52

 A form of energy associated with the motion of atoms or

molecules.
 Heat always moves from a warmer place to a cooler place.
 Hot objects in a cooler room will cool to room temperature.
 Cold objects in a warmer room will heat up to room temperature.
 If a cup of coffee and a red popsickle were left on the table in this
room what would happen to them? Why?
 The cup of coffee will cool until it reaches room temperature. The
popsickle will melt and then the liquid will warm to room
temperature.
Heat transfers in three ways:
Conduction
Convection
Radiation
 Transfer of heat through direct contact.

 Occurs anytime objects at different temperatures are touching

each other.

 As long as the objects are in contact, transfer of heat will continue

until the temperature of the objects is the same.
 Example: If you leave a metal spoon in a pan of soup that you are
heating on the stove, it may burn your fingers. The spoon is in direct
contact with the hot soup and heat is transferred to the spoon.
 Conduction
When you heat a metal strip at one end, the heat
travels to the other end.

As you heat the metal, the particles vibrate, these

vibrations make the adjacent particles vibrate, and so on
and so on, the vibrations are passed along the metal and
so is the heat. We call this? Conduction
 Metals are different

The outer e______

lectrons of metal atoms
drift, and are free to move.

When the metal is

heated, this ‘sea of
inetic
electrons’ gain k_____
energy and transfer it
throughout the metal.

Insulators, such as w___

ood and p____,
lastic do not
have this ‘sea of electrons’ which is why they
do not conduct heat as well as metals.
 Some materials conduct heat better than others.
 Materials that transfer heat well are called
conductors.
 Metals are usually good conductors.
 Wood, paper and plastic are not.
 Materials that stop the transfer of heat are called
insulators (styrofoam, wool, fiberglass).
Why does metal feel colder than wood, if
they are both at the same temperature?
Metal is a conductor, wood is an insulator. Metal
conducts the heat away from your hands. Wood
does not conduct the heat away from your hands as
well as the metal, so the wood feels warmer than
the metal.
 The transfer of energy in a liquid or gas.

 When part of a gas or liquid is heated, the particles it is made up of

move faster and spread out more.

 The moving particles bump into other particles, causing them to move
faster and spread out more.
 When particles in the air spread out,
they become less dense and generally
rise above the unheated, more dense
particles around them.

 The denser masses of the gas or liquid

move in to fill the space left by the
heated particles.

 The particles that move away from the

source of heat become cooler and
more dense.
 Convection
What happens to the particles in a liquid or a
gas when you heat them?

The particles spread out and

become less dense.

This effects fluid movement.

What is a fluid?A liquid or gas.
Fluid movement

Cooler, more d____,

ense fluids
sink through w_____,
armer less
dense fluids.

In effect, warmer liquids and

gases r___
ise up.

Cooler liquids and gases s___.

ink
 Water movement

Cools at the Convection

surface current

Cooler Hot water

water sinks rises
Why is it windy at the seaside?
 Cold air sinks

Where is the Freezer

freezer compartment
compartment
put in a fridge?
It is warmer
at the
It is put at the bottom, so
top, because this warmer
cool air sinks, air rises and
so it cools the a convection
food on the current is
way down. set up.
 Energy transferred in the form of rays or waves or particles.

 We will concentrate on the type of radiation that travels as

electromagnetic waves.
 The third method of heat transfer

How does heat energy get

from the Sun to the Earth?
There are no particles
between the Sun and the
Earth so it CANNOT
travel by conduction or
by convection.

RADIATION
?
 Emission experiment
Four containers were filled with warm water. Which
container would have the warmest water after ten minutes?

Dull metal Shiny black

Shiny metal Dull black

shiny metal container would be the warmest after ten

The __________
minutes because its shiny surface reflects heat radiation
_______ back
dull black container
into the container so less is lost. The ________
emitting heat
would be the coolest because it is the best at _______
radiation.
 Absorption experiment
Four containers were placed equidistant from a heater. Which
container would have the warmest water after ten minutes?

Dull metal Shiny black

Shiny metal Dull black

dull black container would be the warmest after ten

The __________
radiation the best.
minutes because its surface absorbs heat _______
shiny metal container would be the coolest because it is
The _________
the poorest at __________
absorbing heat radiation.
 You can feel the sun warm your skin on a sunny day.
 This is because the energy causes the particles in your skin to
move faster = more heat energy.
 Include visible light, microwaves and infrared light

 Can travel through space.

 The sun is our major source.

PHYSICAL MECHANISM OF
CONVECTION
Conduction and convection both
require the presence of a material
medium but convection requires
fluid motion.
Convection involves fluid motion as
well as heat conduction.
Heat transfer through a solid is
always by conduction.
Heat transfer through a fluid is by
convection in the presence of bulk
fluid motion and by conduction in
the absence of it.
Therefore, conduction in a fluid can
be viewed as the limiting case of
convection, corresponding to the
case of quiescent fluid.
76
convection in daily life

• We turn on the fan on hot

summer days to help our
body cool more effectively.
The higher the fan speed,
the better we feel.
• We stir our soup and blow
on a hot slice of pizza to
make them cool faster.
• The air on windy winter
days feels much colder
than it actually is.
• The simplest solution to
heating problems in
electronics packaging is to
use a large enough fan.

77
 Internal versus External Flow

External flow: The flow of an unbounded fluid over a surface such

as a plate, a wire, or a pipe.
Internal flow: The flow in a pipe or duct if the fluid is completely
bounded by solid surfaces.

• Water flow in a pipe is

internal flow, and
airflow over a ball is
external flow .
• The flow of liquids in a
duct is called open-
channel flow if the duct
is only partially filled
with the liquid and
there is a free surface.
External flow over a tennis ball, and the
turbulent wake region behind.
78
Compressible versus Incompressible Flow
Incompressible flow: If the
density of flowing fluid remains
nearly constant throughout (e.g.,
liquid flow).
Compressible flow: If the density
of fluid changes during flow (e.g.,
high-speed gas flow)
When analyzing rockets, spacecraft,
and other systems that involve high-
speed gas flows, the flow speed is
often expressed by Mach number
c is the speed of sound whose
value is 346 m/s in air at room
temperature at sea level.
Gas flows can often be
approximated as incompressible
if the density changes are under
about 5 percent, which is usually
the case when Ma < 0.3.
Therefore, the compressibility
effects of air can be neglected at
speeds under about 100 m/s.

