D.

THERMODYNAMICS

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 1. THERMODYNAMICS
Thermodynamics (1) - is that branch of the physical
sciences that treats of various phenomena of energy
and the related properties of matter, especially the laws
of transformation of heat into other forms of energy
and vice versa.
Thermodynamics (2) – is the study of heat and work
and those properties of substance that bear a relation to
heat and work.

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 2. THE WORKING SUBSTANCE
Working substance – a substance to which heat can be stored
and from which heat can be extracted
Fluid - is a substance that exists, or is regarded as existing,
as a continuum characterized by low resistance to flow and
the tendency to assume the shape of its container.
Pure Substance – is one that is homogeneous in composition
and homogeneous and invariable in chemical aggregation. A
working substance whose chemical composition remains the
same even if there is a change in phase.
Simple Substance – is one whose state is defined by two
independently variable intensive thermodynamic principles.

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 2. THE WORKING SUBSTANCE (cont..)
 Ideal gas - is mathematically defined as one whose
thermodynamic equation of state is given by pv = RT,
where p is the absolute pressure, v is the specific
volume, R is the gas constant, and T is the absolute
temperature of the gas, respectively. A working
substance which remains in gaseous state during its
operating cycle and whose equation of state is pV= mRT
Incompressible substance - is a substance whose specific
volume remains nearly constant during a thermodynamic
process. Most liquids and solids can be assumed to be
incompressible without much loss in accuracy.

4
 3. THE SYSTEM
System (1) – is that portion of the universe, an atom, a
galaxy, a certain quantity of matter, or a certain volume
in space, that one wishes to study. It is a region
enclosed by specified boundaries, which may be
imaginary, either fixed or moving.
System (2) – is nothing more than the collection of
matter that is being studied. It is a quantity of matter of
fixed mass and identity upon which attention is
focused for study.

5
 Thermodynamic Systems
3.1 Closed System (1) – is one which there is an
exchange of matter with the surroundings – mass does
not cross its boundaries. Also called control mass.
Closed System (2) – is one that has no transfer of mass
with its surrounding, but may have a transfer of energy
(either heat or work) with its surroundings.)

6
 Thermodynamic Systems (cont..)
 Isolated System (1) – A special type of closed system
that does not interact in any way with its surroundings.
Isolated System (2) – is one that is completely
impervious to its surroundings – neither mass nor
energy cross its boundaries.
Isolated System (3) – is one that is not influences in
any way by the surroundings. This means that no
energy in the form of heat or work may cross the
boundary of the system. In addition, no mass may
cross the boundary of the system.

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 Thermodynamic Systems (cont..)
 3.2 Open System (1) – is one across whose
boundaries there is a flow of mass. Each may have
energy crossing its boundary. Also called control
volume.
Open System (2) – is one that may have a transfer of
both mass and energy with its surroundings.

8
 Thermodynamic Systems (cont..)
 Control Volume – is a fixed region in space chosen for
the thermodynamic study of mass and energy balance
for the flowing system.
Control Surface – is the boundary of the control
volume.
Surrounding or Environment – everything external to
the system.
Boundary – distinguishes the system from its
surroundings; may be at rest or in motion, usually
defined by a broken or dashed line.

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 4. THERMODYNAMIC PROPERTIES
Thermodynamic Properties (1) - a quantity which is
either an attribute of an entire system or is a function
of position which is continuous and does not vary
rapidly over microscopic distances, except possibly for
abrupt changes at boundaries between phases of the
system
Thermodynamic Properties (2) – is any characteristic
of the system that can be observed or measured;
macroscopic characteristics of a system such as mass,
volume, energy, pressure and temperature to which
numerical values can be assigned at a given time even
without knowledge of the history of the system.
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 4. THERMODYNAMIC PROPERTIES
(cont..)
 Classification of Properties
1. Intensive Properties – are independent of mass; for
example, temperature, pressure, density, and voltage.
Specific Properties – are those for a unit mass, are
intensive by definition such as specific volume.
2. Extensive Properties – are dependent upon the
mass of the system and are total values such as total
volume and total internal energy.

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 4. THERMODYNAMIC PROPERTIES
(cont..)
 Thermodynamic state - is a set of values of properties of a
thermodynamic system that must be specified to reproduce the
system. The individual parameters are known as state variables,
state parameters or thermodynamic variables. Once a sufficient
set of thermodynamic variables have been specified, values of
all other properties of the system are uniquely determined. The
number of values required to specify the state depends on the
system, and is not always known.

Point Function - A quantity whose value depends on the

location of a point in space, such as an electric field, pressure,
temperature, or density.

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 5. MASS AND WEIGHT
Mass (1) – a property of matter that constitutes one of the
fundamental physical measurements or the amount of matter a
body contains. Units of mass are in lbm, slugs, or kg. Symbol m.
Mass (2) - is the absolute quantity of matter in it, an unchanging
quantity for a particular mass when the speed of the mass is
small compared to the speed of light (no relativistic effect).
Weight (1) – the force acting on a body in a gravitational field,
equal to the product of its mass and the gravitational acceleration
of the field. Units of weight are in lbf or N. Symbol W. Formula
W=mg. Where g = 9.81 m/s2 or 32.2 ft/s2.
Weight (2) - is the force exerted by a body when its mass is
accelerated in a gravitational field.

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 6. VOLUME
Volume – the amount of space occupied by, or
contained in a body and is measured by the number of
cubes a body contains. Units of volume are in ft 3,
gallons, liters, cm3, or m3. Symbol is V.

