ ky P∑
vi

y 3. y 4
0.693 = x1
y2 y 1

1 1 1 -x 1− x
2

2 1 1-x 1− x
2

3 0 x x
2

4 0 x/2 x
Thermodynamics

178.
 x2
0.693 = 4
(1 − x)2
4
0.693 (1 – x)2 = x2
x 2
0.693 = ( )
1− x
x
0.832 =
1− x
0.8324 – 0.8324x = x
X = 0.454
Equilibrium composition-
Y1 = 0.273
Y2 = 0.273
Y3 = 0.227
Y4 = 0.227
At 500 pressure-
Φ3. Φ4
0.693 = ky
Φ2. Φ 1
y 3. y 4
x 500∑
vi
= 0.8158
y2 y 1
y 3. y 4
0.8494 =
y2 y 1
X = 0.59
For h1∞ , put x1 = 0 (in h1)
h1∞ = 420
h2∞ = 640

Q Consider a solution of two species S1 and S2 at 25’C, such that x1 = 0.4

Sol: If V1 = 40 x 10-6 m3/mole, find the V2 = m3/mole, the solution specific

gravity 0.9, mw is 32 and 18 respectively.
Mw = 23.6
Thermodynamics

0.0011 kg/ m3
23.6 kg / k mole
V2 = 1.7 x 10-5 m3/mol

179.
 PROPERTY CHANGE OF MIXING
Molar property-

Δmmixing = m - ∑ ximi
m= ∑ ximi
Property change of mixing is defined as –

Δmmixing (T, P) = m (T, P) - ∑ ximi (T, P)

Δmmixing = ∑ xi mi - ∑ ximi
Δmmixing = ∑ xi (mi - mi)

m = Δmmix + ∑ ximi
CHEMICAL POTENTIAL AND CRITERIA FOR PHASE EQUILIBRIUM-
dG = VdP – SdT
d (ng) = (nv) dP - (ns) dT (for open and closed system, where moles are not going to change)

So,
( )|
∂ ng
= (nv)
∂P T,x

And
( )|
∂ ng
= -(ns)
∂P P,x
x → Composition (const. comp)
ng = Gf (T, P1, n1, n2 + ………) when molecules are going to change

dG = d (ng) = -(ns) dT + (nv)dP + ∑ uidni ……………. (a)

If there is a closed system, but α and β are open to each other as mass from (a) is going to
be in P phase.
Each phase in the system may be treated as an open system because material may be
transferred from one phase to another phase.
Hence, equation (a) can be applied individually for α- phase as well as β- phase.
For α- phase:

∑ ui dni
α α
dG = d (ng)α = (nv)α dP - (ns)α dT +

For β- phase:
Thermodynamics

∑ ui dni
β β
dG = d (ng)β = (nv)β dP - (ns)β dT +

180.
In general, we should denote the temp and pressure of each phase also with the subscript
(α and β) . However, for the present purpose we are assuming, thermal and mechanical
equilibrium exist.
As α phase transfer to β phase, then gibbs free energy will be changed, total gibbs free
energy of the system changes with mass transfer between two phases. The change in total
gibbs energy of two-phase system is sum on change in each system

( ) ( ) ( )
α β
d ng
= d ng + d ng

 


(
= nv α + nv β  dP −  nsα + nsβ dT + ) α α β β
∑ Mi dni + ∑ Mi dni 
( ) ( )
d ng = nv dP − ns dT + ( ) ∑ Mi dni + ∑ Mi dni
α α β β
……..(1)

For whole system

( ) (nv ) dP − (ns) dT ……..(2)
d ng
=
By (1) & (2)

(nv ) dP − (ns) dT + ∑ Miαdniα + ∑ Miβdniβ = (nv ) dP − (ns) dT

∑ Mi dni + ∑ Mi dni
α α β β
0
=

dniα → Change inn
  o ofm
  oles from α  phase
dniβ → Change inn
  o ofm
  oles from β phase

η = ηα + ηβ As no chemical reaction moles will remain constant

0 = dη = dηα + dηβ which means
dηα =−dηβ

∑ (Mi )
α
− Miβ dniα =
0

dniα ≠ 0

∑ (Mi )
α
− Miβ =
0

For system to be in chemical equilibrium, the coefficient of dniα must be equal to Zero.
As in case of equilibrium, change takes place but in same manner
Miα = Miβ
For a system under thermodynamic equilibrium along with equality of temperature and
pressure, the chemical potential of each species should be identical across all phases.
In other words, multiple phases at the same temperature and pressure are in equilibrium,
Thermodynamics

When the chemical potential of each species will be the same in all phases.
α β
Mi= Mi
= Miγ …………Miπ

181.
 Fugacity & fugacity coefficient (pure species)
The term fugacity measures the pressure for the real gases. It is the measure of the escaping
tendency of real gases. The change in gibbs energy can be written as
dG=vdP-SdT
at constant temperature
dG = vdP

For ideal gas for Real gas
RT
dGig = dP dG = RTdlnln f  ……(2)
P

dGig = RTdlnlnP
    ……..(1)
By subtract equation (1) & (2)
ig
dG − dG
= RTdlnln f  −RTdlnlnP
  

( )
d G − Gig =
f
RTdlnln    
P 
Since the residual property is defined as.
mR= m − mg mR It is measure of how much far out real gas from ideal
f
dGig = RTdlnln    
P 
f
GR = RTlnln    
P 
GR f 
= lnln =    lnln φ 
RT P 
f → fugacity of real gas
P → pressure of Ideal gas
The ratio of fugacity to the pressure is called a fugacity coefficient (dimensionless)
P → 0, then ≅ 1.0

f →P
lnlnφ  =0
GR
Thermodynamics

when pressure is very low

RT
dG = vdP {dGig v=
= ig
dP Ideal 
 gas  dG vdP        Real 
 gas     

182.
 Subrating 

dG − dGig =v − vig dP ( )
dGR = vRdP
P
GR = ∫ v dP
R

D

GR P vR

RT
= ∫ D RT
dP

GR P vR f
=
RT ∫ D RT
dP
= lnln φ − lnln    
P
GR P  v − v ig  P v vig  PdP P dP

RT
= ∫
D  RT

 dP =


∫
D  RT

− 

RT  P D∫ (
=z − 1
P
)

Q Given that
gR
=∫
P v
R
dP find the Residual molar Gibbs free energy at
RT D RT

temperature of 300 K & pressure of 0.2 mPa, and the gas is assumed to
BP
Z=1+ , B= 10−4 m3 / mol
RT

Sol:
P dP  BP  dP
∫ (z − 1) P =1 + RT − 1 P
D

gR = 20 m3 / mol
gR
= lnln φ 
RT
f = 0.2016mPa

Q The pressure of the liquid is increased Isothermally so that the molar volume
decreases from 50.45 × 10−9  to 48 × 10−6  m3 / mol during this process Isother-
mal compressibility is 10−9 Pa −1 which can be assumed to be independent of
pressure. Find out change in molar gibbs free energy of liquid in Joules/mol.
Thermodynamics

Sol: α=
−dv
vdP
g = 2450 Joules / mol

183.
 Vapour liquid equilibrium
When two phases are in equilibrium, then the chemical potential of every species in both
phases must be the same at some temperature and pressure.
dg = vdP T = constant
dg = RT dlnlnP
    {Ideal gas}
dg = RT dlnln f   {Real gas}
for α phase
dgl = RT dlnln fl  

dg v = RT dlnln f v  
fl
d[gl − g v ] =
RT dlnln  v  
f
During phase change operation dg = 0
fl
0 >  fl =
RT dlnln  v  == fv
f
fl l v
v
= 1 f= f= f sat
f
fl fv fsat φl =φv =φsat
= sat
=sat sat

p p p

This means that phases can only be in equilibrium fl = f v

Fugacity of liquid and solid for pure spices

At any temperature P = Psat
Since, the fugacity of saturated vapor must equal the fugacity of saturated liquid.
fl = f v
l
f=( sat
P P= v
f=)P Psat( )
Thermodynamics

184.
Q A pulse of concentrated is introduced as tracer into the fluid entering a
reaction vessel having volume 1 m3 & the flow rate = 1 m3/min., the concen-
tration of tracer is measured in the flow having the vessel as shown in the
figure:

The flow model parameter that fits the measured RTO in terms of all of the
following mixing element namely volume of PFR Vp & Vn & Vd.

Sol: Zp = 20 sec
If it would be CSTR
If Tm = 40, *** (60-20) 540, then it is CSTR without dead space.