Ma = 1 Sonic flow
Ma < 1 Subsonic flow
Ma > 1 Supersonic flow
Ma >> 1 Hypersonic flow
79
Laminar versus Turbulent Flow
Laminar flow: The highly
ordered fluid motion
characterized by smooth
layers of fluid. The flow of
high-viscosity fluids such as
oils at low velocities is
typically laminar.
Turbulent flow: The highly
disordered fluid motion that
typically occurs at high
velocities and is
characterized by velocity
fluctuations. The flow of low-
viscosity fluids such as air at
high velocities is typically
turbulent.
Transitional flow: A flow
that alternates between
being laminar and turbulent.
Laminar, transitional, and turbulent flows. 80
LAMINAR AND Laminar flow is encountered when
highly viscous fluids such as oils flow
TURBULENT FLOWS in small pipes or narrow passages.
Laminar: Smooth
streamlines and highly
ordered motion.
Turbulent: Velocity
fluctuations and highly
disordered motion.
Transition: The flow
fluctuates between
laminar and turbulent
flows.
Most flows encountered in
practice are turbulent.

The behavior of
colored fluid
Laminar and injected into the
turbulent flow flow in laminar
regimes of and turbulent
candle smoke. flows in a pipe. 81
 HEAT AND MOMENTUM TRANSFER IN
TURBULENT FLOW

Most flows encountered in engineering practice are turbulent, and thus it is important to
understand how turbulence affects wall shear stress and heat transfer.
However, turbulent flow is a complex mechanism dominated by fluctuations, and the
theory of turbulent flow is still not fully understood.
Therefore, we must rely on experiments and the empirical or semi-empirical correlations
developed for various situations.
Turbulent flow is characterized by disorderly and
rapid fluctuations of swirling regions of fluid, called
eddies, throughout the flow.
These fluctuations provide an additional
mechanism for momentum and energy transfer.
The swirling eddies transport mass, momentum,
and energy to other regions of flow much more
rapidly than molecular diffusion, greatly enhancing
mass, momentum, and heat transfer.
Turbulent flow is associated with much higher
values of friction, heat transfer, and mass transfer
coefficients. 82
Convection:
Heat transfer due to convection involves the
energy exchange between a surface and an adjacent fluid

Forced Convection: When a fluid is made to flow past a

solid surface by an external agent such as a fan or pump

Free/Natural Convection: Warmer (or cooler) fluid next to the

Solid boundary cause circulation because of the density variation
Resulting from the temperature variation throughout a region of
the fluid.

Newton’s Law of Cooling: q/A = h∆T

q: rate of convective heat transfer (W); A: area normal to direction of

heat transfer; h: convective heat transfer coefficient, ∆T: temperature
Difference between the surface and the fluid.
 Natural (or Unforced)
versus Forced Flow

Forced flow: A fluid is forced

to flow over a surface or in a
pipe by external means such
as a pump or a fan.
Natural flow: Fluid motion is
due to natural means such as
the buoyancy effect, which
manifests itself as the rise of
warmer (and thus lighter) fluid
and the fall of cooler (and thus
denser) fluid. In this schlieren image, the rise of
lighter, warmer air adjacent to her body
indicates that humans and warm-
blooded animals are surrounded by
thermal plumes of rising warm air.

84
 Steady versus Unsteady Flow

• The term steady implies no change at a point with time.

• The opposite of steady is unsteady.
• The term uniform implies no change with location over a
specified region.
• The term periodic refers to the kind of unsteady flow in
which the flow oscillates about a steady mean.
• Many devices such as turbines, compressors, boilers,
condensers, and heat exchangers operate for long periods
of time under the same conditions, and they are classified
as steady-flow devices.

85
Thermodynamics
86
 From the greek therme (heat) and dynamis (power,force)
 The capacity of hot bodies to produce work

Sadi Carnot
(1796-1832)

87
Thermodynamics versus Kinetics
 Thermodynamics deals with stability of systems. It tells us ‘what should
happen?’. ‘Will it actually happen(?)’ is not the domain of thermodynamics and
falls under the realm of kinetics.
 At –5°C at 1 atm pressure, ice is more stable then water. Suppose we cool water
to –5°C. “Will this water freeze?” (& “how long will it take for it to freeze?”) is
(are) not questions addressed by thermodynamics.
 Systems can remain in metastable state for a ‘long-time’.
 Window pane glass is metastable– but it may take geological time scales for it
to crystallize!
 At room temperature and atmospheric pressure, graphite is more stable then
diamond– but we may not lose the glitter of diamond practically forever!
Thermodynamics (TD): perhaps the most basic science
 One branch of knowledge that all engineers and scientists must have a grasp of
(to some extent or the other!) is thermodynamics.
 In some sense thermodynamics is perhaps the ‘most abstract subject’ and a
student can often find it very confusing if not ‘motivated’ strongly enough.
 Thermodynamics can be considered as a ‘system level’ science- i.e. it deals with
descriptions of the whole system and not with interactions (say) at the level of
individual particles.
• I.e. it deals with quantities (like T,P) averaged over a large collection of entities
(like molecules, atoms)*.
• This implies that questions like: “What is the temperature or entropy of an
atom?”; do not make sense in the context of thermodynamics (at lease in the usual way!).
 TD puts before us some fundamental laws which are universal** in nature (and
hence applicable to fields across disciplines).

* Thermodynamics deals with spatio-temporally averaged quantities.

