Basic Thermodynamics [BME304] By: Mr. Yuvaraj K. B.

Module-4: Availability, Irreversibility & General Thermodynamic

Relations and Pure Substances

Syllabus
Availability, Irreversibility and General Thermodynamic relations. Introduction, Availability
(Exergy), Unavailable energy, Relation between increase in unavailable energy and increase in
entropy. Maximum work, maximum useful work for a system and control volume, irreversibility.
Problems
Pure Substances: P-T and P-V diagrams, triple point and critical points. Sub-cooled liquid,
saturated liquid, mixture of saturated liquid and vapor, saturated vapor and superheated vapor
states of pure substance with water as example. Enthalpy of change of phase (Latent heat).
Dryness fraction (quality), T-S and H-S diagrams, representation of various processes on these
diagrams. Steam tables and its use. Throttling calorimeter, separating and throttling calorimeter.
Problems.
Notes

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Thermodynamics – 21ME34 Mr. Yuvaraj K.B.

AVAILABLE ENERGY AND EXERGY

There are many forms in which energy can exist. But even under ideal conditions all these
forms cannot be converted completely into work. This indicates that energy has two parts:
— Available part.
— Unavailable part.

Available energy:
‘Available energy’ is the maximum portion of energy which could be converted into useful
work by ideal processes which reduce the system to a dead state (a state in equilibrium with
the earth and its atmosphere). Because there can be only one value for maximum work which
the system alone could do while descending to its dead state, it follows immediately that
‘Available energy’ is a property.

Unavailable energy:
A system which has a pressure difference from that of surroundings, work can be obtained
from an expansion process, and if the system has a different temperature, heat can be
transferred to a cycle and work can be obtained. But when the temperature and pressure
becomes equal to that of the earth, transfer of energy ceases, and although the system
contains internal energy, this energy is unavailable.

Availability (Exergy):
The theoretical maximum amount of work which can be obtained from a system at any state
p1 and T1 when operating with a reservoir at the constant pressure and temperature p0 and T0
is called ‘availability’.

Maximum work in a reversible process:

The available energy (A.E.) or the available part of the energy supplied is the maximum work
output obtainable from a certain heat input in a cyclic heat engine (Fig. 6.1). The minimum
energy that has to be rejected to the sink by the second law is called the unavailable energy
(U.E.), or the unavailable part of the energy supplied.

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Thus unavailable energy is the product of the lowest temperature of heat rejection, and the
change of entropy of the system during the process of supplying heat (Fig. 6.3).

Useful Work:
All of the work W of the system with a flexible boundary would not be available for delivery,
since a certain portion of it would be spent in pushing out the atmosphere (Fig. 8.12). The
useful work is defined as the actual work delivered by a system less the work performed on
the atmosphere. If V1 and V2 are the initial and final volume of the system and p0 is the
atmospheric pressure, then the work done on the atmosphere is p0 (V2 - V1). Therefore, the
useful work Wu becomes

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Maximum Useful Work Obtained when the System Exchanges Heat with a Thermal
Reservoir in Addition to the Atmosphere:

If the open system exchanges heat with a thermal energy reservoir at temperature TR in
addition to the atmosphere, the maximum useful work will be increased by d QR ( l – TO/TR),
where d QR is the heat received by the system. For a steady flow process,

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Dead State:
If the state of a system departs from that of the surroundings, an opportunity exists for
producing work (Fig. 8.13). However, as the system changes its state towards that of the
surroundings, this opportunity diminishes, and it ceases to exist when the two are in
equilibrium with each other. When the system is in equilibrium with the surroundings, it must
be in pressure and temperature equilibrium with the surroundings, i.e., at p0 and T0. It must
also be in chemical equilibrium with the surroundings, i.e., there should not be any chemical
reaction or mass transfer. The system must have zero velocity and minimum potential energy.
This state of the system is known as the dead state, which is designated by affixing subscript
'O' to the properties.
Any change in the state of the system from the dead state is a measure of the available work
that can be extracted from it. Farther the initial point of the system from the dead state in
terms of p, t either above or below it, higher will be the available energy or exergy of the
system (Fig. 8.13). All spontaneous processes terminate at the dead state.