−
(
− t −20 )
tobversed
C(+) = Co e
(
− 50 −20 )
20 −
tobversed
= 20e  
e
tobserved = 30sec
Here tobserved > Tm then there must be a dead space
v
T= 20 =
Vo
1
20 ×  
60
Thermodynamics

185.
 Q A step input tracer test is used to explore the flow pattern of fluid through a
vessel of total volume = 1 m3 having feed rate 1 m3/min

(P) curve (1) PfR +CSTR in series

(Q) curve (2) CSTR with dead space
(3) PfR in series with CSTR & dead space
(4) CSTR

Sol: tobserved = 60sec it is Ideal CSTR if Tm = 60 otherwise not

t
−
τm
In curve (1) C(+) = Co(1 - e )
τm =40 sec it is 40 sec that is less than τobserved
So it is CSTR + Dead space
Thermodynamics

186.
Gate Questions
Gate 2015

Q1 If v, u, s and g represent respectively the molar volume, molar internal ener-

gy, molar entropy and molar Gibbs free energy, then match the entries in the
left and right columns below and choose the correct option.

 ∂u  (I) Temperature
(P) −  
 ∂v S

(II) Pressure
(Q)  ∂g 
 ∂P T

 ∂g  (III) V
(R) −  
 ∂T P

 ∂u  (IV) S
(S) −  
 ∂s V

(A) P - II, Q - III, R - IV, S - I (B) P - II, Q - IV, R - III, S - I

(C) P - I, Q - IV, R - II, S - III (D) P - III, Q - II, R - IV, S - I

Sol: (A)
We know that
We have
=du Tds − pdv
and = dg vdp − sdT
∂u ∂u
So, = −P ⇒ − =P
∂v s ∂v s
∂u
=T
∂s v
∂g ∂g
= V= and S
∂p T ∂T P
Thermodynamics

187.
 Q2 For a gas phase cracking reaction A →B + C at 300OC, the Gibbs free energy of
the reaction at this temperature is ∆GO =
−2750 J / mol . The pressure is 1 bar
and the gas phase can be assumed to be ideal. The universal gas constant R
= 8.314J/mol. K. The fractional molar conversion of A at equilibrium is:
(A) 0.44 (B) 0.50 (C) 0.64 (D) 0.80

Sol: (D)
we have
A 
→ B
+ C
at t = 0, 1 0 0
Let α =fraction of A connverted
=at t t 1− α α α
Thus,
yB yC
KP
= ×P
yA
 α  α 
  
1 + α  1 + α  α2
KP 
= ×P
= ×P
1− α 1 − α2
 
1+ α
Also,
 ∆GO 
lnK = −  
 RT 
 −2750 
K
= exp  − 
 8.314 × 573 
K = 1.78
α2
so, = 1.78 ⇒ α 0.80
=
1 − α2
Thermodynamics

188.
Q3 For a pure liquid, the rate of change of vapour pressure with temperature is
0.1 bar/K in the temperature range of 300 to 350 K. if the boiling point of the
liquid at 2 bar is 320 K, the temperature (in K) at which it will boil at 1 bar
(up to one decimal place) is ______

Sol: 310
We have
dP
Given = 0.1 ⇒ dP = 0.1dT
dT
⇒ P= 0.1T + c (i)
Given
= at T 320K,
= P 2 bar
2 =0.1 × 320 + c
⇒ c= −30
equation (i) becomes
= P 0.1 T − 30
⇒ T= 310K

Q4 Three identical closed systems of a pure gas are taken from an initial tem-
perature and pressure (T1, P1) to a final state (T2, P2), each by a different
path. Which of the following in Always true for the three systems? (∆ rep-
resents the change between the initial and final states: U, S, G, Q and W
are internal energy, entropy, Gibbs free energy, heat added and work done,
respectively.)
(A) ∆U, ∆S, Q are same (B) W, ∆U, ∆G are same
(C) ∆S, W, Q are same (D) ∆G, ∆U, ∆S are same

Sol: (D)
we have
U, S, and G are state variables (point functions)
So
Remain the same between two states 1 and 2.
Thermodynamics

189.
 Q5 Which of the following can change if only the catalyst is changed for a reac-
tion system?
(A) Enthalpy of reaction (B) Activation energy
(C) Free energy of the reaction (D) Equilibrium constant

Sol: (B)
Catalyst changes the activation energy of the reaction
Hence, (B) is the correct answer.

Q6 An ideal gas is initially at a pressure of 0.1 MPa and a total volume of 2m3.
It is first compressed to 1MPa by a reversible adiabatic process and then
cooled at constant pressure to a final volume of 0.2m3. The total work done
(in kJ) on the gas for the entire process (up to one decimal place) is ______
Data: R = 8.314 J/mol-K; heat capacity at constant pressure (CP) = 2.5R

Sol: 750
Given:
1 → 2 : Reversible adiabatic process
2 → 3 : Reversible isobaric process
Given
P1 = 0.1MPa
= 105 Pa
v 1 = 2m3
6
=P2 10
= Pa P3
V3 = 0.2m3
=CP 2.5
= R So Cv 1.5R
2.5
γ CP / C=
= v
= 1.667
1.5
for process 1 − 2 : P1 V1γ =
P2 V2γ
1
 P1  γ  105  1
=V2 =  V1 2x  6  1.667
P   10 
 2  
Thermodynamics

2
⇒ V2 = 0.50 m

190.
 Work done on for process 1-2
P1 V1 − P2 V2 0.1X106 x2 − 106 x106 x0.5
=w 1−2 =
γ−1 0.667
⇒ w 1−2 = − 450kJ
work done for process 2 − 3
w2−3 = P∆V
= 106 X(0.2 − 0.5)
= −300kJ
Net work done = 450+350=750 kJ

Q7 Given that molar residual Gibbs free energy, gR, and molar residual volume
VR, are related as
gR P v 
R
=∫   dP,
RT 0  RT 
Find gR at T = 27 0C and P = 0.2MPa. The gas may be assumed to follow the
viral equation of state, Z = 1+BP/RT, where B= -10 – 4 m3/mol at the given
conditions (R = 8.314 J/mol-K). The value of gR in J/mol is:
(A) 0.08 (B) −2.4 (C) 20 (D) −20

Sol: (D)
gR P VR
Given
RT
= ∫
0 RT
dP

ZRT RT RT
we know, VR =V − V 1g = − =(Z − 1)
P P P
R
V (Z − 1)
or =
RT P
BP (Z − 1) B
And Z =+ 1 ⇒ =
RT P RT
R
g P B
so ,
RT ∫
=
0 ERT
dp

m3
gR = B (P − 0) = − 10−4 x 0.2x106 Pa
mol
gR = − 20J / mol
Thermodynamics

191.
 Q8 A binary mixture of components (1) and (2) forms an azeotrope at 1300C and
x1 = 0.3. the liquid phase non-ideality is described=
by In γ 1 Ax 22 and In γ 1 , γ 2
are the activity coefficient and x1 , x2 are the liquid phase mole fractions. For
both components, the fugacity coefficients are 0.9 at the isotropic composi-
tion. Saturated vapor pressures are at 1300C are P1sat = 70 bar, P2sat= 30 bar
The total pressure in bars for the above azeotropic system (up to two deci-
mal places) is

Sol: 27.52
The general VLE equation
For component 1
φ1 y 1P =x 1 γ 1P1s ............................eq.1
φ2 y 2P =x2 γ 2P1s ............................eq.2
at azeotrope yi = xi
Equation 1 divides by Equation 2

φ1 y 1P x 1 γ 1P1s
=
φ2 y 2P x2 γ 2P2s
Ax 2
0.9P 70 e 2
=
0.9P Ax2
30 e 1
30 A(x2 − x 2 )
=e 2 1
70
Ax 22 2
0.9P 70 e = 70 e−2.12x0.7
P = 27.52 bar
Thermodynamics

192.
Gate 2016

Q1 The partial molar enthalpy (in kJ/mol) of species 1 in a binary mixture is

given by h1 =
2 − 60x 22 + 100x 1 x 22 ,  where x 1 and x 2 are the mole fractions of
species 1 and 2, respectively. The partial molar enthalpy (in kJ/mol, rounded
off to the first decimal place) of species 1 at infinite dilution is ________

Sol: Infinitely dilute solution of component (1)

x 1 → 0 & x2 → 1

2 − 60 x (1)2 + 100 x 0 x (1)2

So h1 =

h1 = − 58

Q2 A binary liquid mixture of benzene and toluene contains 20 mol% of ben-

zene. At 350 K the vapour pressures of pure benzene and pure toluene are 92
kPa and 35 kPa, respectively. The mixture follows Raoult’s law. The equilib-
rium vapour phase mole fraction (rounded off to the second decimal place)
of benzene in contact with this liquid mixture at 350 K is _____

Sol: 0.396
From Raoult’s law
p i = xi .piv

pi pi
& we’ =
yi =
p ∑ pi
Mol fraction of benzene in vapor phase is given by

pB xBpBV
⇒ y=
B
=
xBPBV + xTpTT
∑ p
i
0.2 × 92
= = 0.396
0.2 × 92 + 0.8 × 35
Thermodynamics