** They apply to the universe a whole as well! (Though the proof is lacking!).
 0th
 Definition of temperature
 Systems at different temperatures exchange energy until
reaching a thermal equilibrium
 1st
 Conservation of energy
 heat is a form of energy
 2nd
 Entropy of an isolated system never decreases
 perpetual motions of machines is impossible
 3rd
 Entropy at absolute zero temperature (0 K)
 it is impossible to cool a system until zero
 System
 a set of interacting or interdependent entities,
real or abstract, forming an integrated whole
 Closed System
 System that is isolated from its
surroundings

 In thermodynamics
 a closed system can exchange heat and work
(energy), but not matter, with its surroundings
 Isolated system cannot exchange anything

 Control Volume
 Region of space through which mass flows
Work (J)
 Measure of motion accomplishment of a system due to the
action of a force over a distance and time (Dynamics)
 (…) work expresses the useful effect that a motor is capable of
producing. This effect can always be linked to the elevation of a
weight to a certain height(…) the product of the weight
multiplied by the height to which it is raised” (Sadi Carnot)
Power (W=J/s)
 The rate at which work is done

Energy (J)
 Amount of work that can be accomplished by a force
 Is the capacity of a system to perform work
 Open, closed and isolated systems

 To a thermodynamic system two ‘things’ may be added/removed:

 energy (heat, work)  matter.
 An open system is one to which you can add/remove matter (e.g. a open beaker to which
we can add water). When you add matter- you also end up adding heat (which is contained
in that matter).
 A system to which you cannot add matter is called closed.
Though you cannot add/remove matter to a closed system, you can still add/remove heat
(you can cool a closed water bottle in fridge).
 A system to which neither matter nor heat can be added/removed is called isolated.
A closed vacuum ‘thermos’ flask can be considered as isolated.

Type of boundary Interactions Mass

Open All interactions possible (Mass, Work, Heat)
Closed Matter cannot enter or leave Interactions possible
Semi-permeable Only certain species can enter or leave Work
Insulated Heat cannot enter or leave
Rigid Mechanical work cannot be done* Heat
Isolated No interactions are possible**
* By or on the system
** Mass, Heat or Work
 Matter is easy to understand and includes atoms, ions, electrons, etc.
 Energy may be transferred (‘added’) to the system as heat, electromagnetic radiation etc.
 In TD the two modes of transfer of energy to the system considered are Heat and Work.
 Heat and work are modes of transfer of energy and not ‘energy’ itself.
 Once inside the system, the part which came via work and the part which came via
heat, cannot be distinguished*. More sooner on this!
 Before the start of the process and after the process is completed, the terms heat and
work are not relevant.
 From the above it is clear that, bodies contain internal energy and not heat (nor work!).
 Matter when added to a system brings along with it some energy. The ‘energy density’
(energy per unit mass or energy per unit volume) in the incoming matter may be higher or lower than the
matter already present in the system.

* The analogy usually given is that of depositing a cheque versus a draft in a bank. Once credited to an account, cheque and draft have no
meaning. (Also reiterated later).
Energy released by burning one tonne of crude oil (Toe)
 Approximately 42 GJ (oil properties can vary)

 International Energy Agency:

 10 Gcal

 41,868 GJ

 11,630 MWh

 7,4 barrels of oil

Primary
 Energy contained in raw fuels

Final
 Energy available after conversion and transportation systems

Útilization
 Energy after utilization
Property – macroscopic characteristic of a system
 Extensive properties
 The value for the overall system is the sum of the values for its
parts (mass, volume, energy)
 Intensive properties
 The values are not additive, may vary from one place to the
other at any time (pressure, temperature, specific volume)

State – a condition of a system, described by the properties

 usually a snapshot in time x(t)=(P,T)

Process – change of properties and therefore state of the system

 brings the system from x(t) to x(t+1)
Specific volume

 volume occupied by a unit of mass (mass / volume)

 water 4º - 1dm3/kg
 Iron -128,2 cm3/kg

Density

 mass by unit of volume (volume/mass)

 Water at 4º - 1000kg/m3 / water at 20º - 998kg/m3
 Iron - 7800kg/m3
Pressure (Pa=N/m2)
 Effect of a force in a surface
 Caused by the collision of molecules to the boundaries of a
system

Temperature (K)
 At the microscopic scale, is a measure of
the energy of the particles
 solid state (vibration of molecules)
 liquid (translation movement)
 gas (vibration and rotation movements
 Thermal equilibrium – system does not change temperature
Few points about temperature scales and their properties
 Celsius (Farenheit, etc.) are relative scales of temperature and zero of these scales do not have
a fundamental significance. Kelvin scale is a absolute scale. Zero Kelvin and temperatures
below that are not obtainable in the classical sense.
 Classically, at 0K a perfect crystalline system has zero entropy (i.e. system attains its minimum
entropy state). However, in some cases there could be some residual entropy due to degeneracy
of states.
 At 0K the kinetic energy of the system is not zero. There exists some zero point energy.
 Pressure
 Pressure* is force per unit area (usually exerted by a fluid on a wall**).
 It is the momentum transferred (say on a flat wall by molecules of a gas) per unit area, per unit time. (In
the case of gas molecules it is the average momentum transferred per unit area per unit time on to the flat wall).
 P = momentum transferred/area/time.
 Pressure is related to momentum, while temperature is related to kinetic energy.
Wall of a container

‘Crude schematic’
of particles
impinging on a
wall.

* ‘Normal’ pressure is also referred to as hydrostatic pressure.

** Other agents causing pressure could be radiation, macroscopic objects impinging on a wall, etc.
Heat (J)
 is the process of energy transfer from one body or system due
to thermal contact
 can be defined as thermal energy
 energy of a body that increases with temperature

Specific heat
 energy required to increase 1 degree of a 1unit (kg or mol) of a
substance
 Can be measured at constant pressure (Cp)
 Water - 4,186 J/(g·K) (25 º C) / 2,080 J/(g·K) (100º C)
 Can be measured at constant volume (Cv)
 Work output
Thermal Efficiency 0≤ ≤1
Heat input

Heat output
η = 1−
Heat Engines
Heat input
TLow
Carnot Efficiency
η = 1−
THigh
Some devices use work to move heat from one place to other
 inverse process of thermal machines

Heat Pumps

Heat output TH
COPheating = =
Work input TH − TC
Air conditioners

Heat output TC
COPcooling = =
Work input TH − TC
When two systems are put in contact with each other, there will be
a net exchange of energy between them unless or until they are in
thermal equilibrium, that is, they are at the same temperature

 "If A and C are each in thermal equilibrium with B, A is also in

thermal equilibrium with C.“
 single temperature and pressure can be attributed to the
whole system
Measure of internal energy of a closed system
 sum of internal energy plus the product of pressure and
volume
 For constant pressure, the enthalpy increases with heat

Specific enthalpy (J/kg)

 Energy per unit of mass (PCI)
 Low (hidrocarbonets)
 Fuel 42MJ/kg
 Propane 46 MJ/kg
 High
The total amount of energy in a closed system remains constant
over time (are said to be conserved over time)

