BASIC CONCEPT OF THERMODYNAMICS

THE BIG IDEA

Heat flows from hot to cold and not from cold to hot
 What is Thermodynamics?
The study of heat and its transformation into mechanical energy is called
thermodynamics.

The foundation of thermodynamics is the conservation of energy and the fact

that heat flows from hot to cold. It provides the basic theory of heat engines

Thermodynamics deals with the effects of work, heat, and energy on matter
(solid, liquid or gas) within a specified region of interest called system.

The system might be a mechanical device, a biological organism or a specified

quantity of material such as the refrigerant in an air conditioner or steam
expanding in a turbine. Figure 1 shows a thermodynamic system.
Figure 1: A thermodynamic system: Steam Engine
 What is a System, surrounding and boundary?
System is a restricted region of space or a finite portion of matter one
has chosen to study or the part of the universe, with well-defined
boundaries, one has chosen to study. In other words a system is a
quantity of matter or a region in space chosen for study.

Surrounding is the rest of the universe outside the region of interest (i.e.
the rest of space outside the system or the mass or region outside the
system).

Boundary or Wall is the surface that divides the system from the
surroundings. This wall or boundary may or may not allow interaction
between the system and the surroundings. Figure 2 shows the above.
Figure 2: Showing Surrounding, system and boundary
 Thermodynamic Coordinates or properties
These are macroscopic coordinates or properties used to describe
or characterise a system. Since they are macroscopic properties or
coordinates, they can be observed and measured. Some examples
are Temperature (T), Pressure (P), Volume (V), density (ρ), mass
(m), specific heat capacity at constant volume (VC), specific heat
capacity at constant pressure (PC), thermal conductivity (k),
thermal diffusivity (α), and chemical potential (µ).
 Thermodynamic System
This is a system that could be described in terms of
thermodynamic coordinates or properties. Thermodynamic
Systems can be categorised into the followings depending on the
type of boundary:

Open System: This is a system that its boundary allows transfer of

mass and energy into or out of the system. In other words, the
boundary allows exchange of mass and energy between the
system and the surrounding. (i.e. both mass and energy can cross
the selected boundary).Example is an open cup of coffee
Figure 3: An Open System
Closed System: This is a system that its boundary allows exchange
of energy alone (inform of heat) between the system and its
surrounding (i.e. the boundary allows exchange of energy alone).
This type of boundary that allows exchange of heat is called
diathermal boundary. Example is a tightly capped cup of coffee

Figure 4: A closed System

Isolated System: This is a system that its boundary allows neither
mass nor energy between it and the surrounding. In other words,
neither mass nor energy can cross the selected boundary. Example
is a coffee in a closed, well-insulated thermos bottle.

Figure 5: Isolated System

 Thermodynamic Processes
A system undergoes a thermodynamic process when the system
undergo some kind of energetic change within the system,
generally associated with changes in pressure, volume, internal
energy, temperature, or any sort of heat transfer.

There are several specific types of thermodynamic processes that

happen frequently enough and in practical situations. Each has a
unique trait that identifies it, and which is useful in analyzing the
energy and work change related to the process. These are

Isobaric process: This is a thermodynamic process that occurs at

constant pressure (i.e. ∆P = 0 during this process).
Isochoric process: This is a thermodynamic process that occurs at
constant volume (i.e. ∆V= 0 during this process). This implies that
during this process no work is done on or by the system.

Isothermal process: This is a thermodynamic process that takes

place at constant temperature (i.e. ∆T = 0 during this process).

Adiabatic process: This is a thermodynamic process in which there

is no heat transfer into or out of the system. For this process,
change in quantity of heat is zero (i.e. ∆Q = 0 during this process).

Isentropic process - a process where the entropy of the fluid

remains constant.
Polytropic process - when a gas undergoes a reversible process in
which there is heat transfer, it is represented with a straight line,
PVn = constant.

Throttling process - a process in which there is no change in

enthalpy, no work is done and the process is adiabatic.

