07-08-2018

Thermofluids
Thermodynamics - Properties

Dr. D. Gangacharyulu
Professor
Department of Chemical Engineering

Syllabus - Thermodynamics
• Introduction: Properties of matter, the state postulate, energy,
processes and thermodynamic systems;

• Properties of Pure Substances: property tables, property diagrams,

Mollier diagram, phase change, equations of state (ideal gas);

• Energy: Energy transfer by heat, work and mass;

• First Law of Thermodynamics: Closed system, open system, steady-

flow engineering devices;

• Second Law of Thermodynamics: Statements of the Second Law,

heat engines, refrigeration devices, reversible versus irreversible
processes, the Carnot cycle, entropy and entropy change.

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Books
• Textbook
 Cengel, Y.A. and Boles, M.A., Thermodynamics: An
Engineering Approach, McGraw-Hill (2011)

• Reference Book
 Rao, Y. V. C., An Introduction to Thermodynamics,
Universities Press (2004)

Course Learning Outcomes (CLOs)

• Thermodynamics:

 Upon completion of this course, the students will be able to:

1. estimate fluid properties and solve basic problems using

property tables, property diagrams and equations of state,

2. analyze and solve problems related to closed systems and

steady-flow devices by applying the conservation of energy
principle,

3. analyze the second law of thermodynamics for various

systems and to evaluate the performance of heat engines,
refrigerators and heat pumps.

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Thermodynamics Laws
• Thermodynamics is the branch of physics that deals with the relationships
between heat and other forms of energy.
• Four basic laws have been established
First law The first law states that the amount of energy added to a system is equal to
the sum of its increase in heat energy and the work done on the system.
The first law is an example of the principle of conservation of energy.
Second law The second law states that heat energy cannot be transferred from a body
at a lower temperature to a body at a higher one without the addition of
energy. Thus, warm air outside can transfer its energy to a cold room, but
transferring energy from a cold room to the warm air outside requires
extra energy (as with an air conditioner).
Third law The third law states that the entropy of a pure crystal at absolute zero is
zero. Since there can be no physical system with lower entropy, all entropy
thus has a positive value by definition.
Zeroth law The zeroth law states that if two bodies are in thermal equilibrium with
some third body, then they are also in equilibrium with each other. This law
has its name because it was implicitly assumed in the development of the
other laws, and is in fact more fundamental than the others, but was only
later established as a law itself.
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Dead-weight pressure gauge

Temperature gauge Calibration

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Transformer

Cooling of transformer

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Electrical motors

Fan

Fan

Fins
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Closed Air Circuit Aircooled (CACA) Heat Exchanger of

Electrical motor

Heat exchanger

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Heat exchanger

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Cooling systems of I.C. Engines

Radiator

After cooler

Oil cooler

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Thermodynamics
• Purpose of thermodynamics :

 Calibration of instruments ?
• Zeroth Law of thermodynamics
• It states that if two thermodynamic systems are
each in thermal equilibrium with a third, then they
are in thermal equilibrium with each other.

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Contd…
Energy conversion – (1) Heating element, (2) Electrical motor, (3) I.C. engine
motor
• First law of thermodynamics.

• It is called as law of conservation of energy.

• The law of conservation of energy states that the total energy of

an isolated system is constant.

• Energy can be transformed from one form to another, but cannot be

created or destroyed.

• The first law is often formulated by stating that:

– the change in the internal energy of a closed system is equal to
– the amount of heat supplied to the system, minus
– the amount of work done by the system on its surroundings.
 U = H – W

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Contd…
 Current flow between two potentials?I = E/R
 Fluid flow between two pressures? v = p/R
 Heat flow between two temperatures? q = T/R

• Second law of thermodynamics

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Thermodynamics
• Thermodynamics can be defined as the science of energy.

• Although everybody has a feeling of what energy is, it is difficult to give a

precise definition for it.

• Energy can be viewed as the ability to cause changes.

• The name thermodynamics stems from the Greek words “therme” (heat)
and “dynamis” (power),
 which is most descriptive of the early efforts to convert heat into
power.

• Today the same name is broadly interpreted to include all aspects of

energy and energy transformations, including:
 power generation,
 refrigeration, and
 relationships among the properties of matter.

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Systems and Control volumes

• A system is defined as a quantity of matter or a region in space chosen for
study.

• The mass or region outside the system is called the surroundings.

• The real or imaginary surface that separates the system from its
surroundings is called the boundary.

• These terms are illustrated in Figure.

• The boundary of a system can be fixed or movable.

• Note that the boundary is the contact surface shared by both the system
and the surroundings.

• Mathematically speaking, the boundary has zero thickness, and thus it can
neither contain any mass nor occupy any volume in space.

