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THERMODYNAMICS
CONTENTS
Thermodynamic system, surroundings, universe,
system boundary
1
Types of thermodynamic system
Macroscopic and microscopic point view
Properties of system
Intensive and Extensive properties
BASIC CONCEPTS State of system
IN THERMODYNAMICS Thermodynamic process, path and cycle
Thermodynamic equilibrium
Quasi-static process
Concept of continuum
Point function and path function
Working substance
Pressure
Mass Density
Weight Density
Specific volume
Specific gravity
Solved Examples
Zeroth law of thermodynamics
Thermometric property
2
Electrical resistance thermometer
Thermocouple
Ideal gas thermometers
Constant volume gas thermometers
TEMPERATURE Constant pressure gas thermometers
Temperature scales
Thermodynamic temperature scales
Ideal gas
Ideal gas temperature
International Practical temperature scales
Solved Example
Energy transfer by work
3
WORK AND HEAT
Energy transfer by heat
Indicator diagram
Free expansion
Solved Example
TRANSFER
4
FIRST LAW OF
First law for cyclic process
First law for a system undergoing change of state
Work and heat transfer for various process for
closed system
THERMODYNAMICS PV graph for various processes
Internal energy
Enthalpy
Specific heats for various processes
Solved Examples
Flow work
5
FIRST LAW APPLIED
Steady flow process
Mass balance
Energy Balance
Steady flow energy equation
TO Nonflow energy equation
FLOW PROCESSES Applications of SFEE
Flow work vs Nonflow work
Variable flow processes
Examples of Variable Flow processes
Solved examples
Limitations of first law
Second law helps….
6
Thermal energy reservoirs
Directional law for spontaneous process
Difference between heat and work
Cyclic heat engine
SECOND Reversed heat engine
LAW Kelvin Planck’s statement
OF
PMM2
THERMODYNAMICS
Clausius statement
Equivalence of 2 statements
Reversible process
Carnot cycle and reversed Carnot cycle
Carnot theorem
Heat Transportation
Irreversibility
Causes of irreversibility
Types of irreversibility
Solved Examples
Clausius Inequality
Concept of Entropy
Entropy in terms of thermodynamic properties
TS diagram for various processes
7
ENTROPY
Applications of Entropy Principle
Entropy generation
Solved Example
Available energy
Dead State
Available energy referred to a cycle
Decrease in available energy when heat is
transferred through a finite temperature
difference
Available energy from a finite energy source
8
AVAILABLE ENERGY,
Quality of energy
Law of degradation of energy
Maximum work in reversible process
Reversible work by an open system exchanging
AVAILABILITY heat only with the surroundings
AND Reversible work in steady flow
IRREVERSIBILITY process
Reversible work in a closed system
Useful Work
Maximum work obtainable when system
exchanges heat with a thermal reservoir in
addition to atmosphere
Availability
Availability in a steady flow process
Availability in nonflow process
Availability in chemical reaction
Irreversibility and Gouystodola
theorem
Second law efficiency
Solved examples
Pure Substance
9
PURE SUBSTANCE
Phase
Various terms related to study of pure
substance
Various property diagram
Dryness fraction
10
PROPERTIES
Amagatleduc’s law of partial
volumes
OF GAS MIXTURE
Maxwell equation
TdS Equation
11
Heat Capacity Relationship
Energy Equation
Clausius Claypeyron Equation
Internal energy change for an ideal
THERMODYNAMIC gas
RELATIONS Enthalpy change
Entropy changes
Joule –Thomson coefficient
SOLVED PROBLEMS
THERMODYNAMIC SYSTEM
System is that part of universe which is under investigation or under the study of
observer.
Properties of the system are observed when the exchange of energy i.e. work or heat,
takes place.
There is no arbitrary rule for selection of system but proper selection makes the
calculations easy.
SURROUNDINGS
The remaining portion of universe which is external to the system is called as
surrounding.
The exchange of energy takes place between system and surroundings; hence
surroundings may be influenced by the changes taking place in system.
Figure 1.1
SYSTEM BOUNDARY
System and surroundings in the universe are separated by System boundary.
A system boundary has zero thickness.
Boundary may be Real or Hypothetical and Fixed or Moving.
It is a surface, and since a surface is a two-dimensional object, it has zero volume.
Thus, it attains neither mass nor volume.
Figure 1.2
If heat (energy) exchange doesn’t take place across body it is called adiabatic boundary
otherwise it will be diathermic boundary.