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Availability (Exergy):
Whenever useful work is obtained during a process in which a finite system undergoes a
change of state, the process must terminate when the pressure and temperature of the system
have become equal to the pressure and temperature of the surroundings, p 0 and T0, i.e., when
the system has reached the dead state. An air engine operating with compressed air taken
from a cylinder will continue to deliver work till the pressure of air in the cylinder becomes
equal to that of the surroundings, p0. A certain quantity of exhaust gases from an internal
combustion engine used as the high temperature source of a beat engine will deliver work
until the temperature of the gas becomes equal to that of the surroundings, T0.

The availability (A) of a given system is defined as the maximum useful work (total work
minus pdV work) that is obtainable in a process in which the system comes to equilibrium
with its surroundings. Availability is thus a composite property depending on the state of
both the system and surroundings.

1. Availability in a Steady Flow Process:

The reversible (maximum) work associated with a steady flow process for a single flow is
given by Eq. (8.25)

With a given state for the mass entering the control volume, the maximum useful work
obtainable (i.e., the availability) would be when this mass leaves the control volume in
equilibrium with the surroundings (i.e., at the dead state). Since there is no change in volume,
no work will be done on the atmosphere. Let us designate the initial state of the mass entering
the C.V. with parameters having no subscript and the final dead state of the mass leaving the
C.V. with parameters having subscript 0. The maximum work or availability, A, would be

where φ is called the availability function for a steady flow system and VO= 0. This is the
availability of a system at any state as it enters a C. V. in a steady flow process. The
availability per unit mass would be

If subscripts I and 2 denote the states of a system entering and leaving a C.V., the decrease in
availability or maximum work obtainable for the given system surroundings combination
would be

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2. Availability in a Nonflow Process:

Let us consider a closed system and denote its initial state by parameters without any
subscript and the final dead state with subscript 'O'. The availability of the system A, i.e., the
maximum useful work obtainable as the system reaches the dead state, is given by Eq. (8.40).

Second Law Efficiency:

A common measure on energy use efficiency is the first law efficiency, η I. The first law
efficiency is defined as the ratio of the output energy of a device to the input energy of the
device. The first law is concerned only with the quantities of energy, and disregards the forms

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AVAILABLE ENERGY AND EXERGY

1) One kg of air is compressed polytropically from 1 bar pressure and temperature of 300 K
to a pressure of 6.8 bar and temperature of 370 K. Determine the irreversibility if the sink
temperature is 293 K. Assume R = 0.287 kJ/kg K, cp = 1.004 kJ/kg K and cv = 0.716 kJ/kg
K.

2) A system at 500 K receives 7200 kJ/min from a source at 1000 K. The temperature of
atmosphere is 300 K. Assuming that the temperatures of system and source remain constant
during heat transfer find out :
(i) The entropy produced during heat transfer ;
(ii) The decrease in available energy after heat transfer.

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3) Calculate the decrease in available energy when 20 kg of water at 90°C mixes with 30 kg
of water at 30°C, the pressure being taken as constant and the temperature of the
surroundings being 10°C.
Take Cp of water as 4.18 kJ/kg K.

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4) In a certain process, a vapour, while condensing at 420°C, transfers heat to water

evaporating at 250°C. The resulting steam is used in a power cycle which rejects heat at
35°C. What is the fraction of the available energy in the heat transferred from the process
vapour at 420°C that is lost due to the irreversible heat transfer at 250°C?

5) The moment of inertia of a flywheel is 0.54 kg-m2 and it rotates at a speed 3000 RPM in a
large heat insulated system, the temperature of which is l5°C. If the kinetic energy of the
flywheel is dissipated as frictional beat at the shall: bearings which have a water equivalent of
2 kg, find the rise in the temperature of the bearings when the flywheel bas come to rest.
Calculate the greatest possible amount of this heat which may be returned to the flywheel as
high-grade energy, showing how much of the original kinetic energy is now unavailable.
What would be the final RPM of the flywheel, if it is set in motion with this available
energy?