Quasi-static Process: This is a process that is carried out in such a

way that at every instant, the system departs only infinitesimal
from an equilibrium state (i.e. almost static). Thus a quasi-static
process closely approximates a succession of equilibrium states.
Non-quasi-static Process: This is a process that is carried out in such
a way that at every instant, there is finite departure of the system
from an equilibrium state.

Reversible Process: A reversible process can be defined as one which

direction can be reversed by an infinitesimal change in some
properties of the system.

Irreversible Process: An irreversible process can be defined as one

which direction cannot be reversed by an infinitesimal change in
some properties of the system.
Cyclic Processes: These are series of processes in which after certain
interchanges of heat and work, the system is restored to its initial state.
Of all these, the four most Basic Thermodynamic Processes are;
 Isobaric process (constant pressure)
 Isochoric process (constant Volume)
 Isothermal Process (constant temperature)
 Adiabatic process (constant heat)
Summary of the Basic Thermodynamic processes and their equations
 LAWS OF THERMODYNAMICS
The Zeroth Law of Thermodynamics
If Two systems A and B are in thermal equilibrium with a third system T,
then A and B are in thermal equilibrium with each other.

Zeroth law of thermodynamics states that if two systems are separately in

thermal equilibrium with a third system, they are in thermal equilibrium with
each other.
Two system are in thermal equilibrium if they have the same temperature.
 LAWS OF THERMODYNAMICS
The First Law of Thermodynamics
 Thermodynamic Systems Interact with surroundings
 Heat exchange takes place
 Q = heat added to the system and some other form of energy transfer
 Mechanical Work is done, e.g. W = workdone by the system
 Hence the first law of Thermodynamics states that
“The change in internal energy of a closed system will be equal to the
energy added to the system minus the work done by the system on its
surroundings”.
∆U = Q - W
 The First Law of Thermodynamics

Heat absorbed Q = ∆U + W Work done

by the system by the system

Change in the system’s

internal energy

 For Infinitesimal, Quasi-Static Processes

đQ = dU + đW
Total Energy is Conserved

“Energy can neither be created nor destroyed. It can only be changed from
one form to another”.
The First law says nothing about the Direction of Energy Transfer!
This law of conservation of energy, written in a form useful to systems
involving heat transfer has signs for Q and W.
APPLICATION OF THE FIRST LAW IN THERMODYNAMIC PROCESSES

Work done during volume changes (Isobaric expansion)

dW  Fdx  pAdx
Adx  dV
dW  pdV

V2

W   pdV
V1

Depends upon process!

Work = Area under curve!

expansion at constant
pressure
reversed => compression
Isothermal Expansion
expansion at constant temperature
reversed => compression
V2

W  pdV
V1

with pV = nRT
V2 V
nRT 2
1
W dV  nRT  dV 
V1
V V1
V
V2
W  nRT ln( )
V1
can be rewritten, with p1V1  p2V2
p1
W  nRT ln( )
V2
Adiabatic Processes
dQ  0 V  1 T  const  ideal gas law
dW  pdV   dU   nCV dT  1 pV
V  const  pV   const
nRT nR
dV   nCV dT
V CV
W   U  nCV ( T1  T2 )  ( p1V1  p 2V2 )
R dV dT R C p  CV R
 0    1
CV V T CV CV
dV dT
(  1)   0
V T
(  1) ln V  ln T  const
lnV  1 T   const  V  1 T  const
Summary of basic thermodynamic processeses for an ideal gas

special W Q
Isobaric p  const p(V2  V1 ) nC p T
Isochoric V  const 0 nCV T
V2
nRT ln
V1
Isothermal T  const W
p1
nRT ln
p2
U
Q0
Adiabatic  1  CV 0
TV , pV const ( p1V1  p2V2 )
R
 Human Metabolism and The First Law
The metabolic rate is the rate at which internal energy is transformed in
the body.
 The Second Law of Thermodynamics
• The second law states that the entropy of an isolated system
increases in any irreversible process and is unaltered in any
reversible process.”
• This is sometimes called
The Principle of Increasing Entropy
DS ³ 0
Change in entropy of the system

• This gives the Preferred (natural) Direction of Energy Transfer

• This determines whether a process can occur or not.