 The increase in the internal energy of a system is equal to the

amount of energy added by heating the system minus the
amount lost as a result of the work done by the system on its
surroundings.
 Energy cannot be created nor destroyed
 Energy can change form (for example chemical to thermal)
Thermodynamics
 Measure of uniformity of the distribution (quality) of energy

Information
 For a system whose exact description is unknown, its entropy is defined as
the amount of information needed to exactly specify the state of the system
Temperature differences between systems in contact with each
other tend to even out and that work can be obtained from these
non-equilibrium differences, but that loss of heat occurs, in the form
of entropy, when work is done

 In a system, a process that occurs will tend to increase the total

entropy of the universe
 Heat generally cannot flow spontaneously from a material at lower
temperature to a material at higher temperature (Clausius)
 It is impossible to convert heat completely into work in a cyclic process
(Kelvin)
 Reversible (ideal)
 system and surroundings can be restored to the initial state from the final
state without producing any changes in the thermodynamics properties
 it should occur infinitely slowly due to infinitesimal gradient
 all the changes in state occurred in the system are in thermodynamic equilibrium
with each other

 Irreversible (natural)
 All processes in nature are irreversible
 Finite gradient between the two states of the system
 heat flow between two bodies occurs due to temperature gradient between the
two bodies;
 As a system approaches absolute zero, all processes
cease and the entropy of the system approaches a
minimum value
 decreasing entropy of a system requires increasing the
entropy of surroundings
 The absolute pressure and volume of a gas (ideal) are inversely
proportional, if the temperature is kept constant within a closed
system

 Ideal Gas law

 k - Boltzman constant (8.314 J·K−1mol-1)
 n – number of moles

PV = nRT
Isobaric Isometric/ Isochoric Isothermal
ΔT = 0 but Q ≠ 0

Adiabatic Cyclic
ΔT ≠ 0 but Q = 0 If clockwise – heat engine
If counterclockwise – heat pump
 Carnot Theorem
 No engine operating between two heat reservoirs can be more efficient
than a Carnot engine operating between those same reservoirs

Pressure-Volume Temperature-Entropy
 There are no ideal cycles
 Irreversible systems, losses of heat
 Heat and Work
 Work (W) in mechanics is displacement (d) against a resisting force (F). W = F × d
 Work has units of energy (Joule, J).
 Work can be expansion work (P∆V), electrical work, magnetic work etc. (many sets of
stimuli and their responses).
 Heat as used in TD is a tricky term (yes, it is a very technical term as used in TD).
 The transfer of energy as a result of a temperature difference is called heat.
 “In TD heat is NOT an entity or even a form of energy; heat is a mode of transfer of
energy” [1].
 “Heat is the transfer of energy by virtue of a temperature difference” [1].
 “Heat is the name of a process, not the name of an entity” [1].
 “Bodies contain internal energy (U) and not heat” [2].
 The ‘flow’ of energy down a temperature gradient can be treated mathematically by
considering heat as a mass-less fluid [1] → this does not make heat a fluid!

Expansion work
To give an example (inspired by [1]):
assume that you start a rumour that there is ‘lot of’ gold under the class room floor. This rumour ‘may’ spread when persons talk to each other.
The ‘spread of rumor’ with time may be treated mathematically by equations, which have a form similar to the diffusion equations (or heat
transfer equations). This does not make ‘rumour’ a fluid!
[1] Four Laws that Drive the Universe, Peter Atkins, Oxford University Press, Oxford, 2007. [2] Physical Chemistry, Ira N Levine, Tata McGraw Hill Education Pvt. Ltd., New York (2002).
  Work is coordinated flow of matter.
 Lowering of a weight can do work
 Motion of piston can do work
 Flow of electrons in conductor can do work.
 Heat involves random motion of matter (or the constituent entities of matter).
 Like gas molecules in a gas cylinder
 Water molecules in a cup of water
 Atoms vibrating in a block of Cu.

 Energy may enter the system as heat or work.

 Once inside the system:
• it does not matter how the energy entered the system* (i.e. work and heat are terms
associated with the surrounding and once inside the system there is no ‘memory’ of how
the input was received and
• the energy is stored as potential energy (PE) and kinetic energy (KE).
 This energy can be withdrawn as work or heat from the system.

* As Aktins put it: “money may enter a back as cheque or cash− but once inside the bank there is no difference”.
 Spontaneous and Driven processes

 A spontaneous process is one which occurs ‘naturally’, ‘down-hill’ in energy*. I.e. the
process does not require input of work in any form to take place.
• Melting of ice at 50°C is a spontaneous process.
 A driven process is one which wherein an external agent takes the system uphill in energy
(usually by doing work on the system).
• Freezing of water at 50°C is a driven process (you need a refrigerator, wherein electric
current does work on the system).
 Later on we will note that the entropy of the universe will increase during a spontaneous
change. (I.e. entropy can be used as a single parameter for characterizing spontaneity).

Spontaneous process
(Click to see)

* The kind of ‘energy’ we are talking about depends on the conditions. As in the topic on Equilibrium, at constant temperature and pressure the
relevant TD energy is Gibbs free energy.
 Heat Capacity

 Heat capacity is the amount of heat (measured in Joules or Calories) needed to raise an
unit amount of substance (measured in grams or moles) by an unit in temperature
(measured in °C or K). As mentioned before bodies (systems) contain internal energy and not heat.
 This ‘heating’ (addition of energy) can be carried out at constant volume or constant
pressure. At constant pressure, some of the heat supplied goes into doing work of
expansion and less is available with the system (to raise it temperature).
 Heat capacity at constant Volume (CV):  ∂E 
CV =  
It is the slope of the plot of internal energy with temperature.  ∂T V
 Heat capacity at constant Pressure (CP):
 ∂H 
It is the slope of the plot of enthalpy with temperature. C =  
 ∂T  P
P

 Units: Joules/Kelvin/mole, J/K/mole, J/°C/mole, J/°C/g.