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6) Two kg of air at 500 kPa, 80°C expands adiabatically in a closed system until its volume is
doubled and its temperature becomes equal to that of the surroundings which is at 100 kPa,
5°C. For this process, determine (a) the maximum work, (b) the change in availability, and (
c) the irreversibility. For air, take c. = 0.718kJ/kg K, 11 = c.T where cv is constant, and
pV= mRT where p is pressure in kPa, V volume in m3, m mass in kg, Ra constant equal to
0.287 kJ/kg K, and T temperature in K.

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7) Air expands through a turbine from 500 kPa, 520°C to 100 kPa, 300°C. During expansion
l0 kJ/kg of heat is lost to the surroundings which are at 98 kPa, 20°C. Neglecting the K.E.
and P.E. changes, determine per kg of air (a) the decrease in availability, (b) the maximum
work, and (c) the irreversibility
For air, Ice CP = 1.005 kJ/kg K. h= CP T where CP is constant, and the p, V and T
relation as in previous exercise.

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8) A mass of IOOO kg of fish initially at 1 bar, 300K is to be cooled to - 20°C. The freezing
point of fish is - 2.2°C, and the specific beats of fish below and above the freezing point are
1.7 and 3.2 kJ/kg K respectively. The latent heat of fusion for the fish can be taken as 235
kJ/kg. Calculate the exergy produced in the chilling process. Take T0 = 300 K and Po= 1bar.

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9) 15 kg of water is heated in an insulated tank by a churning process from 300 K to 340 K. If

the surrounding temperature is 300 K, find the loss in availability for the process.

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10) 5 kg of air at 550 K and 4 bar is enclosed in a closed system.

(i) Determine the availability of the system if the surrounding pressure and temperature are
1 bar and 290 K respectively.
(ii) If the air is cooled at constant pressure to the atmospheric temperature, determine the
availability and effectiveness.

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THE PURE SUBSTANCE

OBJECTIVE: Introduce the concept of a pure substance and Illustrate the P-v , T-v and P-T
property diagrams and P-v-T surfaces of pure substances. Demonstrate the procedures for
determining thermodynamic properties of pure substances from tables of property data.

STRUCTURE:
4. Introduction
4.1 Application of 1st law of thermodynamics for a closed system

4. Introduction: The system encountered in thermodynamics is often quite less complex and consists of
fluids that do not change chemically, or exhibit significant electrical, magnetic or capillary effects. These
relatively simple systems are given the generic name the Pure Substance.
“A system is set to be a pure substance if it is (i) homogeneous in chemical composition, (ii)
homogeneous in chemical aggregation and (iii) invariable in chemical aggregation.”

Pure Substances
Define Pure Substance:
A substance that has a fixed chemical composition throughout is called a pure substance such as water, air,
and nitrogen.
A pure substance does not have to be of a single element or compound. A mixture of two or more phases of
a pure substance is still a pure substance as long as the chemical composition of all phases is the same.

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Phases of a Pure Substance

A pure substance may exist in different phases. There are three principal phases solid, liquid, and gas.
A phase: is defined as having a distinct molecular arrangement that is homogenous throughout and
separated from others (if any) by easily identifiable boundary surfaces.
A substance may have several phases within a principal phase, each with a different molecular structure.
For example, carbon may exist as graphite or diamond in the solid phase, and ice may exist in seven
different phases at high pressure.
Molecular bonds are the strongest in solids and the weakest in gases.
Solid: the molecules are arranged in a three-dimensional pattern (lattice) throughout the solid. The
molecules cannot move relative to each other; however, they continually oscillate about their equilibrium
position.
Liquid: the molecular spacing in liquid phase is not much different from that of the solid phase (generally
slightly higher), except the molecules are no longer at fixed positions relative to each other.
Gas: the molecules are far apart from each other, and a molecular order does not exist. Gas molecules move
randomly, and continually collide with each other and the walls of the container they are in.
Molecules in the gas phase are at a considerably higher energy level than they are in liquids or solid phases.
Phase-Change Processes of Pure Substances:
Consider a process where a pure substance starts as a solid and is heated up at constant pressure until it all
becomes gas. Depending on the prevailing pressure, the matter will pass through various phase
transformations. At P0:
1. Solid
2. Mixed phase of liquid and solid
3. Sub-cooled or compressed liquid (means it is not about to vaporize)4. Wet vapor or saturated liquid-
vapor mixture, the temperature will stop rising until the liquid is completely vaporized.