 Various Statements of the Second Law
1. “No series of processes is possible whose sole result is the absorption of
heat from a thermal reservoir and the complete conversion of this energy to
work.” that is no engine is 100% efficient There are no perfect engines!

2. “It is impossible to extract an amount of heat Q H from a hot reservoir and

use it all to do work W. Some amount of heat Q C must be exhausted to a
cold reservoir.”

3. “It is not possible for heat to flow from a colder body to a warmer body
without any work having been done to accomplish this flow. Energy will not
flow spontaneously from a low temperature object to a higher temperature
object.” There are no perfect Refrigerators!. This statement about refrigerators
also applies to air conditioners and heat pumps which use the same principles.
4. The total entropy of an isolated system never decreases
Application of 2nd Law: Heat Engines and the Carnot Cycle
A heat engine is a device that converts heat into work. A classic
example is the steam engine. Fuel heats the water; the vapor
expands and does work against the piston; the vapor condenses
back into water again and the cycle repeats
.
 Components of Heat Engines

All heat engines have:

• a high-temperature reservoir
• a low-temperature reservoir
• a cyclical engine
These are illustrated schematically here.
 Heat Engines and Efficiency (e)

An amount of heat Qh is supplied from the hot reservoir to the

engine during each cycle. Of that heat, some appears as work, and
the rest, Qc, is given off as waste heat to the cold reservoir.

The efficiency is the fraction of the heat supplied to the engine that
appears as work.

The efficiency can also be written as:

In order for the engine to run, there must be a temperature difference;
otherwise heat will not be transferred. The maximum work a heat engine can
do is then:

If the two reservoirs are at the same temperature, the efficiency is zero; the
smaller the ratio of the cold temperature to the hot temperature, the closer
the efficiency will be to 1.
 The maximum work a heat engine can do is then:

If the two reservoirs are at the same temperature, the efficiency is zero; the
smaller the ratio of the cold temperature to the hot temperature, the closer
the efficiency will be to 1.
 Carnot Engines
The Carnot engine was created to examine the efficiency of a heat engine.
It is idealized, as it has no friction. Each leg of its cycle is reversible.
The Carnot cycle consists of:
• Isothermal expansion
• Adiabatic expansion
• Isothermal compression
• Adiabatic compression

Carnot Cycle
 Efficiency of an ideal or Carnot Engine

For an ideal reversible engine, the efficiency can be written in terms of the
temperature:

From this we see that 100% efficiency can be achieved only if the cold
reservoir is at absolute zero, which is impossible.

Real engines have some frictional losses; the best achieve 60-80% of the
Carnot value of efficiency.
 Refrigerators, Air Conditioners, and Heat Pumps
While heat will flow spontaneously only from a
higher temperature to a lower one, it can be made to
flow the other way if work is done on the system.
Refrigerators, air conditioners, and heat pumps all
use work to transfer heat from a cold object to a hot
object.

If we compare the heat engine and the refrigerator,

we see that the refrigerator is basically a heat engine
running backwards – it uses work to extract heat
from the cold reservoir.
 Comparing Heat Engines and Refrigerators

Cold reservoir (the inside of the refrigerator) and Hot reservoir (exhausts) to
the kitchen. Note that- more heat is exhausted to the kitchen than is removed
from the refrigerator.
 Ideal Refrigerator and Coefficient of Performance ( COP)
An ideal refrigerator would remove most of the heat from the interior while
requiring the smallest amount of work. This ratio of heat output to work input
is called the coefficient of performance, COP:

Refrigerator performance is measured by the coefficient of performance

(COP):

Substituting:
 Air Conditioners
 Air conditioners and Refrigerators do work to
extract heat from a cooler region and send it to a
warmer region:
 An air conditioner is essentially identical to a
refrigerator; the cold reservoir is the interior of the
house or other space being cooled, and the hot
reservoir is outdoors.
 Exhausting an air conditioner within the house will
result in the house becoming warmer, just as keeping
the refrigerator door open will result in the kitchen
becoming warmer.
 Heat Pumps
A heat pump is the same as an air conditioner, except with the
reservoirs reversed. Heat is removed from the cold reservoir
outside, and exhausted into the house, keeping it warm. Note
that the work the pump does actually contributes to the
desired result (a warmer house) in this case.