 Heat capacity is an extensive property (depends on ‘amount of matter’)
 If a substance has higher heat capacity, then more heat has to be added to raise its
temperature. Water with a high heat capacity (of CP = 4186 J/K/mole =1 Cal/°C/Kg) heats
up slowly as compared to air (with a heat capacity, CP = 29.07J/K/mole) ⇒ this implies that
oceans will heat up slowly as compared to the atomosphere.
 As T→0K, the heat capacity tends to zero. I.e near 0 Kelvin very little heat is required to
raise the temperature of a sample. (This automatically implies that very little heat has to
added to raise the temperature of a material close to 0K.
This is of course bad news for cooling to very low temperatures− small leakages of heat will lead to drastic increase in temperature).
 The Laws of Thermodynamics The First Law

 The internal energy of an isolated system is constant.

 A closed system may exchange energy as heat or work. Let us consider a close system at
rest without external fields.
 There exists a state function U such that for any process in a closed system:
∆U = q + w [1]
 q → heat flow in to the system
 w → work done on the system (work done by the system is negative of above- this is just ‘one’ sign convention)
q & w are not state functions → i.e. they depend on the path of a process.
 U is the internal energy. Being a state function for a process ∆U depends only of the final
and initial state of the system. ∆U = Ufinal – Uinitial. In contrast to U, q & w are NOT state
functions (i.e. depend on the path followed).
 For an infinitesimal process eq. [1] can be written as: dU = dq + dw
 The change in U of the surrounding will be opposite in sign, such that:
∆Usystem + ∆Usurrounding = 0
 Actually, it should be ∆E above and not ∆U {however, in many cases K and V are zero
(e.g. a system at rest considered above) and the above is valid- as discussed elsewhere}.
 It is to be noted that in ‘w’ work done by one part of the system on another part is not included.
 The Second Law The second law comes in many equivalent forms

 It is impossible to build a cyclic machine* that converts heat into work with 100%
efficiency → Kelvin’s statement of the second law.
 Another way of viewing the same:
it is impossible to construct a cyclic machine** that completely (with 100% efficiency)
converts heat, which is energy of random molecular motion, to mechanical work, which is
ordered motion.
 The unavailable work is due to the role of Entropy in the process.

Heat q Kelvin’s
Heat reservoir Cyclic engine × statement of the
second law
Not possible
100% Work (w)

Heat q Heat q’
Heat reservoir Cyclic engine Cold Reservoir  Possible
Called the source Called the sink
Work (w)
* For now we are ‘building’ ‘conceptual machines’ !
** These ‘engines’ which use heat and try to produce work are called heat engines.
Another statement of the second law → the Clausius statement

 Heat does not ‘flow*’ from a colder body to a hotter body, without an concomitant change
outside of the two bodies→ Clausius’s statement of the second law.(a)
 This automatically implies that the spontaneous direction of the ‘flow of heat*’ is from a
hotter body to a colder body.(b)
 The Kelvin’s and Clausius’s statements of the second law are equivalent. I.e. if we violate
Kelvin’s statement, then we will automatically violate the Clausius’s statement of the
second law (and vice-versa).

* Used here in the ‘common usage sense’.

(b) is obvious, but not (a) → though they represent the same fact.
A combined (Kelvin + Clausius) statement of the II Law

 The entropy* of a closed system will increase during any spontaneous change.
If we consider the Universe to be a closed system (without proof!!)**, then
 The entropy of the universe will increase during any spontaneous change (process).

* Soon we will get down to this mysterious quantity.

** For all we know the Universe could be ‘leaky’ with wormholes to other parallel Universes!
 The efficiency of a heat engine

 The efficiency of a heat engine is the amount of work output divided by the amount of heat
input.
 This efficiency depends only on the ratio of the temperature of the sink to the temperature
of the source. The maximum efficiency achievable is given by the formula below.
 This is surprising as:
• there is no mention of the medium of the system (or its properties),
• the formula has only temperatures and
• the temperature of the sink seems to play a major role (as the presence of the sink is
usually not intentional or obvious→ in a steam engine sink is the air around the engine and
source is the hot steam).
Important message Sink (characterized by its temperature) is as important as the source.
 To increase the maximum possible efficiency of a heat engine, either the temperature of the
source has to be increased on the temperature of the sink has to be decreased.

woutput  Tsink 
ηheat engine = ηheat
max
engine = 1 −  
qinput  source 
T
Clausius statement of the second law

 Heat cannot spontaneously flow from a cold (low temperature) body to a hot body.
 To make heat flow from a cold body to a hot body, there must be accompanying change
elsewhere (work has to be done to achieve this).
 Q&A What is the difference between ‘heat engine’ and ‘work engine’?

 Actually both the engines we are going to describe here are usually known as heat engines.
 We are differentiating two types of engines to see which one produces work and which one
actually transfers heat.
 In the heat engine as the temperature of the cold body tends to zero Kelvin, more and more
work has to be done to transfer the heat from the cold body to the hot body.

‘Work engine’ ‘heat engine’

Like a steam engine Like a refrigerator

Heat reservoir Hot body

Source
Heat q Heat q

Cyclic engine Work (w) Cyclic engine Work (w)

Heat q’ Heat q’

Cold Reservoir Sink Cold Body

The main objective here is
The main objective here to transfer heat from a
is to produce work cold body to a hot body
 The Third Law

 For substances in internal equilibrium, undergoing an isothermal process, the entropy

change goes to zero as T (in K) goes to zero.

lim ∆S =0
T →0

 The law is valid for pure substances and mixtures.

 Close to Zero Kelvin, the molecular motions have to be treated using quantum mechanics
→ still it is found that quantum ideal gases obey the third law.

Phenomenological description of the third law.

 There does not exist any finite sequence of cyclical process, which can cool a body to zero
Kelvin (absolute zero).
 Humorous look at
the three laws

 The first law says: “you cannot win”.

 The second law says: “you can at best break even- that too at zero Kelvin”.
 Third law says: “zero Kelvin is unattainable”.

Q&A What is the difference in the ‘status’ of quantities like T, U, S, H, A & G?

 T, U & S are fundamental quantities of thermodynamics.