14
 7. SPECIFIC VOLUME AND DENSITY
Density (r) of any substance – is its mass (not weight)
per unit volume. Units of density are lbm/ft3 or kg/m3.
Symbol r. m
 
V
Specific Volume – is the total volume of a substance
divided by the total mass of a substance. Units of
specific volume are in ft3/lbm or m3/kg. Symbol is v.
 Vor 1
v v
m 

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 7. SPECIFIC VOLUME AND DENSITY
Specific Weight (g) of any substance – is the force of
gravity on unit volume. Units of specific weight are
ft3/lbf or m3/N. Symbol
V is g.
  1
 or W v 
g
Specific Gravity (1) – is a measure of the relative
density of a substance as compared to the density of
water at a standard temperature. Symbol is SG.

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 7. SPECIFIC VOLUME AND DENSITY
Specific Gravity (2) – a dimensionless parameter, it is
defined as the ratio of the density (or specific weight)
of a substance to some standard density (or specific
weight).
For Liquid
 liquidsubstances:
 liquid
 SG   at std

 H2O at std
H2O

For Gaseous substances:

 gas  gas
SG  
 air at std  air at std

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 8. STANDARD DENSITIES
Density of water
At approx. 4oC (39.2oF) pure water has it's highest
density (weight or mass) = 1000 kg/m3 or 62.4 lb/ft3.
Density of air
At 70 °F (21.1 C) and 14.696 psia (101.325 kPaa), dry
air has a density of 0.074887 lbm/ft3 (1.2 kg/m3).

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 9. PRESSURE
Pressure – is a measure of the force exerted per unit
area on the boundaries of a substance (or system). It is
caused by the collisions of the molecules of the
substance with the boundaries of the system. Units of
pressure are psi, kg/cm2, kN/m2 or kPa. Symbol is p.
Formula p = F/A.

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 10. ATMOSPHERIC PRESSURE
Atmospheric pressure - is the force per unit area
exerted against a surface by the weight of air above
that surface in the Earth's atmosphere.
The standard atmosphere (symbol: atm) - is a unit of
pressure and is defined as being equal to 101.325 kPa.
[1] The following units are equivalent, but only to the
number of decimal places displayed: 760 mmHg (torr),
29.92 inHg, 14.696 psi.

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 10. ATMOSPHERIC PRESSURE (cont..)
 Barometric pressure - is often also referred to as
atmospheric pressure. Units is normally in Bar. 1 Bar =
100 kPaa.
Air pressure above sea level can be calculated as p =
101325(1 - 2.25577x10-5h)5.25588, where p = air pressure
(Pa) and h = altitude above sea level (m).

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 10. ATMOSPHERIC PRESSURE (cont..)
 Also  h 
 
 p  po e  ho 

where:
p = atmospheric pressure, (measured in bars)
h = height (altitude), km
p0 = is pressure at height h = 0 (surface pressure) = 1.0
Bar (Earth)
h0 = scale height = 7 km (Earth)
Or for every 1,000 feet, there is a corresponding
pressure decrease of approximately 1 in Hg.
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 11. BAROMETER
Barometer - is an instrument used to measure
atmospheric pressure. It can measure the pressure
exerted by the atmosphere by using water, air, or
mercury.

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 12. ABSOLUTE AND GAUGE
PRESSURES

24
 12. ABSOLUTE AND GAUGE
PRESSURES (cont..)
Absolute pressure, pabs - is measured relative to the
absolute zero pressure - the pressure that would occur
at absolute vacuum. All calculation involving the gas
laws requires pressure (and temperature) to be in
absolute units. It the sum of the gauge and atmospheric
pressure.

Gauge pressure - the amount by which the total

absolute pressure exceeds the ambient atmospheric
pressure.
Formula pabs = patm + pg
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 12. ABSOLUTE AND GAUGE
PRESSURES (cont..)
 Vacuum pressure (negative gauge pressure) - the
amount by which the total absolute pressure is less
than the ambient atmospheric pressure.
 Formula pabs = patm – pv
Pressure gauge - is often used to measure the pressure
difference between a system and the surrounding
atmosphere.

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 13. TEMPERATURE
Temperature – is a measure of the molecular activity of
a substance. It is a relative measure of how “hot” or
“cold” a substance is and can be used to predict the
direction of heat transfer. It is an intensive property
that is a measure of the intensity of the stored
molecular energy in a system.
Temperature Scales:
1. Fahrenheit (F) Scale – 180 units – from 32 F to 212
F.
2. Celsius (C) Scale or Centigrade Scale – 100 units –
from 0 C to 100 C.
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 13. TEMPERATURE (cont..)
Relationship:


 
  F  32   9   C
5


 
C   F  32  
5
9
Absolute zero - is the theoretical temperature at which
entropy reaches its minimum value. The laws of
thermodynamics state that absolute zero cannot be
reached using only thermodynamic means.
Absolute temperature - is the temperature measured
relative to the absolute zero.

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 13. TEMPERATURE (cont..)
Absolute Temperature Scales:
1. Kelvin (K) Scale – the absolute temperature scale
that corresponds to the Celsius scale.
2. Rankine (R) Scale – the absolute temperature scale
that corresponds to the Fahrenheit scale.
Relationship:

R  F  460

K  C  273
 273 K  273.15 K
* 460 R  459.67 R
*

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 13. TEMPERATURE (cont..)
Temperature Change:

 
C  
K   
5 
   F   
5 
  R
9 9
 
9
 
9
F  R    C    K
5 5
Ice point – the temperature of a mixture of ice and air-
saturated water at 1 atm = 0 C or 32 F.
Steam (boiling) point – the temperature pure liquid
water in contact with its vapour at 1 atm = 100 C or
212 F.