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Closed system
• Systems may be considered to be closed or open, depending on
whether a fixed mass or a fixed volume in space is chosen for study.

• A closed system (also known as a control mass) consists of a fixed

amount of mass, and no mass can cross its boundary.

• That is, no mass can enter or leave a closed system,

as shown in Figure.

• But energy, in the form of heat or work, can cross the boundary;
and the volume of a closed system does not have to be fixed.

• If, as a special case, even energy is not allowed to cross the

boundary, that system is called an isolated system.

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Open system
• An open system, or a control volume, as it is often
called, is a properly selected region in space.

• It usually encloses a device that involves mass flow such

as a compressor, turbine, or nozzle.

• Flow through these devices is best studied by selecting

the region within the device as the control volume.

• Both mass and energy can cross the boundary of a

control volume.
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Open systems Continue…

(a) A control volume (b) A control volume

with real and with fixed and
imaginary moving boundaries
An open system (a control volume)
boundaries
with one inlet and one exit. An
open system (a control volume)
with one inlet and one exit.

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Properties of a state
• Any characteristic of a system is called a property.

• A property can be defined as any quantity that depends on

the state of the system and is independent of the path by
which the system arrived at the given state.

• Property is any quantity whose changes are defined only by

the end states and by the process

• Some familiar properties are:

 Temperature, T
 Pressure, p
 Volume V, and
 Mass, m,

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• Less familiar properties are:

 Density, 
 Viscosity, 
 Thermal conductivity, k
 Velocity, v
 Elevation, h
 Modulus of elasticity, E
 Thermal expansion coefficient, 
 Electric resistivity, 
 Etc.

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Thermal expansion coefficient, 

• The coefficient of thermal expansion:
1  v 
  
v  T  p
• For gases, assuming they follow ideal gas law:
  = 1/T in Kelvin = 1/(ToC+273.15)
  = T-1, K = (ToC+273.15)-1

• For liquids:

1  2 
ave  T2  T1 
 1 = density of fluid at T1, and
 2 = density of fluid at T2.

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Types of Thermodynamic Properties

• Thermodynamic properties can be divided into TWO
general classes:

 Intensive properties: independent of the mass of the

system.

 Extensive properties: dependent on the mass, or, size,

or varies directly with the mass.

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Intensive properties
• Examples:
 Temperature, T (oC)
 Pressure, p (Pa)
 Density,  (kg/m3)

• Extensive properties per unit mass is also called as

intensive property
 Example: specific volume, v (m3/kg)

• i.e.,  = 1/v = 1÷v

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Extensive properties
• Examples:
 Total mass, m (kg)
 Total volume, V, (m3)
 Total momentum, M (kg-m/s) (MLT-1)
• Momentum = mass × velocity = m × v

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How?
• An easy way to determine whether a property is intensive or
extensive is to divide the system into two equal parts with an
imaginary partition, as shown in figure.

Criterion to differentiate intensive and

extensive properties.

• Each part will have the same value of intensive properties as the
original system, but half the value of the extensive properties.
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• Generally, uppercase letters are used to denote extensive

properties (with mass m being a major exception), and
lowercase letters are used for intensive properties (with
pressure P and temperature T being the obvious
exceptions).

• Extensive properties per unit mass are called specific

properties.

• Some examples of specific properties are specific volume

(v = V/m) and specific total energy (e = E/m).
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Density
• Density is defined as mass per unit volume.
 Density:  = m/V (kg/m3)

• The reciprocal of density is the specific volume v, which

is defined as volume per unit mass.
 Specific volume: v = V/m = 1/ (m3/kg)

• For a differential volume element of mass m and

volume V, density can be expressed as:
 Density,  = m/V.

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Specific Gravity
• Sometimes the density of a substance is given relative to the
density of a well-known substance (or Reference material).

• Then it is called specific gravity, or relative density.

• It is defined as the ratio of the density of a substance to the

density of some standard substance at a specified
temperature (usually water at 4°C, for which water = 1000
kg/m3).
 Specific gravity: SG = /water

• Substances with specific gravities less than 1 are lighter than

water, and thus they would float on water.

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Specific gravity values (examples)

Fluid Temperature (oC) Specific gravity (SG)

Mercury 25 13.633
Acetone 25 0.787
Alcohol, ethyl (ethanol) 25 0.787
Oil, Castor 25 0.959
Dichlorodifluoromethane refrigerant
25 1.315
R-12
Sea water 25 1.028

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Pressure - Pressure Gauge

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Pressure
• In most thermodynamic investigations, absolute pressure
(total pressure) is considered.

• Pressure gauges and vacuum gauges, however, read the

difference between the absolute pressure and the
atmospheric pressure existing at the gauge.