193.
 Q3 An ideal gas is adiabatically and irreversibly compressed from 3 bar and 300
K to 6 bar in a closed system. The work required for the irreversible com-
pression is 1.5 times the work that is required for reversible compression
from the same initial temperature and pressure to the same final pressure.
The molar heat capacity of the gas at constant volume is 30 J mol‒1 K‒1 (as-
sumed to be independent of temperature); universal gas constant R is 8.314
J mol‒1 K‒1; ratio of molar heat capacities is 1.277. The temperature (in K,
rounded off to the first decimal place) of the gas at the final state in the
irreversible compression case is _______

Sol: 373
We know that
Wirr = 1.5 Wrev
(Change in I.E.)irr = 1.5 (change in I.E.)rev
CV (T2′ −= T1 ) 1.5 CV (T2 − T1 )

T=
2
′ − T1 1.5 CV (T2 − T1 )

( )
γ −1
P2 γ
=
T2′ − T1 1.5 (T1 P1
− T1 )

 .277
 6  1.277 

T2′ − 300 = 1.5 × 300 ×   − 1 = 73
 3 
 
T2′ = 373K
Thermodynamics

194.
Q4 A gas obeying the Clausius equation of state is isothermally compressed
from 5 MPa to 15 MPa in a closed system at 400 K. The Clausius equation of
RT
state is P = where P is the pressure, T is the temperature, v is the
v − b(T)
molar volume and R is the universal gas constant. The parameter b in the
above equation varies with temperature as b(T)
= b0 + b 1 T with b0 =4 × 10‒5
m3mol‒1 and b 1 = 1.35 × 10‒7 m3mol‒1K‒1. The effect of pressure on the molar
 ∂h   ∂v 
enthalpy (h) at a constant temperature is given by   = v − T  . Let hi
 ∂P T  ∂T 
and hf denote the initial and final molar enthalpies, respectively. The change
in the molar enthalpy (in J mol‒1, rounded off to the first decimal place) for
this process is ______

Sol: 400
We know that
RT
P =
v −b
P (v − b) = RT
RT
=v +
P
RT
= + b0 + b1T
P
R 
=  + b1  T + b0
 P 
∂h ∂v
= v −T
∂P T ∂T P

 R   R 
=  + h1  T + b0  − T  + b1  = b0
 P   P 
dhT = b0dPT
(hf − hi )T = b0 (Pf − Pi )T
=4 × 10−5 × (15 − 5) × 106 =400 J / mol
Thermodynamics

195.
 Q5 A binary system at a constant pressure with species ‘1’ and ‘2’ is described
gE
by the two-suffix Margules equation, = 3x 1 x 2 ,where g E is the molar
RT
excess Gibbs free energy, R is the universal gas constant, T is the tempera-
ture and x 1 and x 2 are the mole fractions of species 1 and 2, respectively.
g1 g2
At a temperature T, = 1 and = 2, where g 1 and g 2 are the molar Gibbs
RT RT
free energies of pure species 1 and 2, respectively. At the same temperature,
g represents the molar Gibbs free energy of the mixture. For a binary mix-
ture with 40 mole % of species 1, the value (rounded off to the second
g
decimal place) of is
RT

Sol: 1.647
gE= g − gid

gE g gid
⇒ = −
RT RT RT
g
⇒ 1.647
=
RT
g gE gid
⇒ = +
RT RT RT

⇒
g
= +
gE ∑ {( ) }
xigi + RT xi ln xi +
RT RT RT

⇒
g
= +
g E x g
1 1
+ x g
2 2 ( )
+ RT x 1 ln x 1 + x2 ln x2
RT RT RT
g g g
⇒ = 3x 1x2 + x 1 1 + x2 2 + x 1 ln x 1 + x2 ln x2
RT RT RT
g
⇒ = 3 × 0.4 × 0.6 + 0.4 × 1 + 0.6 × 2
RT
+0.4 × ln(0.4) + 0.6 × ln(0.6)
Thermodynamics

196.
Gate 2017

Q1 The volumetric properties of two gases M and N described by the general-

ized compressibility chart which expresses the compressibility factor (Z) as
a function of reduced pressure and reduced temperature only. The operating
pressure (P) and temperature (T) of two gases M and N along with their crit-
ical properties (PC,Tc) are given in the table below.

Gas P (bar) T (K) PC (bar) TC (K)

M 25 300 75 150

N 75 1000 225 500

ZM and ZN are the compressibility factor of the gases M and N under the giv-
en operating conditions respectively.
The relation between ZM and ZN is
(a) ZM = 8ZN (b) ZM = 3ZN
(c) ZM = ZN (d) ZM = 0.333ZN

Sol: (C)
For gas M; P = 25 bar, Pc = 75 bar
P 25 1
Pr
= = =
Pc 75 3
For Gas N; P = 75 bar, PC = 225 bar
75 1
= Pr =
225 3
T
For Gas M; T = 300 K, TC = 150 K, Tr = = 2
TC

T
For Gas N; T = 1000 K, TC = 500 K, Tr = = 2
TC
Pr
Compressibility factor, Z = k
Tr
Thermodynamics

197.
 Q2 Water is heated at atmospheric pressure from 400C to 800 C using two
different process. In process I, the heating is done by a source at 800C. In
process II, the water is first heated form 400C to 600C by a source at 600C,
and then from 600C to 800 C by another source at 800C. Identify the correct
statement.
(a) Enthalpy change of water in process I is greater than enthalpy change in
process II
(B) Enthalpy change of water in process II is greater than enthalpy change in
process I
(c) Process I is closer to reversibility
(d) Process II is closer to reversibility

Sol: (D)

Q3 The vapour pressure of a pure substance at a temperature T is 30 bar. The

actual and ideal gas values of g /RT for the saturated vapour at this tem-
perature T and 30 bar are 7.0 and 7.7 respectively. Here, g is the molar Gibbs
free energy and R is the universal gas constant the fugacity of the saturated
liquid at these conditions, rounded to 1 decimal place is ___bar

Sol: 14.9
As we know
 1
K  
= Zm = 3 K
2 6
 1
K 
3 K
Zn =   = ⇒ Zm =Zn
2 6
 g   g 
=
  7,
=   7.7
 RT   RT 
f  gR 
φx =i exp  
Thermodynamics

P  RT 
 

198.
 fi  gR 
φx = = exp  
p  RT 
 
R
g  g   g 
= −  =7 − 7.7
RT  RT   RT ig
gR f
= − 0.7 = i = ρ × p ( −0.7)
RT P
fi
= 30 exp ( −0.7)
= 14.9 bar

Q4 The pressure of a liquid is increased isothermal compressibility. the molar

volume of the liquid decreases from 50.45 × 10-6 m3/mol to 48 × 10-6 m3/mol
during this process. The isothermal compressibility of the liquid is 10-9 Pa-1,
which can be assumed to be independent of pressure The change in the
molar Gibbs free energy of the liquid, rounded to nearest integer,is ____J/
mol.

Sol: 2511.4
−1  dv 
As we =
know β   → (1)
V  dp T
For isothermal process pv = const
−dv V
Pdv +Vdp = 0 =
dp P1
From equation
1 1
β= ⇒ P1= = 100 Pa
P1 β
At constant temperature
Thermodynamics

199.
 Q5 A sparingly soluble gas (solute) is in equilibrium with a solvent at 10 bar. The
mole fraction of the solvent in the gas phase is 0.01 At the operating tem-
perature and pressure, the fugacity coefficient of the solute in the gas phase
and the Henry’s law constant are 0.92 and 1000 bar, respectively. Assume
that the liquid phase obeys Henry’s law. The mole percentage of the salute
in the liquid phase rounded to 2 decimal places, is ____

Sol: 0.91
=H 1000
= bar, φ 0.92 for dilute solution
We can use Henry law for solute Hx = φyP
1000 x = 0.92 (1-0.01) (10)
Here, y and x are mole fraction of solute in gas liquid respectively x = 9.108 x
10-3
Mole percentage of solute in liquid phase = 100 (9.108 × 10-3) = 0.91

Gate 2018

Q1 Under isothermal conditions, a vertical tube of length L = 100 m contains a

gas of molecular weight equal to 60. The pressure and temperature at the
top of the tube are 100 kPa and 250C respectively. Consider the universal gas
constant and acceleration due to gravity as 8.314 J mol-1 K-1 and 9.81 m s-2re-
spectively. If the gas is ideal, the pressure (in kPa) at the bottom of the tube
will be ______

Sol: 102.375
Densityf o the gas ρ
= PM 100KPa × 60k / k.mol
= (kg / m3 )
RT KPa - m3
8.314 × × 298k
Kmol - k
= 2.4127 kg / m3
Pr essure at Bottomof vessel= P0 + ρgh
Thermodynamics

=100 kpa + 2.421kg / m3 × 9.81m / s2 × 100m(Kpa)

= 100 + 2.3756
P = 102.375kPa

200.
Q2 Consider the following properties: (P) temperature (Q) specific gravity (R)
chemical potential (S) volume. The option which lists ALL the intensive
properties is
(A) P (B) P and Q
(C) P, Q, and R (D) P, Q, R and S

Sol: (C)
G  Gibbs free energy 
ì=   intensive
N  No of molecules 

T ρ T ρ
Tρµ
→ µ µ
V
V/2 V/2

Q3 In a closed piston-cylinder system, methane was observed to obey the fol-

lowing equation of state P(V-nb) = nRT where b = 0.029 m3/mol. The temper-
ature and volume are 500°C and 5 m3 respectively for 100 moles of methane.
At this state of the system, the isobaric rate of change of temperature with
volume is (0C/m3) _____ (rounded off to second decimal place).