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 13. TEMPERATURE (cont..)
Triple point - The temperature and pressure at which a
substance can exist in equilibrium in the liquid, solid,
and gaseous states. The triple point of pure water is at
0.01 degrees Celsius and 4.58 millimeters of mercury
and is used to calibrate thermometers.

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 14. ENERGY
Energy - is defined as the capacity of a system to
perform work or produce heat.
Stored Energy – otherwise known as possessed energy,
it is the energy that is retrieved and stored within the
system; thus, dependent upon the mass flow.
Potential Energy (1) – is defined as the energy of
position. Symbol is P.E.
Potential Energy (2) – energy due to the elevation and
position of the system

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 14. ENERGY (cont..)
mgz
PE 
gc
Where m = mass (lbm, kg)
 z = height above some reference level (ft, m)
 g = acceleration due to gravity (ft/sec2, m/s2)
 gc = gravitational constant.
 = 32.17 ft-lbm/ft-sec2
 = 1 kg-m/s2-N

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 14. ENERGY (cont..)
 Kinetic Energy (1) – is the kinetic energy of motion.
Symbol is K.E.
Kinetic Energy (2) – energy or stored capacity for
performing work; possessed by a moving body, by
virtue of its momentum.

mv 2
KE 
2gc

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 14. ENERGY (cont..)
 Where m = mass (lbm, kg)
 v = velocity (ft/s, m/s)
 g = acceleration due to gravity (ft/sec2, m/s2)
 gc = gravitational constant.
 = 32.17 ft-lbm/lbf-sec2
 = 1 kg-m/s2-N
Joule’s Constant “J” – 778 ft-lbf/ Btu

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 14. ENERGY (cont..)
Internal Energy (1) – is a microscopic forms of energy
including those due to the rotation, vibration,
translation, and interactions among the molecules of a
substance.
Internal Energy (2) – heat energy due to the movement
of the molecules within the substance brought about its
temperature.
Internal Energy (3) – energy stored within a body or
substance by virtue of the activity and configuration of
its molecules and the vibration of the atoms within the
molecules.
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 14. ENERGY (cont..)
 Specific Internal Energy – is the substance internal
energy per unit mass. Unit is Btu/lbm or kJ/kg. Symbol
is u.

P-V Energy – is also called flow energy or flow work.

Specific P-V Energy – is the substance P-V energy per
unit mass.

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 14. ENERGY (cont..)
 Enthalpy (1) – is the amount of energy possessed by a
thermodynamic system for transfer between itself and
its environment. It is equal to H = U + PV.
Enthalpy (2) – the sum of the internal energy of a body
and the product of pressure and specific volume. Unit
is Btu/lbm or kJ/kg. Symbol is h.

Specific Enthalpy – is defines as h = u + pv.

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 14. ENERGY (cont..)
 Where u = specific internal energy
 p = pressure
 v = specific volume

Chemical Energy – stored energy that is released or

absorbed during chemical reactions.
Nuclear Energy – energy due to the cohesive forces of
the protons and neutrons within the atoms.

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 15. HEAT AND WORK
Transitory Energy – otherwise known as energy in transit or
in motion; energy that loses its identity once it is absorbed or
rejected within the system; independent of mass flow stream.
Heat (1) - is the transfer of energy that occurs at the
molecular level as a result of a temperature difference.
Symbol Q. Unit is Btu, Btu/hr, kJ or kW.
Heat (2) – energy in transition between a system and its
surroundings because of a difference in temperature.
Q is positive (+) when heat is added to the body
Q is negative (-) when heat is rejected by the body
Heat transferred per unit mass = Q
q
m
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 15. HEAT AND WORK (cont..)
Work – is defined for mechanical system as the action
of a force on an object through a distance. Symbol is
W. Unit is ft-lb, kJ.
W  Fd

Where F = force (lbf, N)
 d = displacement (ft, m )
• Work is a process done by or on a system.
Power – is the rate of doing work. Unit is hp or kW.
 Power  Work
Time

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 16. TYPES OF WORK
Non-flow Work , WNF – work done in a non-flow
system with moving boundary. Typical example of
which is the piston-cylinder assembly.
Flow Work, WF – work done in pushing a fluid across
a boundary, usually into or out of a system. WF = pDV
= p(V2-V1)
Steady-flow Work, WSF – additional work done in an
open system; used for steady flow systems where there
is neither accumulation nor diminution of mass and
energy within the system.

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 17. SPECIFIC HEAT
Heat Capacity – is the ratio of the heat (Q) added to or
removed from a substance to the change in
temperature ( ).
Specific Heat (1) – is the heat capacity of a substance
per unit mass. Unit is Btu/lbm-F or Btu/kg-C.
Specific Heat (2) – is the heat required to raise the
temperature of unit mass of a substance by a unit
temperature.

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 17. SPECIFIC HEAT (cont..)
Specific heat at constant pressure – is the change of
enthalpy for a unit mass between two equilibrium
states at the same pressure per degree change of
temperature.
Q
Cp 
T
Q
cp 
mT

q
cp 
T

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 17. SPECIFIC HEAT (cont..)
Specific heat at constant volume – is the change of
internal energy for a unit mass per degree change of
temperature when the end states are equilibrium states
of the same volume.

Q Q q
 Cv  cv  cv 
T m T T

Specific heat ratio –
 cp h
k 
cv u

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 18. ENTROPY
Entropy (1) – is a measure of inability to do work for a
given heat transferred.
Entropy (2) – is a measure of randomness of the
molecules of a substance or measures the fraction of
the total energy of a system that is not available for
doing work.
Entropy (3) – a property used to measure the state of
disorder of a substance; a function of both heat and
temperature.