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5.Superheated vapor (a vapor that is not about to condense).

Fig. 1: T-v diagram for the heating process of a pure substance.

 At a given pressure, the temperature at which a pure substance starts boiling is called the saturation
temperature, Tsat.
 Likewise, at a given temperature, the pressure at which a pure substance starts boiling is called the
saturation pressure, Psat.
 During a phase-change process, pressure and temperature are dependent properties, Tsat = f (Psat).
 The critical point is the point at which the liquid and vapor phases are not distinguishable
 The “triple point” is the point at which the liquid, solid, and vapor phases can exist together. On P-v or
T-v diagrams, these triple-phase states form a line called the triple line.
Table 1: Critical and triple point for water and oxygen.

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Critical Point Triple Point

P (atm) T (K /°C) P (atm) T (K /°C)

H2O 218 647.30/(374.14) 0.006 273.17 (0.01)

O2 50.136 154.80/(−118.36) 0.0015 54.16/(−219)

Vapor Dome
The general shape of a P-v diagram for a pure substance is very similar to that of a T-v diagram.

P
critical point
SUPERHEATED
sat. vapor line VAPOR REGION

COMPRESSED
LIQUID
REGION T2 = const. >T1

SATURATED
sat. liquid LIQUID-VAPOR
line REGION T1 = const

P-v diagram of a pure substance.

The P-T or Phase Change Diagram

This is called phase diagram since all three phases are separated from each other by three lines. Most pure
substances exhibit the same behavior.
 One exception is water. Water expands upon freezing.

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phase diagram of pure substances.

There are two ways that a substance can pass from solid phase to vapor phase i) it melts first into a liquid
and subsequently evaporates, ii) it evaporates directly without melting (sublimation).
 the sublimation line separates the solid and the vapor.
 the vaporization line separates the liquid and vapor regions
 the melting or fusion line separates the solid and liquid.
 these three lines meet at the triple point.
 if P<PTP , the solid phase can change directly to a vapor phase
 at P<PTP the pure substance cannot exist in the liquid phase. Normally (P>PTP ) the substance
melts into a liquid and then evaporates.
 matter (like CO2) which has a triple point above 1 atm sublimate under atmospheric conditions
(dry ice)
 for water (as the most common working fluid) we are mainly interested in the liquid and vapor
regions. Hence, we are mostly interested in boiling and condensation.

Property Tables
For most substances, the relationships among thermodynamic properties are too complex to be expressed by
simple equations. Thus, properties are frequently presented in the form of tables, see Table A-4.

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The subscript “f” is used to denote properties of a saturated liquid and “g” for saturated vapor. Another
subscript, “fg”, denotes the difference between the saturated vapor and saturated liquid values of the same
property.
For example:
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = difference between vg and vf ( vfg = vg – vf)
Enthalpy: is a property defined as H = U + PV (kJ) or h = u + Pv (kJ/kg) (per mass unit).
Enthalpy of vaporization (or latent heat): represents the amount of energy needed to vaporize a unit mass of
saturated liquid at a given temperature or pressure. It decreases as the temperature or pressure increase, and
becomes zero at the critical point.