Sol: 368.166
P(v-nb)=nRT, T=5000C=773k

b=0.029m3 /mol
nRT
P=
(v-nb)
100mol×8.314m3 -pg/molk×773k
=
(5-100×0.029)m3
=306034.3pa (or) 306.3kpa

dT P 303.03×103Pa
= =
dv nR m3-Pa
100×8.314
Thermodynamics

molk
dT
=368.166(k/m3 )
dv

201.
 Q4 G denotes the Gibbs free energy of a binary mixture, nT denotes the total
number of moles present in the system, µ 1 is the chemical potential of the
component
( µ 1 ≠ 0 and µ 1  µ2 ), x i is the mole fraction of the component. The correct
G
variation of (J/mol) at constant temperature and pressure is given by
nT

Sol: Specific gibbs free energy

g=Xa g 2 +Xb gb +RT ∑ X ilnXi (mixing is zero for ideal gas)
xa = 0, xb =1
g = 0+1×gb

xa = 0, xa =1
g = ga
Option (C) cannot be the answer since G/Nr be for real system should be
decreasing functions
Thermodynamics

 JG/Nr 
(or)  <0-ve slope
 ∂x 
 1 

202.
Gate 2019

Q1 Consider a rigid, perfectly insulated, container portioned into two equal

parts by a thin membrane (see figure). One part contains one mole of an
ideal gas at pressure Pi and temperature Ti while the other part is evacuated.
The membrane ruptures, the gas fills the entire volume and the equilibrium
pressure is Pf=Pi/4. If Cp (molar specific heat capacity at constant pressure),
Cv(molar specific heat capacity at constant volume) and R(universal gas
constant) have the same units as molar entropy, the change in molar entro-
py(Sf-Si) is

a. CP ln2 + R ln4 b. -Cv ln2+R ln4

c.R ln 4 d. CP ln2

Sol: c
du = δq-δw
There is no heat exchange with surrounding and no work is done against sur-
rounding, So
du=0 (before and after membrane separation)
ui = uf  
For an ideal system u=u(T) (internal energy is a function of t only and not
pressure)
For free expansion against vaccum of an ideal gas internal energy and there-
fore, temperature remains constant.
Thermodynamics

It’s just that volume increase is exactly compensated by pressure decrease,

so that =
Pv
i i
P=v
f f (RT )

203.
 But entropy change (due to irreversibility of the process)
T P
∆s CPln  2 − Rln  2 [ for an ideal gas only]
=
T1 P1
T1=T2

P
∆s CPln 1 − Rln  2
=
P1
P1
P2 = (Given)
4
P1
1
∆s =−Rln 4 = -R ln ( ) = R ln4
P1 4

Q2 For a single component system, vapor (subscript g) and liquid (subscript f)

coexist in mechanical, thermal and phase equilibrium when
a. ug=uf (equality of specific internal energy)
b. hg=hf (equality of specific enthalpy)
c. sg=sf (equality of specific entropy)
d. gg=gf (equality of specific Gibbs free energy)

Sol: d
For VLE(vapor-liquid equilibrium)
Ug>>uf
Hg>>hf
Sg>>sf
But gg=gf
Where,
G= vapor( may be saturated vapor)
L= liquid (also may be saturated liquid)
Large amount of heat is added during L->V phase transition
Thermodynamics

204.
Q3 For a binary non-ideal A-B mixture exhibiting a minimum boiling azeotrope,
the activity coefficients, (i=a,B), must satisfy
a. ϒ A > 1, ϒB > 1 b. ϒ A < 1, ϒB >1
c. ϒ A = 1, ϒB = 1 d. ϒ A < 1 , ϒB < 1

Sol: a
Binary mixture, minimum boiling azeotrope
A. 
ϒA > 1, ϒB > 1 : Positive deviation from Raoult’s law (min. boiling azeo-

trope)
B. 
ϒA < 1, ϒB >1 : Either positive or negative deviation from Raoult’s law de-
pending on relative magnitude of rA and rB , as a function of composition
( )
ϒA = 1, ϒB = 1     : Raoult ′slaw ideal solution

C. 
ϒA < 1 , ϒB < 1 : Negative deviation from Raoult’s law (maximum boiling
azeotrope)

Q4 Consider a sealed rigid bottle containing CO2 and H2O at 10 bar and ambient
temperature. Assume that the gas phase in the bottle is pure CO2 and fol-
lows the ideal gas law. The liquid phase in the bottle contains CO2 dissolved
in H2O and is an ideal solution. Henry’s constant at the system pressure and
temperature is HCO2=1000bar. The equilibrium mole fraction of CO2 dissolved
in H2O is ………………. (Rounded off to two decimal places)

Sol: 0.01
HCO2= 1000bar
yiP = xiHi
yi = 1.0 (Pure CO2)
(1.0) (10 bar) = xi (1000 bar)
10
=xi   =  0.01
1000
Thermodynamics

205.
 Q5 Carbon monoxide (CO) reacts with hydrogen sulphide (H2S) at a constant
temperature of 800 K and a constant pressure of 2 bar as:
CO +  H2 S  COS + H2
The Gibbs free energy of the reaction Δgreaction =22972.3 J/mol and univer-
sal gas constant R=8.314 J/(mol K). Both the reactants and products can be
assumed to be ideal gases. If initially only 4 mol of H2S and 1 mol of CO are
present, the extent of the reaction (in mol) at equilibrium is …………. (round-
ed off to two decimal places)

Sol: 0.2888
CO(g) +H2S(g) ⇋ COS(g) + H2(g)
T= 800 K,
P= 2 bar,
Δg°= 22972.3 J/mol
−∆g°
K= exp [ ]
RT
mol.k 1
K= exp[ 22972.3 J/mol ×  ×  }
8.314 J 800K  
K = exp [-3.4539]
K=0.0316
vi
 f 
K= ∏ i
 i
 f°


 i 
vi
∅ yiPi 
K= ∏ i

 P° 

 
∅i (
 =1  for ideal gas
)
vi
 yiP 
K= ∏ i

 1b

  ar 
CO(g) +H2S(g)= COS(g) + H2(g)
Thermodynamics

206.
 nio ni yi

CO(g) 1 1-x (1-x)/2

H2S(g) 4 4-x (4-x)/5

COS(g) 0 X x/5

H2(g) 0 x x/5
vi
 yiP  yCOS yH2
K= ∏ i

 1b

  ar 
=
yCO yH2S
 x x
  
yCOS . yH2 5 5 x2
K= =     = 
yCO  yH2S 1−x 4 −x
 
1− x 4 − x ( )( )
2 5
Or,
x
0.0316 =
( 1 − x )( 4 − x )
x2
Or, 4 – 5x + x2 = = 31.6456 x2
0.0316
30.6456 x2 + 5x − 4 =
0
−5 ±    52 − 4 30.6456 −4 ( )( )
X=
2 × 30.6456
X = 0.2888

Thermodynamics

207.
 Q6 For a binary system at constant temperature and pressure , the molar vol-
ume (in m3/mol) is given by:
V= 30xA+ 20 xB +xAxB (15xA-7xB), where xA and xB are the mole fractions of
components A and B, respectively. The volume change of mixing Δvmix (in m3/
mol) at xA=0.5 is ……………….. ( Rounded off to one decimal place).

Sol: 1
V= 30xA+ 20 xB +xAxB (15xA-7xB)

∆H = M −  ∏ xH i i

Where,
ΔH= Property change on mixing
M= Molar property of the mixture
For molar volume,
2
∏
∆vmix =  vmix −   xv
i− 1 i i
=  vmix − ( xA v A + xB vB )

Molar volume of pure compounds,

V= 30 xA +20 xB +xAxB (15 xA-7xB)
For pure A (xA=1, xB=0)
vA= 30 (1) + 20 (0) + 0= 30m3/mol
For pure B (xA=0, xB=1)
vB= 30 (0) + 20 (1) +0= 20 m3/mol
Molar volume of the mixture at xA=0.5 and xB= 0.5
Vmix= 30(05) +20 (0.5) + (0.5)(0.5) (15×0.5- 7×0.5)
Vmix= 26 m3/mol
Δvmix= vmix – (xAvA+xBvB)
Δvmix = 26- (0.5×30 +0.5×20)
Δvmix= 1 m3/mol of the mixture
Thermodynamics

208.
Q7 Consider a vessel containing steam at 180°C. The initial steam quality is 0.5
and the initial volume of the vessel is 1 m3. The vessel loses heat at a con-
stant rate q under isobaric conditions so that the quality of steam reduces
to 0.1 after 10 hours. The thermodynamic properties of water at 180°C are
(subscript g: vapor phase; subscript f: liquid phase)

Specific volume v g = 0.19405 m3 / kg v f = 0.001127 m3 / kg

Specific internal energy ug = 2583.7 kJ / kg uf = 762.08 kJ / kg

Specific enthalpy hg = 2778.2 kJ / kg hf = 763.21 kJ / kg

The rate of heat loss q (in kJ/hour) is …………………. (Rounded off to the
nearest integer).