• This is shown graphically in figure given in next slide.

• Pressures below atmospheric and slightly above atmospheric,

the pressure differences are measured with a manometer,
which contains water, mercury, alcohol, oil, or other fluids.
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• Absolute pressure = Atmospheric pressure + Pressure

gauge pressure
 pabs = patm + pgauge or

 pgauge = pabs ‒ patm

• Absolute pressure = Atmospheric pressure – Vacuum

gauge pressure
• pabsolute = patmospheric – pvac or
• pvac = patm – pabs

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Figure - Pressures

Pabs,1
Ordinary pressure gauge
p = (pabs,1 – patm)

Patm Reference line

Ordinary vacuum gauge

p = (patm – pabs,2)
Pabs,2
Barometer reads
atmospheric pressure

0
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Figure - Pressures

pgauge

Atmospheric pressure
pabsolute
pvacuum

pabsolute patmosphere

0
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Atmospheric Pressure
(Barometer)

Figure: The basic barometer

• The atmospheric pressure can be measured by inverting a
mercury-filled tube into a mercury container that is open to
the atmosphere as shown in figure.
• The unit of mmHg is also called the torr.
• Therefore, 1 atm = 760 mmHg = 760 torr.
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Atmospheric Pressure
• Atmospheric pressure is measured by a device called a
barometer
 thus, the atmospheric pressure is often referred to as
the barometric pressure.
• The pressure at point B is equal to the atmospheric
pressure.
• The pressure at C can be taken to be zero since there is
only mercury vapor above point C and the pressure is
very low relative to Patm and can be neglected to an
excellent approximation.
• Writing a force balance in the vertical direction gives:
Patm = gh
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Temperature
• A temperature is an objective
comparative measure of hot or cold.

• It is also defined as Degree of hotness of

any system.

• It is measured by a thermometer.

• the most common scale of temperature:

• Celsius (denoted °C; formerly
called centigrade),
• Fahrenheit (denoted °F), and,
• especially in science, Kelvin (denoted K).
A typical Celsius thermometer measures a winter day
temperature of−17°C 40

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Temperature scales
oC oF oR
K
Normal H2O 100.00 373.15 211.95 671.67
Boiling point

Normal H2O 0.00 273.15 32.00 491.67

Ice point

Absolute ‒ 273.15 0.00 ‒ 459.67 0.00

zero
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Comparison of temperature scales

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Temperature conversion
• K = oC + 273.15

• oR = oF + 459.67
o
C o F  32

100 180

o
C
9

5 o
F  32  o
C  0.5556  o
F  32 
9 
o
F    o C   32
5 
o

F  1.8  o C  32
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• It is common practice to round the constant in:

 Kelvin scale to 273, and that in
 Rankine scale to 460.

• The temperature scales in the two unit systems are

related by:
 T (oR) = 1.8 T (K)
 T (oF) = 1.8 T (oC) + 32

• At the same time the differential in temperature:

 T (K) = T (oC)
 T (oR) = T (oF)

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Differential in temperature

T = 100oC = T = 373.15 K

T = 60oC = T = 333.15 K
T =20oC T =20 K
T= 40oC = T = 313.15 K

T = 0oC = T = 273.15 K

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State and Equilibrium

• Consider a system not undergoing any change.

• At this point, all the properties can be measured or

calculated throughout the entire system.

• It gives us a set of properties that completely describes

the condition, or the state, of the system.

• At a given state, all the properties of a system have fixed

values.

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A system at two different states

• If the value of even one property changes, the state will

change to a different one.

• The figure shows a system at two different states.

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A closed system reaching thermal equilibrium.

20oC 23oC 32oC 32oC

30oC 32oC
35oC 40oC 32oC 32oC
42oC 32oC

(a) Before (b) After

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• Thermodynamics deals with equilibrium states.

• The word equilibrium implies a state of balance.

• In an equilibrium state there are no unbalanced

potentials (or driving forces) within the system.

• A system in equilibrium experiences no changes when it

is isolated from its surroundings.

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Equilibriums in Thermodynamics

• Thermal equilibrium

• Mechanical equilibrium

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• Phase equilibrium

• Chemical equilibrium

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Types of equilibriums:
 Thermal equilibrium
• if the temperature is the same throughout the
entire system.
• the system involves no temperature differential,
which is the driving force for heat flow.

 Mechanical equilibrium
• if there is no change in pressure at any point of the
system with time.
• the pressure may vary within the system with
elevation as a result of gravitational effects.
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 Phase equilibrium
• system involves two phases (Water + Steam).
• mass of each phase reaches an equilibrium
level and stays there.

 Chemical equilibrium
• if its chemical composition does not change
with time, that is, no chemical reactions occur.