 H, A & G do not give us new fundamental concepts, but are for better ‘accounting’ in
thermodynamics.
Working Principle

 Energy is added to the gas stream

 Combustion increases the temperature,
velocity, and volume of the gas flow
 Turbine rotates, powering the compressor
 Energy is then extracted in the form of shaft
power, compressed air and thrust
 Gas-turbine is used in aircraft propulsion and electric
power generation.
 High thermal efficiencies up to 44%.
 Suitable for combined cycles (with steam power plant)
 High power to weight ratio, high reliability, long life
 Fast start up time, about 2 min, compared to 4 hr for
steam-propulsion systems
 High back work ratio (ratio of compressor work to the
turbine work), up to 50%, compared to few percent in
steam power plants.
Schematic for an open gas-turbine cycle
 Brayton cycle is the ideal cycle for gas-turbine
engines in which the working fluid
 undergoes a closed loop. That is the
combustion and exhaust processes are
modeled by
 constant-pressure heat addition and rejection,
respectively
 Gas turbines are described thermodynamically
by the Brayton cycle
 In this cycle:
1. air is compressed isentropically
2. combustion occurs at constant pressure
3. heated air expands through the turbine
4. heat is rejected into the atmosphere
The Brayton ideal cycle is made up of four
internally reversible processes:
1-2 isentropic compression (in compressor)
2-3 const. pressure heat-addition (in combustion
chamber)
3-4 isentropic expansion (in turbine)
4-1 const. pressure heat rejection (exhaust)

T-s and P-v diagrams for ideal Brayton cycle

 The maximum temperature in the cycle T3 is
limited by metallurgical conditions because
 the turbine blades cannot sustain temperatures
above 1300 K.
 Higher temperatures (up to1600 K can be
obtained with ceramic turbine blades).
 The minimum temperature is set by the air
temperature at the inlet to the engine.
 Irreversibilities exist in actual cycle.
 Most important differences are deviations of actual
compressor and turbine from idealized isentropic
compression/expansion
 Pressure drop in combustion chamber

Actual Brayton cycle

  The high pressure air leaving the compressor can
be heated by transferring heat from exhaust
gases in a counter-flow heat exchanger which is
called a regenerator

Schematic for a Brayton cycle with regenerator T-s diagram for a Brayton cycle with regeneration
 The net work output of the cycle can be increased by
reducing the work input to the compressor and/or by
increasing the work output from turbine (or both).
 Using multi-stage compression with intercooling reduces
the work input the compressor.
 As the number of stages is increased, the compression
process becomes nearly isothermal at the compressor
inlet temperature, and the compression work decreases.
 Likewise utilizing multistage expansion with reheat (in a
multi-turbine arrangement) will increase the work
produced by turbines.
 When intercooling and reheating are used,
regeneration becomes more attractive since a
greater potential for regeneration exists.
 The back work ratio of a gas-turbine improves as a
result of intercooling and reheating.
 However; intercooling and reheating decreases
thermal efficiency unless they are accompanied with
regeneration.
A gas-turbine engine with two-stage compression with intercooling, two-stage expansion with reheating, and regeneration.

T-s diagram for an ideal gas-turbine cycle with intercooling, reheating, and regeneration
 Very high power-to-weight ratio
 More size efficient
 Moves in one direction only, with fewer
moving parts
 Low operating pressures
 High operation speeds
 Low lubricating oil cost and consumption
 More expensive compared to a similar-sized
reciprocating engine
 More complex machining operations
 Usually less efficient than reciprocating
engines, especially at idle
 Delayed response to changes in power
settings
 Rankine Cycle
• A vessel is filled with an amount of water
( ) and warmed at constant pressure
up to boiling
• a continuing supply of heat changes
water phase from liquid to gas (steam),
the temperature remains constant
• result : a steam at temp. Tp, pressure
Pp, volume Vp and energy stored as
internal heat or enthalpy Qp
• one m3 of water is transformed under
such conditions into 1700 m3 of steam

146
• A vessel is filled with the same water amount
( ) and warmed at constant volume up to
boiling
• a continuing supply of heat changes water
phase from liquid to gas (steam),
• result :
– steam temperature Tv >Tp,
– pressure Pv > Pp,
– Vv =Vp volume unchanged
– energy stored as internal heat or enthalpy Qv > Qp

147
• Steam generation is a phase change or water from liquid
to gas, thanks to a continuous supply of heat,
• the higher both pressure and temperature are, the higher
is the energy stored in the steam,
• the steam turbine purpose is to convert this thermal
energy into rotational mechanical energy
• the purpose of the generator is to convert this rotational
mechanical energy into electric energy

148
 The Water-Steam Cycle inside the boiler

• From F to A to B
– liquid water warm-up
Temp. K
•• B :: evaporation
B evaporation begins
begins
B C •• B to
B to C
C ::
–– mixture
mixture of
of water
water
(decreasing) and
(decreasing) and
steam (increasing)
steam (increasing)
A called saturated
called saturated
steam
steam
F
Entropy
 The Water-Steam Cycle inside the boiler (cont)

D •• C : evaporation
evaporation
completed, steam
completed, steam
Temp. K still saturated
still saturated
•• C to D
B C
–– steam
steam is
is
superheated
superheated
•• D
A –– superheated
superheated
steam sent
steam sent to
to
F turbine
turbine
Entropy
 The Water-Steam Cycle outside the boiler

D •• D to E
–– expansion
expansion in
in the
the
Temp. K steam turbine
steam turbine
•• E to F
B C
–– steam
steam is
is
condensed and
condensed and
cooled in
cooled in the
the
condenser
condenser
A
E •• F
F
–– water
water available
available for
for
Entropy aa new
new cycle
cycle
Single Rankine Reheat Steam Cycle

D
Temp. K

B C

A
E
F
Entropy
 Double Reheat Steam Cycle
• D to I
• D to I
D K – expansion in the
– expansion in the
HP steam turbine
Temp. K HP steam turbine
• I to K
C • I –tosteam
K returns to
B
– steam returns
the boiler and to
is
the boiler and is
reheated
I
•
reheated
K to L
A • K– to L
expansion in the
L IP/LP steam
– expansion in the
F turbine
IP/LP steam
Entropy turbine
Flows and Heat Exchange
in the Boiler
 156

Figure: Typical Steam Cycle

ELO
2.4
• Three basic types of components in
power cycles
– Turbines

– Pumps

– Heat exchangers

• Each of these components produces

a characteristic change in the
properties of the working fluid

• It is possible to calculate efficiencies Figure: Typical Steam Cycle

of each individual component

– Compare actual work produced by
the component to the work produced
by an ideal component
ELO
2.4
Ideal versus Real
Turbine
• KE and PE changes and
heat lost by the working fluid
in the turbine are negligible
• In an ideal case, the
working fluid does work
reversibly by expanding at a
constant entropy
• Entropy of the working fluid
entering the turbine: Sin
equals the entropy of the
Figure: h-s Diagram for Ideal and Real Turbine
working fluid leaving the
turbine Sout