Figure 1.4
GATE TIP
Open system
Heat and work crosses the boundary. Mass transfer also takes place i.e. mass of
system is not fixed
Known as FLOW SYSTEM.
Volume of the system does not change.
Closed System
Heat and work (energy) crosses the boundary. No mass transfer takes place.
Known as NON FLOW SYSTEM.
Volume of the system change.
Isolated System
Heat and work does not cross the boundary.. No mass transfer takes place
Ques 3: Which of these Cases would be best suited for using a control volume approach in the
thermodynamic analysis of the system?
(a) Compression of air in a cylinder
(b) Expansion of gases in a cylinder after combustion
(c) Air in a balloon
(d) Air Filling in a Cycle tyre from any compressor
Solutions
1) (b) As we know that In closed system only energy transfer will happen.
2) Statement (b) is true. Because for isolated system ,system should be a closed system at first.
3) All Systems (a) to (c) are closed systems, so we can’t use control mass for these cases. Only
system (d) is an open system with a fixed boundary because here mass flow and energy transfer
both are taking place so option (d) will be answer.
PROPERTIES OF SYSTEM
Properties are the descriptive and measurable characteristics of the system.
Properties describe the state of a system i.e. has a definite value when system is in a
particular state.
These are macroscopic in nature and hence, can be measured very easily.
Their differential is exact i.e. value can be determined by simply integrating from one
state to another.
They depend only upon the state of system but not on the path followed by the process,
hence are Point function or State function.
Guru Gyan
Thus, Properties are macroscopic characteristics of a system such
as mass, volume, energy, pressure and temperature etc. to which
numerical values can be assigned at a given time without knowledge
of the past history of the system.
EXTENSIVE PROPERTIES are mass dependent. Hence their value depends upon the
size of the system.
An extensive property when expressed as per unit mass becomes an intensive property
(Specific property).
Extensive properties are expressed in upper case letter except mass.
e.g. mass (m), energy (E), enthalpy (H), entropy (S) etc.
.
Ques 1: Here two systems S1 and S2 as shown in Figure 2.1.Both the systems are in similar
states. S3 is the combined system of S1 and S2. Is the value of property for S3 same as that for
S1 and S2 or will have some other value?
Ans.2 - Specific Enthalpy is defined as enthalpy per unit mass so it will not depend on mass and
Pressure will not depend on mass also. Thus both Specific Enthalpy and Pressure both will be
treated as intensive property.
STATE OF A SYSTEM
State of a system is the condition of system at any point of time.
The state of a simple compressible system can be completely specified by two
independent, intensive properties. (This is also called two property rule or state
postulates)
When one or more than one property of system changes, then a change of state of
system takes place.
Note:
A system is called a simple compressible system in the absence of electrical, magnetic,
gravitational, motion, and surface tension effects. (These effects are nearly negligible in
the most of the engineering problems )
Two properties are independent if one property can be varied while the other one is held
constant.
Temperature and specific volume, for example, are always independent properties, and
together they can fix the state of a simple compressible system
Figure 1.6
When change of state takes place in such a way that the initial and final states of system
are identical, then the process is called thermodynamic cycle.
Figure 1.7
Dialogue box…..
I.C. Engine does not execute thermodynamic cycle. Explain.
QUASI-STATIC PROCESS
When a process proceeds in such a manner that the system remains infinitesimally close
to an equilibrium state at all times, it is called a quasi-static, or quasi-equilibrium,
process.
Guru Gyan:
A process is said to be reversible if the system and its surroundings
are restored to their respective initial states by reversing the
direction of the process. A reversible process has to be quasi-static,
but a quasi – static process is not necessarily quasi-static.
Reversible Process
A process in which an infinitesimal change in the driving potential can reverse the direction of
the process.
Example: A piston expanding against an external pressure. The driving potential is the pressure
difference which is infinitesimal. At any stage, if the external pressure is increased
infinitesimally, the piston should start moving the opposite way.
Or Else: Heat transfer occurring due to a temperature difference between two bodies. The
temperature difference between the two bodies is infinitesimal. If the temperature of body
receiving energy is changed infinitesimally, the direction of heat transfer also changes.
NOTE: A reversible process is necessarily quasi-static though the opposite is not true. For
example, consider heat exchange between a really well insulated vessel at temperature T1 and
the surroundings which are at T2 far lesser than T1. Changing either T1 or T2 does not reverse
the direction of the process, though it is slow enough to be quasi-static.
CONCEPT OF CONTINUUM
Despite the large gaps between molecules, a substance can be treated as a continuum
because of the very large number of molecules even in an extremely small volume.