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The State Postulate

• The state of a system is described by its properties.
• But it is not need to specify all the properties in order
to fix a state.
• Once a sufficient number of properties are specified,
the rest of the properties assume certain values
automatically.
• That is, specifying a certain number of properties is
sufficient to fix a state.
• The number of properties required to fix the state of a
system is given by the state postulate:
 The state of a simple compressible system is completely
specified by two independent, intensive properties,
temperature and specific volume.
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Processes and Cycles

• Any change that a system undergoes from one equilibrium state to
another is called a process.
• The series of states through which a system passes during a process is
called the path of the process (Figure).
• To describe a process completely, it should specify the initial and final
states of the process, as well as the path it follows, and the interactions
with the surroundings.

A process between states 1 and 2

and the process path. The P-V diagram of a compression process.
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Quasi-static
• 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.

• A quasi-equilibrium process can be viewed as a sufficiently

slow process that allows the system to adjust itself internally
so that properties in one part of the system do not change
any faster than those at other parts.

(infinitesimal = extremely small:

The amounts of radioactivity present were infinitesimal.)

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Different Processes
• The prefix iso- is often used to designate a process for
which a particular property remains constant.

• An isothermal process is a process during which the

temperature T remains constant;

• An isobaric process is a process during which the

pressure P remains constant; and

• An isochoric (or isometric) process is a process during

which the specific volume v remains constant.
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• A system is said to have undergone a cycle if it returns to

its initial state at the end of the process.

• For a cycle, or cyclic process, the initial and final states

are identical.

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The Steady-Flow Process

• The terms steady and uniform are used frequently in
engineering, and thus it is important to have a clear
understanding of their meanings.

• The term steady implies no change with time.

• The opposite of steady is unsteady, or transient.

• The term uniform implies no change with location over a

specified region.

• These meanings are consistent with their everyday use

(steady flow, uniform properties, etc.).
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Continuum
• Matter is made up of atoms that are widely spaced in the gas phase.

• Yet it is very convenient to disregard the atomic nature of a substance and

view it as a continuous, homogeneous matter with no holes, that is, a
continuum.

• The continuum idealization allows us to treat properties as point

functions.

• This idealization is valid as long as the size of the system is large relative to
the space between the molecules.

• This is the case in practically all problems, except some specialized ones.

• The continuum idealization is such as “the density of water in a glass is the

same at any point.”

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Point functions & Path functions

• Properties are point functions (i.e., they depend on the state
only, and not on how a system reaches that state), and they
have exact differentials designated by the symbol d.

• A small change in volume is represented by dV, and the total

volume change during a process between states 1 and 2 is:
2

 dV  V
1
2  V1  V

• That is, the volume change during process 1–2 is always the
volume at state 2 minus the volume at state 1, regardless of
the path followed (Figure given in the next slide).

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Properties are point functions; but heat and work are path
functions (their magnitudes depend on the path followed).
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• Path functions have inexact differentials designated by

the symbol .

• Therefore, a differential amount of heat or work is

represented by Q or W, respectively,
– instead of dQ or dW.

• The total work done during process from state-1 to

state-2 , however, is:
2

 W  W 12 but not W 
1
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Sign convention
• Heat and work are directional quantities, and thus:

• The complete description of a heat or work interaction

requires the specification of both the magnitude and
direction.

• Formal sign convention are:

 Heat transfer to a system and work done by a system
are positive.

 Heat transfer from a system and work done on a

system are negative.
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• Heat absorbed by the system = q +ve (positive)

• Heat evolved by the system = q −ve (negative)

• Work done by the system = w +ve (positive)

• Work done on the system = w −ve (negative)

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• Let us see here the sign conventions used for heat

energy and work energy transfer
 Following figure displayed here indicates the sign
conventions for heat and work energy interactions in
thermodynamics.

Surrounding

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Sign Conversions

Boundary
Boundary

Heat Heat
Positive Negative
System System
Work Work
Positive Negative
Surroundings
Surroundings

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• Sign convention for heat energy transfer

 If heat energy is added to the system from surrounding, quantity of
heat energy transferred will be considered as positive.

 If heat energy is rejected from the system to the surrounding, quantity

of heat energy transferred will be considered as negative.

• Sign convention for work energy transfer

 If work is done by the system over its surrounding, quantity of work
energy transferred will be considered as positive.

 If work is done over the system from its surrounding, quantity of work
energy transferred will be considered as negative.

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• The following conventions are adopted for study of

thermodynamic process.

a) Work done by a system is taken as positive; work done on

the system is negative.

b) Heat gained by the system is taken as positive. Heat lost

by the system is negative.

c) Increase in internal energy is taken as positive. Decrease

in internal energy is taken as negative.

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