ELO
2.4
 An actual turbine does less work because of
 Friction losses in the blades
 Leakage past the blades
 Mechanical friction

 Turbine efficiency (ηt) is the ratio of the actual work done by

the turbine Wt.actual to the work that would be done by the
turbine if it were an ideal turbine Wt.ideal

ELO
2.4
• Turbine efficiency ηt is
normally given by the
manufacturer
– Permits actual work done to
be calculated directly by
multiplying turbine efficiency ηt
by work done by an ideal
turbine under the same
conditions
• Turbine efficiency is generally
– 60% to 80% for small turbines
– 90% for large turbines

Figure: Entropy Diagram Measures System Efficiency

ELO
2.4
• The actual and idealized
performances of a turbine
may be conveniently
compared using a T-s
diagram
– Ideal case is a constant
entropy represented by a
vertical line
– Actual turbine involves an
increase in entropy
– The smaller the increase in
entropy, the closer the turbine
efficiency ηt is to 1.0 or 100%

Figure: Entropy Diagram Measures System Efficiency

ELO
2.4
Real Versus Ideal Pump
• Assume the change in the KE, PE and heat losses of the working
fluid while in the pump are negligible
• It is also assumed that the working fluid is incompressible
• For the ideal case, it can be shown that the work done by the
pump equals the change in enthalpy across the ideal pump

Figure: Work Done by the Pump Equals Change In Enthalpy Across the Ideal Pump

ELO
2.4
• An ideal pump provides a basis for analyzing the performance of
actual pumps
• A pump requires more work because of unavoidable losses due
to friction and fluid turbulence
• The work done by a pump equals the change in enthalpy across
the actual pump
𝑊𝑊𝑝𝑝.𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 = 𝐻𝐻𝑜𝑜𝑜𝑜𝑜𝑜 − 𝐻𝐻𝑖𝑖𝑖𝑖 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

𝑊𝑊̇ 𝑝𝑝.𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 = 𝑚𝑚̇ ℎ𝑜𝑜𝑜𝑜𝑜𝑜 − ℎ𝑖𝑖𝑖𝑖 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

Pump Efficiency
• Pump efficiency (ηp) is the ratio of the work required by the pump
if it were an ideal pump Wp.ideal to the actual work required by the
pump Wp.actual
𝑊𝑊𝑝𝑝.𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
𝜂𝜂𝑝𝑝 =
𝑊𝑊𝑝𝑝.𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎

ELO
2.4
• Pump efficiency (ηp) relates work required by an ideal pump to
actual work required by the pump
– Minimum amount of work theoretically possible to actual work required
by pump
• Pump efficiency does not account for losses in the prime mover
such as a motor or turbine
• Motor efficiency (ηm) is the ratio of actual work required by the
pump to the electrical energy input to the pump motor

ELO
2.4
Motor Efficiency
𝑊𝑊𝑝𝑝.𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
𝜂𝜂𝑚𝑚 =
𝑊𝑊𝑚𝑚.𝑖𝑖𝑖𝑖 𝐶𝐶

Where:
𝜂𝜂𝑚𝑚 = motor efficiency (no units)
Wp.actual = actual work required by the pump (ft-lbf)
Wm.in = electrical energy input to the pump motor (kWh)
C = conversion factor = 2.655 x 106 ft-lbf/kWh

ELO
2.4
Motor Efficiency
 Like pump efficiency (ηp), motor efficiency (ηm) is always less
than 1.0 or 100% for an actual pump motor
 The combination of pump efficiency and motor efficiency relates
the ideal pump to the electrical energy input to the pump motor
𝑊𝑊𝑝𝑝.𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖𝑖
𝜂𝜂𝑚𝑚𝜂𝜂𝑝𝑝 =
𝑊𝑊𝑚𝑚.𝑖𝑖𝑖𝑖 𝐶𝐶

Where:

𝜂𝜂𝑚𝑚 = motor efficiency (no units)

𝜂𝜂𝑝𝑝 = pump efficiency (no units)

Wp.ideal = ideal work required by the pump (ft-lbf)

Wm.in = electrical energy input to the pump motor (kWh)

106 ft-lbf/kWh
C = conversion factor = 2.655 x ELO
2.4
 Designed to transfer heat between two working fluids

 Several heat exchangers are used in power plant steam cycles

 Steam generator or boiler - heat source used to heat and vaporize
feedwater
 Condenser – turbine exhaust steam is condensed before being returned to
steam generator
 Numerous smaller heat exchangers are used throughout the steam cycle

 Factors determining rate of heat transfer

 Mass flow rates of the fluids flowing through the heat exchanger

 Temperature difference between the two fluids

 Subcooling is the process of cooling condensed vapor beyond what is

required for the condensation process.

ELO
2.4
• Factors determining rate of heat transfer
– Mass flow rates of the fluids flowing through the heat exchanger
– Temperature difference between the two fluids

𝑚𝑚̇ 1 ℎ𝑜𝑜𝑜𝑜𝑜𝑜,1 − ℎ𝑖𝑖𝑖𝑖,1 = −𝑚𝑚̇ 2 (ℎ𝑜𝑜𝑜𝑜𝑜𝑜,2 − ℎ𝑖𝑖𝑖𝑖,2 )

Figure: Typical Parallel and Counter-Flow Heat Exchangers Different Flow Regimes and Associated
Temperature Profiles in a Double-Pipe Heat Exchanger

ELO
2.4
The rate of heat transfer between
two liquids in a heat exchanger
will increase if the… (Assume
specific heats do not change.)
A. Inlet temperature of the hotter
liquid decreases by 20 °F.
B. Inlet temperature of the
colder liquid increases by 20
°F.
C. Flow rates of both liquids
decrease by 10 percent.
D. Flow rates of both liquids
increase by 10 percent. Figure: Typical Parallel and Counter-Flow Heat Exchangers
Different Flow Regimes and Associated Temperature
Profiles in a Double-Pipe Heat Exchanger

ELO
2.4
 Condenses turbine wet vapor exhaust.
 Rejected heat transfers to the environment by the circulating
water flowing through the condenser tubes.
 Condensate, the liquid formed, is subcooled slightly during the
process.