1- Saturated Liquid-Vapor Mixture

During vaporization, a mixture of part liquid part vapor exists. To analyze this mixture, we need to know
the proportions of the liquid and vapor in the mixture. The ratio of the mass of vapor to the mass of the total
mixture is called quality, x:
m vapor
x mtotal  mliquid  mvapor  m f  m g
m total
Saturated liquid-vapor mixture is treated as a combination of two sub-systems (two phases). The properties
of the “mixture” are the average properties of the saturated liquid-vapor mixture.
V  V f  Vg
mt v ave  m f v f  m g v g
m f  mt  m g  mt v ave  mt  m g v f  m g v g
dividing by m t
v ave  1  x v f  xv g and x  m g / mt
v ave  v f  xv fg m 3
/ kg 
or,
v ave  v f
x
v fg

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P or critical point
T

sat.
sat. vapor
liquid states
states

sat. vapor

sat. liquid

Fig. 4: The relative amounts of liquid and vapor phases (quality x) are used to calculate the mixture
properties.
Similarly,
u ave  u f  xu fg
have  h f  xh fg
Or in general, it can be summarized as yave = yf +x.yfg. Note that:
0  x 1
y f  y ave  y g
Note: pressure and temperature are dependent in the saturated mixture region.

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Fig. 5: Quality defined only for saturated liquid-vapor mixture.

Example 1: Saturated liquid-vapor mixture

A closed, rigid container of volume 0.5 m3 is placed on a hot plate. Initially the container holds a two-phase
mixture of saturated liquid water and saturated water vapor at P1= 1 bar with a quality of 0.5. After heating,
the pressure in the container is P2=1.5 bar. Indicate the initial and final states on a T-v diagram, and
determine:
a) the temperature, in °C, at each state.
b) the mass of vapor present at each state, in kg.
c) if heating continues, determine the pressure, in bar, when the container holds only saturated vapor.
Solution:
Assumptions:
1. Water in the container is a closed system.
2. States 1, 2, and 3 are equilibrium states.
3. The volume of container remains constant.
Two independent properties are required to fix state 1 and 2. At the initial state, the pressure and quality are
known. Thus state 1 is known, as mentioned in the problem. The specific volume at state 1 is found using
the given quality:
v1  v f 1  x1 v g1  v f 1 
From Table A - 5 at P  1 bar  100 kPa
v1  0.001043  0.5 (1.694  0.001043)  0.8475 m 3 / kg
At state 2, the pressure is known. Volume and mass remain constant during the heating process within the
container, so v2=v1. For P2= 0.15 MPa, Table A-5 gives vf2= 0.001053 and vg2=1.1593 m3/kg. Since
vf2 < v2 < vg2
State 2 must be in the two-phase region as well. Since state 1 and 2 are in the two-phase liquid-vapor
region, the temperatures correspond to the saturation temperatures for the given. Table A-5:
T1 = 99.63 °C and T2 = 111.4 °C
To find the mass of water vapor present, we first find the total mass, m.
V 0.5m 3
m   0.59kg
v 0.8475m 3 / kg
m g1  x1 m  0.50.59kg   0.295kg

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3
P2 = 1.5 bar

2
P1 = 1 bar
1

The mass of vapor at state 2 is found similarly using quality x2. From Table A-5, for P2 = 1.5 bar, we have:
v vf2
x2 
vg 2  v f 2
0.8475  0.001053
x2   0.731
1.159  0.001053
mg 2  0.731 0.59kg   0.431 kg
If heating continued, state 3 would be on the saturated vapor line, as shown in on the T-v diagram above.
Thus, the pressure would be the corresponding saturation pressure. Interpolating in Table A-5 at vg =
0.8475 m3 /kg, we get P3 = 2.11 bar.
2- Superheated Vapor
Superheated region is a single phase region (vapor only), temperature and pressure are no longer dependent.
See Table A-6 for superheated vapor properties.
If T>> Tcritical or P<<Pcritical, then the vapor can be approximated as an “ideal gas”.
3- Compressed (or Sub-cooled) Liquid
The properties of a liquid are relatively independent of pressure (incompressible).
A general approximation is to treat compressed liquid as saturated liquid at the given saturation
temperature.