Sol: PI=PII
TI=TII=180°C therefore, quality is >0 as long as the pressure is constant (giv-
en) temperature must also be the same as in state I
Isobaric condensation of steam (closed system)
du = δq-δw
du= δq-Pdv
(du+Pdv)=δq
Or, dh=δq (at constant P)
i.e: heat transferred=change in enthalpy of steam
Mass of steam in piston – cylinder
M=V/v= (total volume) (m3)/sp. Volume (m3/kg)
For a two phase mixture
V= (1-xv)vl+ xvvv
or this can also be written as:
v= (1-x) vf +x vg
State 1
T=180°C
Vf=0.001127 m3/kg ; x=0.5
Vg= 0.19405 m3/kg
VI= (1-0.5) 0.001127 + 0.5×0.19405
V1= 0.0976 m3/kg
Mass of the steam inside the vessel
Thermodynamics

M= V/v= 1 m3/ 0.0976 m3/kg= 10.2471 kg

Sp. Enthalpy at state 1
hI= (1-x)hf +x hg

209.
 hI= (1-0.5)×763.21 kJ/kg + 0.5×2778.2 kJ/kg
hI=1770.705 kJ/kg
State 2
hII= (1-x)hf +x hg
hII= (1-0.1)763.21 +0.1×2778.2
hII=964.709 kJ/kg
Energy balance
Δq= dh
Or Δq= (hII-hI)= (964.709-1770.705) kJ/kg
Δq= -805.996 kJ/kg
ΔQ= m.Δq= 10.2471 kg × (805.996) kJ/kg
ΔQ= -8259.121 kJ
Rate of heat transfer = -8259.121 kJ× (1/10 h)
Rate of heat transfer= -825.91 kJ/h
Negative sign indicated that heat has been removed from the vessel

Q8 A fractionator recovers 95 mol% n-propane as the distillate from an equimo-

lar mixture of n-propane and n-butane. The condensate is saturated liquid
at 55°C. The Antoine equation of the form
B
( )
ln psat in bar  = A −  
T ( in K ) + C

, and the constants are provided below:

A B C

n-propane 9.1058 1872.46 -25.16

n-butane 9.0580 2154.90 -34.42

Assuming Raoult’s law, the condenser pressure (in the bar) is ……………………
(Rounded off to one decimal place)

Sol: Raoult’s law is valid (given)

P = xIPIsat +x2P2sat
T = 55°C
1872.46
=   1sat 9.1058 −  
lnP
Thermodynamics

( )
55 + 273.15 − 25.16

  1sat = 2.92586
lnP

210.
 P1sat = 18.650 bar
2154.90
  2sat 9.0580 −  
lnP
=
(55 + 273.15) − 34.42
P2sat = 5.5939 bar
P = x 1P1sat +  x2P2sat
P = 0.95×18.650 + (1-0.95) ×5.5939
P = 18 bar

GATE 2020

Q1 Mole fraction and activity coefficient of compound 1 in a binary liquid mix-

ture are x1 and ϒ1 respectively. GE is excess molar Gibbs energy of the mix-
ture. R is the universal gas constant and T is the absolute temperature of the
mixture. Which one of the following is always true?
GE GE
a.  = 0 b.  = 0.5 c.  γ 1  =0 d.  γ 1  =0.5
RT RT

Sol: a
GE= G −  GID
Molar excess Gibbs free energy= Molar Gibbs free energy of the binary mix-
Molar Gibbs free energy of the ideal mix
As, xr=1
(the mixture becomes almost pure component)
G = G ID ; GE = 0
limx→1   GE / RT =0 Thermodynamics

211.
 Q2 Consider two Carnot engines C1 and C2 in the figure:

The efficiencies of the engine C1 and C2 are 0.40 and 0.35, respectively. If the
temperature of Reservoir R1 is 800 K the temperature (in K) of Reservoir R3
us ………………….. (Rounded off to nearest integer)

Sol: ηc = 1 −
Tc
TH
T1=800 K
η1= 0.40 = 1- T2 / T1
T2= 480 K
η2= 0.35= 1- T3 / T2
T3=T2(1-0.35)
T3= 312 K
Thermodynamics

212.
Q3 A pure gas obeys the equation of state given by
PV BP
= 1 + 
RT RT
Where P is the pressure, T is the temperature, v is the molar volume of the
gas , R is the universal gas constant , and B is a parameter independent of
T and P. the residual molar Gibbs energy , GR, of the gas is given by the rela-
tion:
GR dP
=  ∫ ( Z − 1)
P

RT 0 P
Where Z is the compressibility factor and the integer are evaluated at con-
stant T. If the value of B is 1×10-4 m3 mol-1, the residual molar enthalpy (in J
mol-1) of the gas at 1000KPa and 300 K is
a. 100 b. 300 c. 2494 d. 30000

Sol: a
PV BP
= 1 + 
RT RT
BP
Z= 1+
RT
GE P dP
=   z−1
RT 0 ∫(
P
)
GE P    BP  dP

RT 0 ∫
=    1 +   − 1
 RT  P
GE P BP dP B
=  
RT 0 ∫
=  
RT P RT
P−0 ( )
GE BP E
=   =  G= BP
RT RT
 m3 Pa 
GR =
 1 × 10−4 × 1000k
  Pa ×1000 
 mol kPa 

m3 J

= GR 100P
=   a.   100
mol mol
Thermodynamics

213.
 Q4 Consider one mole of an ideal gas in a closed system. It undergoes a change
in state from L to N through two different non-isothermal processes, as
shown in the P-V diagram (where P is the pressure and v is the molar volume
of the gas) . Process I is carried out in a single step, namely LN whereas pro-
cess II is carried out in two steps LM and MN. All the steps are reversible.
The net heat flowing into the system for process I is QI and that for process
II is QII. The value of QI-QII (in J) is

a. 250 b. 500 c. 1000 d. 1500

Sol: First law:

du = δq-δw
: u is a state function
Δu I= Δu II
δqI − δwI =  δqII −  δwII
δqI − δqiI =  δqII −  δqI
QI − QII = WI − W2

W= ∫ Pdv = area under the curve in the PV diagram

QI − QII = WI − W2 = area inside the triangle
1

QI − QII =
2
 base height( )( )
(
1  0.03 − 0.02 m3   )
= QI − QII
2

mol  
(
    200 − 100 kPa 
 )
 
Thermodynamics

kJ
QI − QII = 0.5
mol
J
QI − QII = 0.5 ×1000 = 500
mol
214.
GATE 2020

Q1 Mole fraction and activity coefficient of compound 1 in a binary liquid mix-

ture are x1 and ϒ1 respectively. GE is excess molar Gibbs energy of the mix-
ture. R is universal gas constant and T is the absolute temperature of the
mixture. Which one of the following is always true?
GE GE
a.  = 0 b.  = 0.5 c.  γ 1  =0 d.  γ 1  =0.5
RT RT

Sol: A
GE= G −  GID
Molar excess Gibbs free energy= Molar Gibbs free energy of the binary mix-
Molar Gibbs free energy of the ideal mix
As, xr=1
(the mixture becomes almost pure component)
G=G ID ; GE=0
limx→1   GE / RT =0

Q2 Consider two Carnot engines C1 and C2 in the figure:

The efficiencies of the engine C1 and C2 are 0.40 and 0.35, respectively. If the
temperature of Reservoir R1 is 800 K the temperature (in K) of Reservoir R3
us ………………….. (Rounded off to nearest integer)

Sol: ηc = 1 −
Tc
TH
T1=800 K
η1= 0.40 = 1- T2 / T1
T2= 480 K
η2= 0.35= 1- T3 / T2
T3=T2(1-0.35)
T3= 312 K
Thermodynamics

215.
 Q3 A pure gas obeys the equation of state given by
PV BP
= 1 + 
RT RT
Where P is the pressure, T is the temperature, v is the molar volume of the
gas , R is the universal gas constant , and B is a parameter independent of
T and P. the residual molar Gibbs energy , GR, of the gas is given by the rela-
tion:
GR dP
=  ∫ ( Z − 1)
P