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 18. ENTROPY (cont..)
DQ= the amount of heat transferred to or from the
system during the process (Btu or kJ)
 Tabs = the absolute temperature at which the heat was
transferred (R or K).
Ds = the change in specific entropy of a system during
some process (Btu/lbm-oR or kJ/kg.K).
Dq = the amount of heat transferred to or from the
system during the process (Btu/lbm or kJ/kg).

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 19. LAWS OF
THERMODYNAMICS

48
 19.1 ZEROTH LAW OF THERMODYNAMICS –
TEMPERATURE (THERMAL EQUILIBRIUM)
- states that when each of two systems is in
equilibrium with a third, the first two systems must be
in equilibrium with each other. This shared property of
equilibrium is the temperature.
- states that when two bodies have equality of
temperature with a third body, they in turn have
equality of temperature with each other and the three
bodies are said to be in thermal equilibrium. The third
body is usually a thermometer.

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 19.2 FIRST LAW OF THERMODYNAMICS – LAW ON
CONSERVATION OF ENERGY
 - states that, because energy cannot be created or
destroyed [setting aside the later ramifications of the
equivalence of mass and energy (Nuclear Energy)] – the
amount of heat transferred into a system plus the amount of
work done on the system must result in a corresponding
increase of internal energy in the system. Heat and work are
mechanisms by which systems exchange energy with one
another.
- states that during any cycle a system undergoes, the
cyclic integral of heat is proportional to the cyclic integral
of work or for any system, total energy entering = total
energy leaving.

50
 19.3 SECOND LAW OF THERMODYMANICS –
ENTROPY
 - states that the entropy – that is, the disorder – of an
isolated system can never decrease. Thus, when an isolated
system achieved a configuration of maximum entropy, it can
no longer undergo change: It has reached equilibrium.
Significant statements:
- Clausius: It is impossible for a self-acting machine
unaided by an external agency to move heat from one body
to another at a higher temperature.
- Kelvin-Planck: It is impossible to construct a heat engine
which, while operating in a cycle produces no effects except
to do work and exchange heat with a single reservoir.

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 19.3 SECOND LAW OF THERMODYMANICS –
ENTROPY (cont..)
- All spontaneous processes result in a more
probable state
- The entropy of an isolated system never decreases.
- No actual or ideal heat engine operating in cycles
can convert into work all the heat supplied to the
working substance.
- Caratheodory: In the vicinity of any particular state
2 of a system, there exist neighboring states 1 that are
inaccessible via an adiabatic change from state 2.


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 19.4 THIRD LAW OF THERMODYNAMICS -
ABSOLUTE TEMPERATURE
 - states that absolute zero cannot be attained by any
procedure in a finite number of steps. Absolute zero
can be approached arbitrarily closely, but it can never
be reached.
- The entropy of a substance of absolute temperature
is zero.

53
 20. THERMODYNAMIC EQUILIBRIUM
Thermodynamic Equilibrium – is a condition when a
system is in equilibrium with regard to all possible
changes in state.

54
 21. CONSERVATION OF MASS
The law of conservation of mass states that the mass is
indestructible.
Steady State – is that circumstance in which there is no
accumulation of mass or energy within the control
volume, and the properties at any point within the system
are independent of time.
Continuity Equation of Steady Flow
 A11 A2 2
m  1 A11   2 A2 2  
v1 v2
 Usual English units are: u fps, r lb/ft3, v ft3/lb, A ft2, m
lb/sec.

55
 22. HEAT RESERVOIR
Heat reservoir – is a thermodynamic system that
generally serves as a heat source or heat sink for
another system.

56
 23. HEAT OR THERMAL ENGINE
Heat engine or Thermal Engine (1) – is a
thermodynamic system that operates continuously with
only energy (heat and work) crossing its boundaries;
its boundaries are impervious to the flow of mass.
Heat engine or Thermal Engine (2) – a closed system
(no mass crosses its boundaries) that exchanges only
heat and work with its surroundings and that operate in
cycles.

57
 24. ADIABATIC SURFACE AND
PROCESS
Adiabatic surface – is one that is impervious to heat. It
implies perfect insulation.
Adiabatic process – a process that occurs within a
system enveloped by an adiabatic surface.

58
 25. AVAILABILITY
Availability of a closed system – is the maximum work
that the system could conceivably deliver to something
other than the surroundings as its state changes to the
dead state, exchanging heat only with the environment.
Availability of a steady-flow system – is the maximum
work that can conceivably be delivered by, say, a unit
mass of the system to something other than the
surroundings as this unit mass changes from its state at
the entrance to the control volume to the dead state at
the exit boundary, meanwhile exchanging heat only
with the surroundings.
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 26. REVERSIBILITY
Reversibility (1) - a characteristic of certain processes
(changes of a system from an initial state to a final
state spontaneously or as a result of interactions with
other systems) that can be reversed, and the system
restored to its initial state, without leaving net effects
in any of the systems involved.
Reversibility (2) - is a process that can be "reversed"
by means of infinitesimal changes in some property of
the system without loss or dissipation of energy

60
 27. IRREVERSIBILITY
Irreversibility - a change in the thermodynamic state of
a system and all of its surroundings cannot be precisely
restored to its initial state by infinitesimal changes in
some property of the system without expenditure of
energy.
27.1 External irreversibility – is some irreversibility
external to the system.
27.2 Internal irreversibility – is any irreversibility
within the system.

61
 28. AVAILABLE ENERGY
Available energy - is the greatest amount of
mechanical work that can be obtained from a system or
body, with a given quantity of substance, in a given
initial state, without increasing its total volume or
allowing heat to pass to or from external bodies,
except such as at the close of the processes are left in
their initial condition.

62
 29. HELMHOLTZ FUNCTION
Helmholtz function - a thermodynamic property of a
system equal to the difference between its internal
energy and the product of its temperature and its
entropy. Symbol A. Formula A = u – Ts.