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Determination the dryness fraction:

 Separating calorimeter:

The quality of wet steam is usually defined by its dryness fraction. When the dryness fraction, pressure and
temperature of the steam are known, then the state of wet steam is fully defined. In a steam plant it is at
times necessary to know the state of the steam. For wet steam, this entails finding the dryness fraction.
When the steam is very wet, we make use of a separating calorimeter.
Construction of separating calorimeter is as shown in figure:

The steam is collected out of the main steam supply and enters the separator from the top. The steam is
forced to make a sharp turn when it hits the perforated cup (or any other mechanism that produces the same
effect). This results in a vortex motion in the steam, and water separates out by the centrifugal action. The
droplets then remain inside the separator and are collected at the bottom, where the level can be recorded
from the water glass. The dry steam will pass out of the calorimeter into a small condenser for the collection
of the condensate. However, not all the water droplets remain in the collector tank. Some water droplets
pass through to the condenser, and hence this calorimeter only gives a close approximation of the dryness
fraction of the steam.
From the results obtained from the two collectors, the dryness fraction may then be found from

Dryness fraction =

This can be expressed as:

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x=
Where,
M is the mass of dry steam and
m is the mass of suspended water separated in the calorimeter in the same time.
 Throttling calorimeter:
If we have steam that is nearly dry, we make use of a throttling calorimeter as shown in figure. This
calorimeter is operated by first opening the stop valve fully so that the steam is not partially throttled as it
passes through the apparatus for a while to allow the pressure and temperature to stabilize. If the pressure is
very close to atmospheric pressure, the saturation should be around 100°C, it may be assumed that the
steam is superheated.
When the conditions have become steady, the gauge pressure before throttling is read from the pressure
gauge. After throttling, the temperature and gauge pressure are read from the thermometer and manometer
respectively. The barometric pressure is also recorded.
From equation = ,
We have at p1 = at p2

And thus x =

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List of Formulas:
1. Dryness fraction of steam sample entering Separating Calorimeter = x =
Where,M is the mass of dry steam and
m is the mass of suspended water separated in the calorimeter in the same time.
2. Dryness fraction of steam sample entering Throttling calorimeter
We have hW at p1 = hsup at p2

And thus x=

3. Dryness Fraction = x = Mass of dry steam / Mass of wet steam

4. Specific Enthalpy of wet steam at Pressure P = h = hf + x hfg KJ/Kg (Similarly specific entropy, specific
volume can be calculated)
5. Enthaply(h) = Internal energy(u) + (P.v)
6. Specific heat at constant volume = CV = du/dt
7. Specific heat at constant pressure = CP = dh/dt
8. Specific heat at constant pressure for dry steam = CPs = 2.1KJ/Kg.K

OUTCOME: Demonstrate understanding of key concepts including phase and pure substance, state
principle for simple compressible systems, p-v-T surface, saturation temperature and saturation pressure,
two-phase liquid-vapor mixture, quality, enthalpy, and specific heats.Apply the closed system energy
balance with property data.

IMPORTANT QUESTIONS:
1. With a neat sketch explain how Combined separating and throttling calorimeter can be used to
measure the dryness fraction of wet vapour
2. With a neat sketch explain throttling calorimeter can be used to measure the dryness fraction of wet
vapour
3. Draw phase equilibrium diagram of water on P-T Coordinates indicating triple and critical point
4. Steam initially at 1.5 MPa 300˚C expands reversibly and adiabatically in a steam turbine to 40˚C .
Determine the ideal work output of the turbine per kg of steam

FURTHER READING:
1. Basic Engineering Thermodynamics, A.Venkatesh, Universities Press, 2008
2. Basic and Applied Thermodynamics, P.K.Nag, 2nd Ed., Tata McGraw Hill Pub.
3. http://www.nptel.ac.in/courses/112104113/4#

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Problems

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Department of Mechanical Engineering, ATMECE Mysuru Page 97

 BASIC THERMODYNAMICS 2018

Department of Mechanical Engineering, ATMECE Mysuru Page 98

 BASIC THERMODYNAMICS 2018

Department of Mechanical Engineering, ATMECE Mysuru Page 99

 BASIC THERMODYNAMICS 2018

Department of Mechanical Engineering, ATMECE Mysuru Page 100

 BASIC THERMODYNAMICS 2018

Department of Mechanical Engineering, ATMECE Mysuru Page 101