It assumes a continuous distribution of mass within the matter or system with no
empty space, instead of the actual conglomeration of separate molecules.
If the mean free path is very small as compared with some characteristic length in the
flow domain (i.e., the molecular density is very high) then the gas can be treated as a
continuous medium. If the mean free path is large in comparison to some characteristic
length, the gas cannot be considered continuous.
This idealization is valid as long as the size of the system we deal with is large relative to
the space between the molecules.
Thermodynamic properties are point functions since for a given state there is a definite
value for each property and is independent of the path the system follows during the
change of state.
Path Functions
They depend upon the path followed by the system.
They have inexact differential.
Differential amount is represented by symbol i.e. for small work done and small
heat transfer
Work and heat are the path functions.
Change in the value can NOT be expressed as the difference between initial and final
value.
WORKING SUBSTANCE
A working substance refers to a fluid in thermodynamic devices to serve as a medium for
transport of energy between the system and surroundings.
Fluid may be gas, vapour, liquid or any nonreactive mixture of these constituents.
Working substance may change their phase during processes occurring in the system.
Example – refrigerants used in refrigeration and air-conditioners, water vapour used in
steam power plants.
Intensive Property
Independent of mass
Extensive Property
mass dependent.
value depends upon the size of the system.
Specific property
An extensive property when expressed as per unit mass becomes an intensive
property.
Point Functions
They depend only upon the initial and final condition
not on the path followed by the system.
exact differential
Cyclic integral of a property (point function) is always zero
Path Functions
Depend upon the path followed by the system.
Inexact differential.
PRESSURE
Pressure is defined as a normal force exerted by a fluid per unit area
SI unit of Newton per square meter (N/m2), which is called a Pascal (Pa). That is,
Figure 1.9
SOLUTION:
760 mm Hg = 0.760 × 13600 × 9.81 Pa
= 10139.16 Pa
≈ 101.4 kPa
(a) 80 cm Hg gauge
= 0.80 × 13600 × 9.81 × 10-3 + 101.4 kPa
= 106.732+ 101.4 kPa
= 208.132kPa
(b) 50 cm Hg vacuum
= (76 – 50) cm (absolute)
= 0.26 × 13.600 × 9.81 kPa
= 34.68 kPa
Ques 2: Any vertical column having height of 60m and fluid in vertical column having density
1878 kg/m3 exists in a place where g = 9.65 m/s2. What is the pressure at the base of the
column?
Kg/m3
Ques 3: A pump discharges a liquid into a drum having 3 m in diameter and 8.40 m in length,
can hold 3000 kg of the liquid. Find the density of the liquid?
Solution:
ϓs ρg N/m3
Specific weight of a substance may vary with location on earth.
SPECIFIC VOLUME
Volume per unit mass is called specific volume.
m3/Kg
It is the reciprocal of mass density.
SPECIFIC GRAVITY
It is the ratio of the density of a fluid to the density of a standard fluid at a specified
temperature.
For liquids, standard fluid is water at 40C for which ρH2O =1000kg/m3.
SG =
ρ
B
C
X Y
Figure 1.10
Approach: Pressure gauge A has been installed on the wall where pressure due to gases in x and
y are acting in opposite direction, hence it will read a pressure difference of both.
Similarly, Pressure gauges B and C reads the pressure difference between respective chamber
and atmosphere.
SOLUTION:
Let x kPa and y kPa be absolute pressures in compartments X and Y respectively.
Integrating,
Hence, atmospheric pressure exists on earth surface due to the air column lying above the
earth surface.
Ques 3: In a condenser Vacuum Gauge reads around 0.72 mHg. Calculate absolute pressure in
the condenser in kPa (where the atmospheric pressure = 101.3 kPa)?
Solution:
Absolute pressure = atmospheric pressure – vacuum pressure
= 101.3 – 0.66 × 13600 × 9.81 × 10-3 kPa
= 101.3- 96.059 kPa
=5.24 kPa
a. 1, 2
b. 1
c. 2
d. 2, 3
5. Atm is…..
a. 1.01325 Mpa
b. 1.0 Mpa
c. 1.005 Mpa
d. 760 Kpa
7. A 30 m high vertical column of a fluid of density 1878 kg/m3 exists in a place where g =
9.65 m/s2. What is the pressure at the base of the column?
a. 501.45 Kpa
b. 600.25 Kpa
c. 644.67 Kpa
d. 543.68 Kpa
Solution:
P = PG 2 + Atmospheric pressure
= 1.00 + 1.0
= 2.01 bar.