63
 30. GIBBS FUNCTION
Gibbs function - a thermodynamic property of a
system equal to the difference between its enthalpy and
the product of its temperature and its entropy. It is
usually measured in joules. Symbol G. Formula G = h
– Ts.

64
 31. EQUILIBRIUM
Equilibrium - is the condition of a system in which competing
influences are balanced.
Mechanical equilibrium - the state in which the sum of the
forces, and torque, on each particle of the system is zero. Also
means that the system is not accelerating.
Thermal equilibrium - a state where an object and its
surroundings cease to exchange energy in the form of heat,
i.e. they are at the same temperature.
Chemical equilibrium - the state in which the concentrations
of the reactants and products have no net change over time.
Also a system has no tendency to undergo further chemical
reaction.

65
 31. EQUILIBRIUM (cont..)
 Thermodynamic equilibrium - the state of a
thermodynamic system which is in thermal,
mechanical, and chemical equilibrium. Also the system
has no tendency toward spontaneous change –
meaning a change without outside influence.
Quasistatic equilibrium - is a thermodynamic process
that happens infinitely slowly. No real process is
quasistatic, but such processes can be approximated by
performing them very slowly.

66
 32. PERPETUAL MOTION MACHINE OF
THE SECOND KIND
Perpetual motion machine of the second kind – is a
proposed machine that violates the second law of
thermodynamics.

67
 33. BOYLE’S LAW
Boyle’s Law (1) – states that if the temperature of a
given quantity of gas is held constant, the volume of
gas varies inversely with the absolute pressure during a
quasistatic change of state.
Boyle’s Law (2) – states that the volume of a gas
varies inversely with its absolute pressure during
change of state if the temperature is held constant.

p1V1  p2V2

68
 34. CHARLES’ LAW
Charles’ Law (1) – the volume of a gas varies directly
as the absolute temperature during a change of state if
the pressure of the gas is held constant.
V V2
1

T1 T2
Charles’ Law (2) – the pressure of a gas varies directly
as the absolute temperature during a change of state if
the volume of the gas is held constant in.

p1 p2

T1 T2

69
 35. IDEAL GAS LAW
Ideal Gas Law - The equation of state of an ideal gas
which is a good approximation to real gases at
sufficiently high temperatures and low pressures; that
is, PV = RT, where P is the pressure, V is the volume
per mole of gas, T is the temperature, and R is the gas
constant.
pV  mRT

p1V1 p2V2
 T  T
1 2

Where p = pressure, V = volume, m = mass, R = ideal

gas constant, and T = absolute temperature.
70
 36. BASIC PROPERTIES OF IDEAL GAS

8.3143 1545
R kg  K
kJor R ft  lb lb  R
M M

c p  cv  R

cp
 k
cv

kR
cp 
k 1
R
cv 
k 1

71
 36. BASIC PROPERTIES OF IDEAL GAS
(cont..)
Where:
R = gas constant
M = molecular weight
cp = specific heat at constant pressure
cv = specific heat at constant volume
k = specific heat ratio


72
 37. PROPERTIES OF AIR
M  28.97 kg air mole air

k  1.4
R  53.3 ft  lb lb  R  0.287 kJ kg  K

c p  0.24 Btu lb  R  0.24 kcal kg  C  1.0 kJ kg  C

cv  0.171 Btu lb  R  0.171 kcal kg  C  0.716 kJ kg  C

73
 38. AVOGADRO’S LAW AND NUMBER
Avogadro’s Law – states that “equal volumes of all
ideal gases at a particular pressure and temperature
contains the same number of molecules”.
Avogadro’s number, NA – is the number of molecules
in a mole of any substance and is equal to 6.0225 x
1023 gmole-1.

74
 39. JOULE’S LAW
Joule’s Law – states that the change of internal energy
of an ideal gas is a function of only the temperature
change.

75
 40. DALTON’S LAW OF PARTIAL
PRESSURE
Dalton’s Law of Partial Pressure – states that the total
pressure pm of a mixture of gases is the sum of the
pressures that each gas would exert were it to occupy
the vessel alone at the volume Vm and temperature tm
of
pmthe  pb  pc     pi
 pamixture.
i
Tm  Ta  Tb  Tc Vm  Va  Vb  Vc 

pi  X i pm
 Xi  1
i

76
 41. AMAGAT’S LAW OF PARTIAL
VOLUMES
Amagat's Law of Partial Volumes - states that the
volume Vm of a gas mixture is equal to the sum of
volumes Vi of the K component gases, if the
temperature T and the pressure p remain the same.
Vm  Va  Vb  Vc     Vi
i
T  T  T  T p  p  p  p 
m a b c m a b c

V  X iVm
i
X
i
i 1

77
 42. THERMODYNAMIC SYSTEMS AND
PROCESSES
Thermodynamic Process – is the path of the succession of states
through which the system passes.
Cyclic Process or Cycle – is a process where a system in a given
initial state goes through a number of different changes in state
(going through various processes) and finally returns to its initial
values.
Reversible Process – is defined as a process that, once having
taken place, can be reversed, and in so doing leaves no change in
either the system or surroundings.
Irreversible Process – is a process that cannot return both the
system and the surroundings to their original conditions. That is,
the system and the surroundings would not return to their original
conditions if the process was reversed.