RT 0 P
Where Z is the compressibility factor and the integer are evaluated at con-
stant T. If the value of B is 1×10-4 m3 mol-1, the residual molar enthalpy (in J
mol-1) of the gas at 1000KPa and 300 K is
a. 100 b. 300 c. 2494 d. 30000

Sol: A
PV BP
= 1 + 
RT RT
BP
Z = 1+
RT
GE P dP
∫(
=   z−1
RT 0 P
)
GE P    BP  dP

RT ∫
=    1 +   − 1
0
 RT  P
GE P BP dP B
=  
RT ∫=  
0 RT P RT
P−0 ( )
GE BP E
=   =  G= BP
RT RT
 m3 Pa 
GR =
 1 × 10−4 × 1000k
  Pa ×1000 
 mol kPa 

m3 J

= GR 100P
=   a.   100
mol mol
Thermodynamics

216.
 Q4 Consider one mole of an ideal gas in a closed system. It undergoes a change
in state from L to N through two different non-isothermal processes, as
shown in the P-V diagram (where P is the pressure and v is the molar volume
of the gas) . Process I is carried out in a single step, namely LN whereas pro-
cess II is carried out in two steps LM and MN. All the steps are reversible.
First law:

Sol: du= δq-δw

: u is a state function
Δu I= Δu II
δqI − δwI =  δqII −  δwII
δqI − δqiI =  δqII −  δqI
QI − QII = WI − W2

W= ∫ Pdv = area under the curve in the PV diagram

QI − QII = WI − W2 = area inside the triangle
1
QI − QII =
2
(
 base height )( )
( )
1  0.03 − 0.02 m3  
= QI − QII
2

mol  
( )
    200 − 100 kPa 

 
kJ
QI − QII =
0.5
mol
J
QI − QII = 0.5 ×1000 = 500
mol

Q5 The net heat flowing into the system for process I is QI and that for process
II is QII. The value of QI-QII (in J) is
a. 250 b. 500 c. 1000 d. 1500
Thermodynamics

217.
 GATE 2021

Q1 A binary liquid mixture consists of two species 1 and 2 . Let ϒ an x represent

the activity coefficient and the mole fraction of the species, respective-
ly. Using a molar excess Gibbs energy model ln ϒ1 vs x1 and ln ϒ2 vs x1 are
plotted. A tangent line is drawn to the lnϒ1 vs. x1 curve at a mole fraction of
x1=0.2has a slope= -1.728.
The slope of the tangent drawn to the ln ϒ2 vs. x1 curve at the same mole
fraction is ………….. (correct to 3 decimal places)

Sol: 0.432
GE
=  x 1ln γ 1 + x2 l n γ 2
RT

x1  
(
d ln γ 1 ) (
d ln γ 2
+  x2   0
=
)
dx2 dx2
X1= 0.2
X2=0.8

(
d ln γ 1 ) =  −1.728
dx2
Placing the values in the equation:
d ln γ 2 ( )
(
0.2 × −1.728 + 0.8 
dx2
) =0

(
d ln γ 2 ) = 0.432
dx2
Thermodynamics

218.
Q2 A gaseous mixture at 1 bar and 300 K consists of 20 mol% CO2 and 80mol%
inert gas. Assume the gases to be ideal. Take R=8.314 L mol-1K-1.
The magnitude of minimum work required to separate 100 mol of this mix-
ture at 1 bar and 300 K into pure CO2 and inert gas at the same temperature
and pressure is ………………….. KJ (round off to nearest integer)

Sol: T = constant , ΔU=0 and ΔH=0

W = Q= TΔS
ΔG = ΔH-TΔS
ΔG = 0-TΔS

W= -n RT ∑ x ln x
i i

W= -100 ×8.314 × 300 { x 1  ln x 1 + x2 l n x2 }

W= 124.8 KJ = 125 KJ

Q3 The molar heat capacity at a constant pressure Cp(in J mol-1 K-1) for n-pen-
tane a s a function of temperature (T in K) is given by
CP
= 2.46 + 45.4 ×10−3 T − 14.1 × 10−6 T 2 . Take R = 8.314 mol −1K −1
T
At 1000 K the rate of change of molar entropy of n-pentane with respect to
temperature at constant pressure is …………….. J mol-1 K-2 (round off to 2
decimal places)

Sol: 0.28
ds CP
=   , at constant pressure
dT T
C R
ds = P dT − dp ; dp=0
T P 
ds  2.46R 
=   + 45.4 ×10−3 R − 14.1 ×10−6 × R × T 
dT  T 
ds
= 0.28
dT
Thermodynamics

219.
 Q4 The following homogeneous liquid phase reaction are at equilibrium.

The values of rate constant are given K1= 0.1 s-1, K-1= 0.2 s-1, K2= 1 s-1. K-2=10 s-1,
K3=10s-1
The value of rate constant K-3 is ………………… s-1 (corrected to 1 decimal
place)

Sol: A ⇋B
K1 0.1
Keq1
=  =   = 0.5
K −1 0.2
K 1
=   2=   = 0.1
Keq2
K −2 10
K3
Keq
= 3  =  0.05
K −3
K3= 10
K-3= 0.5 s-1

Q5 The van der Waals equation of state is given by

8Tr 3
= Pr   −  2
3v r − 1 v r
Where Pr, Tr and Vr represent reduced pressure, reduced temperature and re-
duced molar volume respectively. The compressibility factor at critical point
(Cz) is 3/8
If Vr=3 and Tr=4/3, then the compressibility factor based on the van der
Waals equation of state is …………. (Rounded off to 2 decimal places)
Thermodynamics

Sol: 0.84

220.
 Q6 The heat of combustion of methane, carbon monoxide and hydrogen are P,Q
and R respectively. For the reaction below,
CH4+ H2O -> CO+3H2
The heat of reaction is given by:
1. P-Q-R
2. P-Q-3R
3. Q+R-P
4. Q+3R-P

Sol: 2

Practice Questions

Q1 Question 1-15 ARE OF 1 MARKS EACH

Which of the following represents the energy in storage?
a) heat b) work
c) internal energy d) none of the mentioned

Sol: c
Explanation: Energy in storage is internal energy or the energy of the system.

Q2 Which of the following can be considered as the definition of energy?

a) Q=ΔE+W b) Q-W=ΔE
c) first law of thermodynamics d) all of the mentioned

Sol: d
Explanation: The first law is a particular formulation of the principle of the
conservation of energy.
Thermodynamics

221.
 Q3 Change in enthalpy of a system is due to heat supplied at
a) constant volume
b) constant pressure
c) both at constant volume and pressure
d) none of the mentioned

Sol: b
Explanation: Change in enthalpy occurs when heat is given to a system at
constant pressure.

Q4 The specific heat of a substance at constant pressure is defined as the rate

of change of ___ with respect to___
a) work,pressure b) enthalpy,temperature
c) enthalpy,pressure d) heat,temperature

Sol: b
Explanation: cp=∂h/∂T at constant pressure.

Q5 In a throttling device, what do we get as SFEE when changes in potential

energy and kinetic energy are taken zero?
a) dQ/dm≠0 b) dW/dm≠0
c) h1=h2 d) none of the mentioned

Sol: c
Explanation: Enthalpy of the fluid before throttling is equal to the enthalpy of
the fluid after throttling.
Thermodynamics

222.
Q6 Turbines and engines ____ positive power output, and compressors and
pumps ____ power input.
a) require,give b) give, require
c) give, give d) require,require

Sol: b
Explanation: This is the basic information about turbines, engines, compres-
sors and pumps.

Q7 For an inviscid frictionless fluid flowing through a pipe, Euler equation is

given by
a) Vdp+VdV+gdZ=0 b) Vdp-VdV+gdZ=0
c) Vdp-VdV-gdZ=0 d) none of the mentioned

Sol: a
Explanation: Euler equation is derived from steady flow energy equation.

Q8 In ____ filling a bottle with air at 300K, the gas temperature rises to 420K
due to flow work being converted to ____ increase.
a) adiabatically, heat b) adiabatically, internal energy
c) constant pressure, heat d) none of the mentioned

Sol: b
Explanation: flow work is converted to increase in molecular internal energy.

Q9 The piston/cylinder contains carbon dioxide at 300 kPa, with volume of 0.2
m3 and at 100°C. Mass is added at such that the gas compresses with PV(1.2)
= constant to a final temperature of 200°C. Determine the work done during
the process.
a) -80.4 kJ b) -40.4 kJ c) -60.4 kJ d) -50.4 kJ
Thermodynamics

Sol: a
Explanation: Work done = (P2V2 – P1V1)/(1-n) and mR = (P1V1)/T1 = 0.1608 kJ/K
Work done = 0.1608(473.2 – 373.2)/(1 – 1.2) = -80.4 kJ.