Figure: Typical Single-Pass Condenser

ELO
2.4
 Steam is condensed
 Latent heat of
condensation
 Specific volume
decreases drastically
 Creates a low pressure,
maintaining vacuum
 Increases plant efficiency

Figure: Typical Single-Pass Condenser End View

ELO
2.4
Condensate Depression
 As the condensate falls toward the hotwell, it subcools (goes
below TSAT) as it comes in contact with tubes lower in the
condenser
 The amount of subcooling is the condensate depression
 TSAT – THOTWELL = the amount of condensate depression

Figure: T-v Diagram for Typical Condenser

ELO
2.4
• T-s diagram shows available
and unavailable energy
represented by the areas
under the curves
• The energy available for
work is the difference
between the total Q added
and Q rejected
• The larger the unavailable (Q
rejected) energy, the less
efficient the cycle

Figure: Rankine Cycle

ELO
2.4
Rankine Cycle
Efficiencies
• Comparing two Rankine
cycles on T-s diagram
• The amount of rejected energy
to available energy of one
cycle can be compared to
another cycle
• The most efficient has the
least amount of unavailable
energy Figure: Rankine Cycle Efficiency Comparisons on a T-s Diagram

• It can be seen that Cycle A

has less rejected heat and
more energy for work

174
ELO
2.4
 The ideal turbine is
replaced with a real turbine.
 The efficiency is reduced.
 The non-ideal turbine incurs
an increase in entropy,
which increases the area
under the T-s curve for the
cycle.
 But the increase in the area
Figure: Rankine Cycle With Real Versus Ideal Turbine
of available energy (3-2-3')
is less than the increase in
area for unavailable energy
(a-3-3'-b).

ELO
2.4
 Processes that comprise
the steam cycle:
 1-2: Heat is added to the
working fluid in the steam
generator under a constant
pressure condition
 2-3: Saturated steam is
expanded in high pressure
(HP) turbine to provide shaft
work output at a constant
entropy
 3-4: Moist steam from the
exit of HP turbine is dried
and superheated in the
moisture separator reheater Figure: Typical Steam Cycle

ELO
2.4
 4-5: Superheated steam
from MSR is expanded in
the low pressure (LP)
turbine to provide shaft
work at a constant entropy
 5-6: Steam exhaust from
the turbine is condensed in
the condenser by cooling
water under a constant
vacuum condition
 6-7: Condensate is
compressed as a liquid by
the condensate

Figure: Typical Steam Cycle

ELO
2.4
 7-8: Condensate is
preheated by the Low
Pressure feedwater
heaters
 8-9: Condensate is
compressed as a liquid by
the feedwater pump
 9-1: Feedwater is
preheated by the High-
Pressure heaters
 1-2: Cycle starts again -
heat is added to the
working fluid in the steam
generator under a constant
pressure condition Figure: Typical Steam Cycle

ELO
2.4
Figure: Typical Steam Cycle Figure: Rankine Steam Cycle (Ideal)

ELO
2.4
• Rankine Ideal Cycle
• Ideal pumps and turbines do not exhibit an increase in entropy
• No condensate subcooling as point 6 is on the saturation line

Figure: Rankine Steam Cycle (Ideal)

ELO
2.4
• This additional heat rejected
must then be made up for in
the steam generator
• Real pumps and turbines
would exhibit an entropy
increase across them
• Subcooling decreases cycle
efficiency but aids in
preventing condensate pump
cavitation

Figure: Steam Cycle (Real)

181
ELO
2.4
Components
 In real systems, a percentage of the overall cycle inefficiency is
due to the losses by the individual components
 Turbines, pumps, and compressors all behave non-ideally due to
heat losses, friction, and windage losses
 All of these losses contribute to the non-isentropic behavior of
real equipment

ELO
2.4
Cycles
Real system compromises are made due to cost and other
factors in the design and operation of the cycle
 Condensers are designed to subcool the liquid by 8-10 °F. This
subcooling allows the condensate pumps to pump without
cavitation.
 But, each degree of subcooling is energy that must be put back by
reheating the water, and this heat (energy) does no useful work and
therefore increases the cycle’s inefficiency.
 Heat loss to the environment, such as thin or poor insulation.
 Again, this is energy lost to the system and therefore unavailable to
do work.
 Friction from resistance to fluid flow and mechanical friction in
machines
 Converts fluid energy into heat that is not available for work

ELO
2.4
Condition Effect Discussion
Superheating More Efficient Increased heat added results
With More in more net work from the
Superheating system, even though more heat
is rejected.
Moisture Use of MSR More work is done by the low-
Separator Has Minor pressure (LP) turbine since
Reheater Effect On inlet enthalpy is higher but
(MSR) Efficiency more heat is rejected.

The principle benefit of MSR

use is protection of the final
blading stages in LP turbine
from water droplet
impingement.
Feedwater More Efficient Less heat must be added from
Preheating With Feedwater the heat source (reactor) since
Preheating the feedwater enters the
steam generator closer to
saturation temperature.
Condenser More Efficient Net work output is higher and
Vacuum With Higher heat rejection is lower as
Vacuum (Lower condenser pressure is lowered.
Backpressure) ELO
2.4
Condition Effect Discussion
Condensate More Efficient Minimal condensate depression
Depression With Minimal reduces both the amount of
Condensate heat rejected and the amount
Depression of heat that must be supplied
to the cycle.
Steam More Efficient At At higher steam temperature,
Temperature/ Higher Steam the inlet and exit entropy from
Pressure Temperature/ the turbine are lower so less
Pressure heat is rejected.

Steam density increases as

pressure increases, so more
turbine work is done.
Steam More Efficient At Enthalpy content increases as
Quality Higher Steam moisture content decreases
Quality and more net work is done.

ELO
2.4
 Minimize the number of auxiliaries running to those necessary to
support the power output level
 Minimize the amount of steam generator blowdown.
 Fix steam leaks
 Fix air leaks into the condenser
 Operate air ejector condensers, gland seal condensers, and
blowdown heat exchangers to recover as much heat as possible

ELO
2.4