78
 42. THERMODYNAMIC SYSTEMS AND
PROCESSES (cont..)
 Adiabatic Process – is one in which there is no heat transfer
into or out of the system. The system can be considered to be
perfectly insulated.
Isentropic Process – is one in which the entropy of the fluid
remains constant. This will be true if the process the system
goes through is reversible and adiabatic. An isentropic
process can also be called a constant entropy process.
Polytropic Process – is a process when a gas undergoes a
reversible process in which there is heat transfer, the process
frequently takes place in such a manner that a plot of the Log
P (pressure) vs Log V (volume) is a straight line. Or stated in
equation form pVn = a constant.

79
 42. THERMODYNAMIC SYSTEMS AND
PROCESSES (cont..)
 Throttling Process – is defined as a process in which there is
no change in enthalpy from state one to state two, h1 = h2; no
work is done, W = 0; and the process is adiabatic, Q = 0.
Isobaric Process – is an internally reversible (quasistatic, if
nonflow) process of a pure substance during which the
pressure remains constant.
Isometric Process (Isochoric Process) – a constant volume
process that is internally reversible (quasi-static if nonflow),
involving a pure substance.
Isothermal Process – is an internally reversible (quasistatic, if
nonflow) constant temperature process of a pure substance.

80
 43. EQUATIONS FOR
THERMODYNAMIC PROCESSES
dQ
Entropy = S   T

Non-Flow Equation,
Q  U  Wnf
Steady-Flow Equation, DK = 0, DP = 0
Q  H  Wsf
Steady-Flow Equation, , 0
K  0 P
Q  H  K  P  Wsf

81
 43. EQUATIONS FOR
THERMODYNAMIC PROCESSES (cont..)
Where:
DU = internal energy
 DH = enthalpy
 DK = kinetic energy
 DP = potential energy
 Wnf = non-flow work
Wsf = steady flow work
Internal Energy
 DU = mcvDT
Enthalpy
 DH = mcpDT

82
 43. EQUATIONS FOR
THERMODYNAMIC PROCESSES (cont..)
 Non-Flow Work
 Wnf   pdV
Steady Flow Work, DK = 0, DP = 0.
 Wsf    Vdp
Steady-Flow Equation,
 K  P  Wsf   Vdp
Note:

H
k
U

83
 44. ISOBARIC PROCESS
Isobaric Process – is an internally reversible
(quasistatic, if nonflow) process of a pure substance
during which the pressure remains constant.

84
 44. ISOBARIC PROCESS (cont..)
 p = Constant

V2 T2
 
V1 T1


H  mcp  T2  T1 

U  mcv  T2  T1 

85
 44. ISOBARIC PROCESS (cont..)
 Non-flow:
 Q  U  Wnf
 W  pdV  p V  V 
nf  2 1

Q  H

Entropy:
 dQ
S  
T

T2 V
S  mcp ln  mcp ln 1
T1 V2

86
 44. ISOBARIC PROCESS (cont..)
Steady Flow:
 Q  H  Wsf


 W   Vdp  0
sf

Q  H
Entropy:
dQ
 S  
T

Specific Heat Ratio:

 k  H  Q
 U U

87
 45. ISOMETRIC PROCESS (ISOCHORIC
PROCESS)
Isometric Process (Isochoric Process) – a constant
volume process that is internally reversible (quasi-
static if nonflow), involving a pure substance.

88
 45. ISOMETRIC PROCESS (ISOCHORIC
PROCESS) (cont...)
 V = Constant

 p2  T2
p1 T1


H  mcp  T2  T1 

U  mcv  T2  T1 

89
 45. ISOMETRIC PROCESS (ISOCHORIC
PROCESS) (cont...)
Non-flow:
 Q  U  Wnf


 Wnf  pdV  0
Q  U
Entropy:
 dQ

S 
T
T2 p
S  mcv ln  mcv ln 2
T1 p1

90
 45. ISOMETRIC PROCESS (ISOCHORIC
PROCESS) (cont...)
Steady Flow:
 Q  H  Wsf

Wsf    Vdp  V  p2  p1 

Q  U

Specific Heat Ratio:
  H H
k 
U Q

91
 46. ISOTHERMAL PROCESS
Isothermal Process – is an internally reversible
(quasistatic, if nonflow) constant temperature process
of a pure substance.

92
 46. ISOTHERMAL PROCESS
(cont..)
pV = constant, T = constant
H  mcp  T2  T1 
U  mcv  T2  T1 
Non-Flow Equation:
 Q  U  Wnf
 p1V1  p2V2  pV  C  mRT
 V2 p1
Wnf  pV ln  pV ln
 V1 p2

Wnf  mRT ln V2  mRT ln p1

V1 p2
Q  Wnf
93
 46. ISOTHERMAL PROCESS
(cont..)
Steady Flow:
 Q  H  W
sf

V2 p1
 Wsf  pV ln V  pV ln p
1 2

V2 p1
Wsf  mRT ln  mRT ln
V1 p2

Q  Wsf

94
 46. ISOTHERMAL PROCESS
(cont..)
Entropy:

V2
S  mR ln
V1

p1
S  mR ln
p2

pV V2 pV p1
S  ln  ln
T V1 T p2

95
 47. ISENTROPIC PROCESS
Isentropic Process – is a reversible adiabatic process
with constant entropy.