223.
 Q10 Helium in a piston/cylinder at 20°C, 100 kPa is brought to 400 K in a reversi-
ble polytropic process with exponent n = 1.25. Helium can be assumed to be
an ideal gas with constant specific heat. Find the specific work.
a) -587.7kJ/kg b) -687.7kJ/kg
c) -787.7kJ/kg d) -887.7kJ/kg

Sol: d
Explanation: Process: PVn = C & PV = RT => TV^(n-1) = C
Cv = 3.116 kJ/kg K, R = 2.0771 kJ/kg K
V2 / V1 = (T1 / T2 )^[1/(n-1)] = 0.2885
P2 / P1 = (V1 / V2)^(n) = 4.73 => P2 = 473 kPa
W = (P2 V2 – P1 V1)/(1-n) = R(T2-T1)/(1-n) = -887.7 kJ/kg

Q11 Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the
rate of waste heat rejection to a nearby river is 50 MW, determine the ther-
mal efficiency for this heat engine.

a) 47.5% b) 27.5%
c) 37.5% d) none of the mentioned

Sol: c
Thermodynamics

Explanation: The thermal efficiency of heat engine = net work output / heat
input
= 30/80 = 0.375 = 37.5 %.

224.
Q12 The function of a heat engine cycle is to _____ continuously at the expense
of _____ to the system.
a) heat input, produce work b) produce work, heat input
c) can be both of the mentioned d) none of the mentioned

Sol: b
Explanation: Net work and heat input are of primary interest in a cycle.

Q13 According to Kelvin-Planck statement, it is ____ for a heat engine to produce

net work in a complete cycle if it exchanges heat only with bodies at ____
a) impossible, single fixed temperature
b) possible, changing temperature
c) impossible, changing temperature
d) possible, single fixed temperature

Sol: a
Explanation: This is the basic definition of Kelvin-Planck statement.

Q14 If the second law were not true

a) a ship could be driven by extracting heat from the ocean
b) run a power plant by extracting heat from the air
c) both of the mentioned
d) none of the mentioned

Sol: c
Explanation: Both of the above possibilities do not violate the first law but
do violate the second law.
Thermodynamics

225.
 Q15 Which of the following statements are true?
a) a heat pump provides a thermodynamic advantage over direct heating
b) COP for both refrigerator and pump cannot be infinity
c) work input for both refrigerator and pump is greater than zero
d) all of the mentioned

Sol: d
Explanation: W is the electrical energy used to drive the pump or refrigerator
which cannot be zero.

Question 1-15 ARE OF 2 MARKS EACH

Q1 2Marks
In a process, an Acid (1) is mixed with water (2) to form equimolar mixture
in an open vessel (constant P). The vessel is equipped with cooling coils in
order to maintain isothermal conditions. The partial molar enthalpy of water
(2) in KJ/mol based on a reference state of pure water at T and P of mixture
is
−100 x 21
H2 =
( 1 + 0.5 x )
2
1

Find the infinite dilution partial molar enthalpies for Acid based on its refer-
ence state i.e, pure 1 at given T and P
A. 100 KJ/mol B. 11.11 KJ/mol
C. 88.89 KJ/mol D. 50 KJ/mol

Sol: B
According to Gibbs-Duhem equation

∑ x dHi 1
=0

=   x 1dH1 + x2dH2 =

0
dH1 dH2
  x 1 = −x2  
dx 1 dx 1
Thermodynamics

dH2  2 
d  −100 x 1 
Now =
dx 1 dx 1  1 + 0.5 x 2
 ( 1 )

226.
 −1600 x 1 
=
(  x1 + 2)
3

From eq(1)
dH1 1600 x2 
=
dx 1
(  x1 + 2)
3

 dH1 
H1 =    ∫   dx
 dx 1  1
 
1600 x2 
=  ∫  dx 1
(  x1 + 2)
3

1600  1 − x 1 ( )  dx

H1 = ∫ 1
(  x1 + 2)
3

800 ( 2x 1 + 1)
H1
= + constant  ---(2)
( 1 )
3
 
x + 2
Reference state ∴ pure 1 @ T,D
(
H1 T,P =0 )
 H
  1 = H1

=  H
 1
(
800 2x 1 + 1 ) + constant
(  1 + 2)
3

800
=0 + constant 
9
−800
constant =
9
From equation

H1
=
(
800 2x 1 + 1 ) − 800
9
(  x1 + 2)
3

∞ 800 800
To find H1  H
= 1 = 3 − =11.11 kJ / mol
Thermodynamics

9
2 ( )

227.
 Q2 A stream of O2 flowing at 24 Kg/s adiabatically mixed with 35 Kg/sec of N2
stream in a steady state flow process. Assume all streams are at 300K. Find
the rate of entropy change, if gases can be assumed to be ideal. [ Answer in
KJ/sec.K and answer to the nearest integer]

Sol: 10.8 to 11.2

N2 →
ÿ
kg 1000gr 1mol
 =
n1
35 × ×
second 1 kg 28 gr
ÿ
mol
n1 = 1250
sec
ÿ
kg 1000gr 1mol
02 =
n2 =
24 × ×
second 1k
 g 32 gr
ÿ
mol
n2 = 750
sec
ÿ ÿ ÿ
mol
n  =n1 + n2 =2000
second 
ÿ
∆s total =∆
n  sIG
mix

∆sIG −R
mix = ∑ y lnln y  
i i

=
 ( ) ( )
−8.314  0.625lnln 0.625 + 0.375lnln 0.375     

+8.314 0.2937 + 0.3678 
=

J
∆sIG 5.499
mix =
mol .K
ÿ
∆stotal =∆
n  sIG
mix

mol J
= 2000 × 5.499
sec mol.K
KJ
= 10.999
sec.K
Thermodynamics

KJ
≈ 11
secsecK
  

228.
Q3 Equation of state for a particular fluid is given by
P ( v −m ) =
RT . The expression for fugacity coefficient is given by
v m
A. B.
v −m v −m
 mP   −mP 
C. expexp     D. expexp   
 RT   RT 

Sol: C
P dP
lnln 
=∅ ∫ (z − 1) P    (1)
0

(
Given P V − m =
RT )
RT 1 P
P= {also = } (2)
V −m V − m RT
PV V
=
z =
RT V − m
V m
And z=
−1 =−1
V −m V −m
 1  mP
z − 1 m =
=  {from eq. (2)
 V − m  RT
Now from eq. (1)
p mP dP mP
= lnln ∅   =  ∫
0 RT P RT
 mP 
∴∅   = expexp   
 RT 

Thermodynamics

229.
 Q4 A methanol-water vapor liquid system is at equilibrium at 80oC and 80kPa.
The mole fraction of methanol in liquid and vapor are 0.6 and 0.7 respec-
tively. Vapor pressure of methanol and water at 80oC are 90kPa and 30kPa
respectively. Assuming the vapor phase to be an ideal gas mixture, find the
excess free energy in J/mol of liquid mixture.

Sol: 215 to 225

Methanol (1) and water (2)
x 1 = 0.6
x 2 = 0.4
y 1 = 0.7
y 2 = 0.3
P1vap = 90 KPa
P2vap = 30 KPa
T = 80oC , P = 80KPa
y 1P = x1 γ 1P1vap
0.7 x 80 = 0.6 × γ 1 × 90
γ 1 = 1.037 ---(i)
y 2P = x2 γ 2P2vap
0.3 × 80 = 0.7 × γ 2 × 30
γ 2 = 1.1428 --- (ii)
GE
= x 1lnln γ 1 +  x2lnln γ 2  
RT
GE

= [ 0.6lnln 1.037 +  0.4lnln 1.1428 
RT
GE

= 0.02179 + 0.0534
RT
GE = 8.314 × 353 × 0.07519
J
GE = 220.69
mol
Thermodynamics

230.
Q5 The Van Laar activity coefficient model for a binary mixture is given by the
form
A*  B *

= lnln γ 1 =    ,  lnln γ 2      
 A* x1   B* x 2 
 1 + *   1 + 
 B x2   A * x 1 

Given γ 1 = 1.5 , γ 2 = 1.2

And x 1 = 0.3 , x = 0.7
Determine the value of A* and B*
A. A* = 1.5 , B* = 0.65 B. A* = 1.6 , B* = 0.75
C. A* = 1.7 , B* = 0.69 D. A* = 1.8 , B* = 0.81

Sol: C
2
 * x2 lnln γ 2  
A =1 +  lnln γ 1  
 x 1 lnln γ 1  
2
 0.7 lnln 1.2 
= 1 + ×  × lnln 1.5 
 0.3 lnln 1.5 

A* = 1.702
2
*
 x 1 lnln γ 1  
B =1 +  lnln γ 2  
 x2 lnln γ 2  
2
 0.3 lnln 1.5 
                    = 1 + ×  × lnln 1.2 
 0.7 lnln 1.2 
B* = 0.6954

Thermodynamics

231.
 Q6 The excess Gibb’s free energy of liquid mixture is given by
GE
= Ax 1 x 2
RT
For what value of A will the mixture exhibit immiscibility?
1 1
A. A < B. A ≥
x 1  x 2  
x 1  x 2  
1 1
C. A < D. A ≥
2x 1  x 2   2x 1  x 2  