96
 47. ISENTROPIC PROCESS
(cont..)
pVk = constant, DS = 0, pV = mRT, Q = 0
 k k 1
k 1
p2  V1   T2   V1   T2   p2  k
   ,     , Or
     
p1  V2   T1   V2   T1   p1 


H  mcp  T2  T1 


U  mcv  T2  T1 

97
 47. ISENTROPIC PROCESS
(cont..)
 Non-flow:
Q  U  Wnf
 1 k   1 k 
p1V1  V2  p1V1  p1 
Wnf     1     1
 
1  k  V1   1  k  p2  
   
 k 1 
 V  1 k  mRT  V  k 1  mRT  p  k
mRT1
 2  1  2  
Wnf   1  1  1   1   1
1k  V1   1k  V2   1  k  p1  
     

mRT1  T2  mR  T2  T1  p2V2  p1V1

Wnf    1  
1k  T1  1k 1k

98
 47. ISENTROPIC PROCESS
(cont..)
But,
R
cv 
k 1
Wnf  mcv  T2  T1   U

Steady Flow:
Q  H  Wsf
 k 1   k 1 
kp V  p  k  kmRT1  
 p2  k  kmRT1  V  k 1  kmRT  T 
Wsf  1 1  2   1    1   1  1 2 
1  k  p1  1k  p  1  1k  
 V2  
 1  k  T1
 1
   1     

kmR T2  T1 
Wsf 
1k
99
 47. ISENTROPIC PROCESS
(cont..)
But
 c  kR
p
k 1

Wsf  mcp  T2  T1   H
Note:
 cp H   Vdp Wsf
k   
cv U  pdV Wnf

100
 48. POLYTROPIC PROCESS
Polytropic Process – is an internally reversible process
during which pVn = C where n is any constant.

101
 48. POLYTROPIC PROCESS
(cont..)
pVn = constant, pV = mRT

n1 n 1
 T2  V1  T2  p2  n
     
 T1  V2  T1  p1 

H  mcp  T2  T1 

U  mcv  T2  T1 

102
 48. POLYTROPIC PROCESS
(cont..)
Non-flow Work:
 Q  U  Wnf
  1 n   1 n 
p1V1 V2  p1V1 p1  
 Wnf     1     1
 
1  n  V1   1  n  p2  
   

 n 1 
 V  1 n  mRT  V  n 1  mRT  p  n
mRT1
 2  
Wnf   1  1  1   1  1  2
 1
1n  V1   1n  V2   1  n  p1  
     

mRT1  T2  mR  T2  T1  p2V2  p1V1

Wnf    1  
1n  T1  1n 1n
103
 48. POLYTROPIC PROCESS
(cont..)
But,
R
cv 
k 1

mR T2  T1  p2V2  p1V1

U  
k 1 k 1

 1
Q 
1 
 p2V2  p1V1    1  1  p2V2  p1V1    n  k   p2V2  p1V1 
 k 1 1  n   k 1 n 1   k  1 n  1

104
 48. POLYTROPIC PROCESS
(cont..)
Steady Flow:

Q  H  Wsf

 n1   n1 
np1V1  p2  n  nmRT1 
 2 
p  n  nmRT1  V  n1  nmRT  T 
Wsf      1   1  1 2 
1  n  p1 
1  1n  p   1  1n  V2   1  n  T1
 1
   1     

nmR T2  T1 
Wsf 
1 n

105
 48. POLYTROPIC PROCESS
(cont..)
But
kR
cp 
k 1
kmR T2  T1  k  p2V2  p1V1 
H  mcp  T2  T1   
k 1 k 1
 1 1   k n 
Q   p2V2  p1V1      p2V2  p1V1 
 k 1 1  n   k 1 n 1 

 n  k   p2V2  p1V1 
Q
 k  1 n  1

106
 48. POLYTROPIC PROCESS
(cont..)
Entropy:
 n  k OrT2 V 

S  mcv   ln S  mcv  n  k  ln 1 
  n  1  T1  V2 
n1
  n  k   p2 
 n  n  k   p2 
S  mcv   ln   mcv   ln 
 n  1   p1   n   p1 
Note:
Steady flow work:
 Wsf  K  P    Vdp

107
 49. CURVES FOR DIFFERENT VALUES
OF n.

108
 50. TABLE OF IDEAL GAS FORMULAS

109
 51. STAGNATION PROPERTIES
Stagnation Properties – are those thermodynamic
properties that a moving stream of compressible fluid
would have if it were brought to rest isentropically (no
outside work, the kinetic energy brings about the
compression).
Stagnation
2 enthalpy
v
h0  h 
2gc J

110
 51. STAGNATION PROPERTIES (cont..)
 Stagnation temperature

v2
T0  T 
2gc Jcp

k 1
T0  p0  k v2
   1
T  p 2gc JcpT

111
 52. MACH NUMBER
Mach Number – is the ratio of the actual speed divided
by the local speed of sound a in the fluid.
M
a

M 1
 [SUBSONIC]

M 1
 [SUPERSONIC]

Acoustic speed: 1
a   gc kRT  2


112
 53. PURE SUBSTANCE
Pure Substance – is a working substance that has a
homogeneous and invariable chemical composition
even there is a change of phase.

113
 54. PHASES OF PURE
SUBSTANCE
Phase (1) - a chemically and physically uniform
quantity of matter that can be separated mechanically
from a non-homogeneous mixture. It may consist of a
single substance or of a mixture of substances.
Phase (2) – a quantity of matter that is homogeneous
throughout in both chemical composition and physical
structure.
Phase (3) - is a distinct and homogeneous state of a
system with no visible boundary separating it into
parts.

114
 54. PHASES OF PURE SUBSTANCE
(cont..)
54.1 Solid - has a definite shape and volume.
54.2 Liquid - has a definite volume but it takes the shape of
a container.
Saturated Liquid – a liquid substance that has its temperature
equal to the saturation temperature at a given pressure.
Compressed Liquid – liquid whose pressure is higher than
the saturation pressure at the given temperature. If the
temperature is held constant , the pressure is increased
beyond the saturation pressure.
 Sub-cooled Liquid – liquid whose temperature is lower
than the saturation temperature at the given pressure.

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 54. PHASES OF PURE SUBSTANCE
(cont..)
 54.3 Gas - fills the entire volume of a container.
Vapor - the state of a substance that exists below its
critical temperature and that may be liquefied by
application of sufficient pressure.
Saturated Vapor – a vapour substance that has its
temperature equal to the saturation temperature at a
given pressure.
Superheated Vapor – vapor whose temperature is
higher than the saturation temperature at the given
pressure.

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 55. PHASE TRANSITIONS
Phase transition - Conversion between these phases.
55.1 Melting or fusion – is the change of phase from
solid to liquid.
55.2 Freezing or solidifying – is the change of phase
from liquid to solid.
55.3 Sublimation – is the change of phase from solid
to gas.
55.4 Deposition – is the change of phase from gas to
solid.
55.5 Condensation – is the change of phase from gas
to liquid.
117 55.6 Vaporization – is the change of phase from
 56. SATURATED TEMPERATURE
Saturation Temperature – the temperature at which
vaporization takes place at a given pressure, this
pressure being called the saturation pressure for the
given temperature.

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 57. SATURATED PRESSURE
Saturation Vapor Pressure - the vapor pressure of a
thermodynamic system, at a given temperature,
wherein the vapor of a substance is in equilibrium with
a plane surface of that substance's pure liquid or solid
phase.

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 58. DEGREES SUPERHEAT AND
DEGREES SUBCOOLING
Degrees Superheat – difference between actual
temperature and saturation temperature.
Degrees Subcooling – difference between saturation
temperature and actual temperature.

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 59. SENSIBLE HEAT
Sensible Heat – the heat added to or removed from a
substance to produce a change in its temperature

121
 60. LATENT HEAT
Latent Heat – the amount of heat added to or removed
from a substance to produce a change in phase.
60.1 Latent heat of fusion, enthalpy of fusion – is the
amount of heat added or removed to change phase
between solid and liquid.
60.2 Latent heat of vaporization, enthalpy of
evaporation – is the amount of heat added or removed
to change phase between liquid and vapor. It is
sometimes called the latent heat of condensation.

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 61. CRITICAL POINT
Critical Point – is the condition of pressure and
temperature at which a liquid and its vapor are
indistinguishable.

123
 62. MOLLIER DIAGRAM
Mollier Diagram (h-s) – is a chart on which enthalpy is
the ordinate and entropy the abscissa.

124
 63. TEMPERATURE-ENTROPY
DIAGRAM

125
 64. ph-Chart

126
 66. PROPERTIES
Specific Volume, v – volume per unit mass.
Internal Energy, u – energy stored within a body or
substance by virtue of the activity and configuration of
its molecules and the vibration of the atoms within the
molecules.
Enthalpy, h – a composite property applicable to all
fluids and is defined by the equation: h = u + pv.
Entropy, s – a property used to measure the state of
disorder of a substance; a function of both heat and
temperature.

127
 67. MIXTURES
Mixture – substance made up of liquid and vapor
portion or two-phase liquid-vapour system.
x= quality or dryness factor or vapour content
y = 1 – x = moisture content or wetness
Properties of mixtures
 v  v f  xv fg
 u  u f  xu fg

h  h f  xh fg

s  s f  xs fg

128
 68. PROCESSES INVOLVING PURE
SUBSTANCES
a. Isobaric or constant pressure process: p1 = p2
b. Isothermal or constant temperature process: T1 = T2
Evaporation and condensation processes occur at constant pressure and constant
temperature.
c. Isometric or constant volume process: V1 = V2
 For constant mass: v1 = v2
 If the final state is a mixture: v1 = (vf + xvfg)2
d. Isentropic or constant entropy process: s1 = s2
Isentropic process is reversible (no friction loss) and adiabatic (no heat loss, that
is, completely insulated system).
e. Throttling or isenthalpic (constant enthalpy) process: h1 = h2
If the final state is a mixture: h1 = (hf + xhfg)2
If the initial state is a mixture, such as in steam calorimeter:
(hf + xhfg)1 = h2

129
 69. ESSENTIAL ELEMENTS OF A
THERMODYNAMIC HEAT ENGINE
69.1 Working substance – matter that receives heat,
rejects heat, and does work.
69.2 Source of heat (Hot body, Heat reservoir, or just
Source) – form which the working substance receives
heat.
69.3 Heat sink (Receiver, Cold body, or just Sink) –
to which the working substance can reject heat.
69.4 Engine – wherein the working substance may
do work or have work done on it.

130
 70. THE CARNOT CYCLE

131
 70. THE CARNOT CYCLE (cont..)
 T1 and
T2  T4  T3 S1  S 4  S 2  S3
 QA  T1  S1  S 4  QR  T2  S2  S3   T2  S1  S4 
 W  QA  QR  T1  S1  S 4   T2  S1  S 4 
 e  W  QA  QR  T1  S1  S4   T2  S1  S4 
 QA QA T1  S1  S4 

 e  T1  T2  TH  TL QA QR

 T1 TH TH TL

Where e = Carnot cycle efficiency

 T1 = TH = highest absolute temperature
 T2 = TL = lowest absolute temperature
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 71. STIRLING AND ERICSSON CYCLE
Ideal Stirling Cycle – is composed of two isothermal
and two isometric processes, the regeneration
occurring at constant volume.
Ideal Ericsson Cycle – consists of two isothermal and
two isobaric processes, with the regeneration occurring
during constant pressure.

133
 72. BASIC WORKING CYCLES FOR
VARIOUS APPLICATIONS

Application Basic Working Cycle

Steam Power Plant Rankine Cycle
Gasoline Engine (Spark-Ignition) Otto Cycle
Diesel Engine (Combustion-Ignition) Diesel Cycle
Gas Turbine Brayton Cycle
Refrigeration System Refrigeration Cycle

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 END

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