Sol: D
We know that for completely miscibility
∂2 ∆G
>0
∂x2
∆G GE
Also = x1lnln x1 +  x2lnln x2 +  
RT RT

∴
∂2 ( ∆G / RT )
=+
1 (
∂2 GE / RT )
∂x21 x1  x2 ∂x21
∴ for stability

(
∂ 2 GE / RT )+ 1
>0
∂x21 x 1  x2

And in given question immiscibility is asked

∴ for immiscibility

(
∂ 2 GE / RT )+ 1
≤ 0 ---(1)
∂x21 x 1  x2

 GE 
Given   = Ax 1  x2
 RT 
 

(
∂   GE / RT )
= A(x2 −  x 1 ) 
∂x 1 

(
∂ 2 GE / RT )= −2A
Thermodynamics

∂x21
∴ from equation (1)

232.
 1
−2A + ≤0
x 1  x2
−1
−A ≤
2x 1  x2
1
∴ A ≥ for immiscibility
2x 1  x2

Q7 MSQ type question

Calculate the change in entropy when 2 gram of ice at 0oC is converted into
steam at 100 oC. The latent heat of fusion of ice = 80 cal/gr . Latent heat of
vaporization = 560 cal/gr and mean specific heat of water b/w 0 oC and 100
o
C is 1.05 cal/ g oC
A. 0.3277 cal/g oC B. 2.122 cal/g oC
C. 1.503 cal/g C
o
D. 4.244 cal/oC

Sol: B and D
dθ
∆S =
T ∫
∆S = Entropy change for melting of ice ( ∆S1 ) + Entropy change for change of
T of water from 0 oC to 100 oC ( ∆S2 ) + Entropy change for vaporization of
water ( ∆S3 )
∆Q 80
∆S1 = = = 0.293
T1 273
dQ cp  dT T
∆S=
2 ∫ =
T ∫ T
= cplnln  2  
T1
373

= ∆S2 1.05lnln 
=  0.3277
273
∆Q 560
∆S3 = = = 1.5013
T2 373
∆S  = ∆S1 + ∆S2 + ∆S3
cal
∆S  =
2.122
g C
°
∆Stotal =n ∆S
Thermodynamics

= 2 × 2.122
cal
= 4.244
 C
°

233.
 Q8 An engine operates between temperature limits of 900K, T2 and another
between T2 and 200K. For both to be equally efficient. The value of T2 (in K)
will be _________.

Sol: 422 to 426

In case of equally efficient
i.e, η 1 = η 2
T 200
1− 1−
=
900 T
T2 900 × 200
=
T = 424.26K

Q9 The normal boiling point of a component ‘X’ is 360K. Heat of vaporization ∆

Hvap = 30 KJ/mol. The pressure required to boil ‘X’ at 300K is ________. Torr
(Round off to two Decimal places.) Ignore the temperature variation of ∆
Hvap.

Sol: 101 to 104

T1 = 360K
∆ Hvap = 30 KJ/mol
T2 = 300K
Using Clasius Clapyreon equation
P2 1 1
∆Hvap 
ln = − 
P1 R
 T1 T2 
=P1 1 =
atm   at  T1 360K
P 30 × 1000  1 1 
=lnln  2  −  
1 8.314  360 300 
Thermodynamics

P2 = 0.1347 atm
=P2 0.1347 × 760 torr
= 102.377 Torr

234.
Q10 A Boiler handles 1kg/sec of Air at 40 ° C and consumes power of 15 KW. The
velocities of inlet and outlet are 50m/sec and 75m/sec respectively. Find the
Exit Air temperature assuming Adiabatic condition Cp = 1.005 KJ/KgK of Air
A. 47.5°C B. 53.3°C C. 67.8°C D. 75°C

Sol: B
From S.F.F.E
ÿ  v2  dQ ÿ  v2  dW
m1 h1 + 1 + gz1  + = m2 h2 + 2 + gz2  +
 2  dt  2  dt
ÿ ÿ
kg
Here m
=1
m
=2
1
sec
z1 = z2
dQ
=0
dt
v 21 v 22 dW
h1 + = h2 + +
2 2 dt

(50)  ( 75) 
2 2

h1 +
2
= h2 +
2
(
+ −15 × 103    )
dW
{As power is consumed = −15KW }
dt

(50)  ( 75) 
2 2

h2 − h1 = ( 15 × 10 ) + 
3
2
−
2
h2 − h1 =
13437.5
(
cp T2 − T1 =
13437.5 )
13437.5
T2 − T1 =
1005
T2 − T1 =
13.37
T
=2
40 + 13.37
=
T2 53.37°C
Thermodynamics

235.
 Q11 The properties of a certain fluid are related as follow
u= 196 + 0.718T
PV = 0.287 (T+273)
Where u is specific internal energy (KJ/Kg) T is in °C , P is pressure (KN/m2)
and V is specific volume (m3/kg). Find the Ratio of specific heat capacities
(Cp/Cv)

Sol: 1.38 to 1.42

 ∂h 
cp =  
 ∂T p

(
 ∂ u + PV
=
) 
 ∂T 
 p
∂
=  196 + 0.718T + 0.287T + 78.351
∂T 
∂
=  1.005T + 274.351
∂T 
cp = 1.005

 ∂U 
cv =  
 ∂T  V
∂

=
∂T
(
196 + 0.718T )
cv = 0.718
cp 1.005
=
γ = = 1.4
cv 0.718
Thermodynamics

236.
Q12 An imaginary engine receives heat and does work on a slowly moving pis-
ton at such rates that the cycle of operation of 1kg of working fluid can be
represented as a circle of 15cm in diameter or a PV diagram on which 1cm =
300KPa and 1cm = 0.2 m3/kg. If heat rejected by an engine in a cycle is 15000
KJ/Kg of working liquid, what will be the thermal efficiency of the engine, if
it is defined as the ratio of work done to the heat input into the cycle.
A. 36.36% B. 41.41% C. 53.53% D. 77.77%

Sol: B
Given Diameter = 15cm
π π
( ) ( )
2 2
Area = D = 15 = 176.71cm2
4 4
1cm = 300 KPa x 0.20 m3/kg
2

= 60 KJ/Kg
Therefore, Work = 176.71 × 60 = 10602.87 KJ/Kg
Heat Rejected = 15000 KJ/kg
Heat input = (10602.87 + 15000) KJ/kg
= 25602.87
work 10602.87
Hence, η =   =  
Heat input 25602.87
η = 0.414128
η = 41.41%

Q13 An ideal gas Cp = 5R/2 is heated in a steady flow heat exchanger from 80 °C
to 200 °C by another stream of same ideal gas entering at 400 °C . The flow
rate of two streams are the same. Calculate total entropy change I.e, sum of
entropy change for hot gas and cold gas stream
A. 0.24R B. 0.73R C. 1.22R D. 0.49R

Sol: A
Entropy change for constant pressure
T2
∂S =
 nCp ln
T1
Thermodynamics

n =  1
5R
Cp =
2

237.
 A. Entropy change of cold gas stream
T1 = 273 + 80 = 353K
T2 = 273 + 200 = 473K
5R 473
( )
     ∂S  =
c
 1 × l n
2 353
    ( ∂S )  =
 0.731R
 
c

B. Entropy change of hot gas stream

T1 = 273 + 400 = 673K
(mCp)h ( T1 − T2 )h  =
( )c ( T2  – T1 )c
 mCp

      673 – T2  =  473 – 353
      T2  =  553
5R 553
∂S = l n
2 673
( ∂s)h  = −0.491R  

( ∂s)total  = ( ∂s)c  +  ( ∂s)h  = 0.24R

Q14 In a closed piston-cylinder system, methane was observed in the following

equation of state P (V – nb) = nRT where b=0.031m3/mol. The temperature
and volume are 550 °C and 10m3 respectively for 50 mole of methane. At this
state of system, the isobaric rate of change of temperature with volume (in
°C /m3) is ________ ?? (Answer upto 3 decimal place)

Sol: 96.5 to 98.0

(
P V –n )
  b  =  nRT

=T 
P V –n (
 b
=
−PV bP
−
)
nR nR R
dT P
| =
dV p=const nR
nRT
P=
(
V – nb   )
Thermodynamics

dT nRT T
= | =
dV p=const ( )( ) ( V – nb)
V – nb nR  

238.
 823 823
= =
10 − 50 × 0.031 8.45
K
= 97.396 3
m

= ° / m3    
97.396 C

Q15 MSQ QUESTION

Which of the following represent a Carnot cycle?

Sol: A., B. and C.

As process 2 → 3 and 4 → 1 is isentropic and isentropic is Reversible adia-
batic, so option a and b are correct.
Also the T-S diagram of the Carnot cycle is given by ‘c’.
So answer A., B. and C. are correct
Thermodynamics

239.