In an ideal heat pump with two operating temperatures (cold and

hot), the Carnot relationship holds; the work needed to add heat Qh
to a room is:

The COP for a heat pump:

 Reversible Heat Engine
 A reversible engine has the following relation between the heat
transferred and the reservoir temperatures:

Rewriting,

 This quantity, Q/T, is the same for both reservoirs, and is defined as the
change in entropy. In a reversible heat engine, it can be shown that the
entropy does not change.
 Real Engine
 A real engine will operate at a lower efficiency than a reversible engine;
this means that less heat is converted to work. Therefore,

 Entropy (S) is the measure of the amount of disorder in a system. As

disorder increases; entropy increases. Any irreversible process results in
an increase of entropy. This will be treated in details later.
The 2nd Law of Thermodynamics can be used to classify Thermodynamic
Processes into three Types namely:

1. Natural Processes (or Irreversible Processes or Spontaneous

Processes): These are natural or real processes that cannot be reversed
once they occur. The energy(heat) loss in this process is unavailable to
do any work.

2. Reversible Processes: These are processes that can be reversed. That is

return the system and its surroundings to their initial states.

3. Impossible Processes: These are processes that cannot occur or cannot

be achieved without the input of work
 The Third Law of Thermodynamics
 Absolute zero is a temperature that an object can get arbitrarily close to,
but never attain.
 Temperatures as low as 2.0 x 10-8 K have been achieved in the laboratory,
but absolute zero will remain ever elusive – there is simply nowhere to
“put” that last little bit of energy. This is the third law of thermodynamics
 The third law of thermodynamics states that “it is impossible to lower the
temperature of an object to absolute zero in a finite number of steps”.
 Adiabatic Processes for an Ideal Gas
When a gas is compressed or expanded so that no heat enters or leaves a system,
the process is said to be adiabatic.

Adiabatic changes of volume can be achieved by performing the process rapidly so

that heat has little time to enter or leave or by thermally insulating a system from its
surroundings.

When work is done on a gas by adiabatically

compressing it as seen in the picture, the gas gains
internal energy and becomes warmer.

When a gas adiabatically expands, it does work on its

surroundings and gives up internal energy, and thus
becomes cooler.
 Example of Adiabatic Processes
 A common example of a near-adiabatic process is the compression and
expansion of gases in the cylinders of an automobile engine.
Compression and expansion occur in only a few hundredths of a second,
too fast for heat energy to leave the combustion chamber.

 For very high compressions, like those in a diesel engine, the

temperatures are high enough to ignite a fuel mixture without a spark
plug. Diesel engines have no spark plug
 Work done During Adiabatic Processes
dQ  0 V  1 T  const  ideal gas law
dW  pdV   dU   nCV dT  1 pV
V  const  pV   const
nRT nR
dV   nCV dT
V CV
W   U  nCV ( T1  T2 )  ( p1V1  p 2V2 )
R dV dT R C p  CV R
 0    1
CV V T CV CV
dV dT
(  1)   0
V T
(  1) ln V  ln T  const
lnV  1 T   const  V  1 T  const
 ENTROPY
Entropy can be defined as the increase in disorder of a system or a
measure of the disorderliness of a system. In this diagram, the end state is
less ordered than the initial state – the separation between low and high
temperature areas has been lost.
 Increase of Entropy Principle
For a general Process
2
Q Define entropy generation Sgen as,
S  S 2  S1  
1
T
2
Q
S system  S 2  S1    S gen
1
T Increase of Entropy
Principle
Entropy Entropy Entropy Generation
change Transfer
(due to heat
transfer)

•The principle states that for an isolated or a closed adiabatic System +

Surroundings; a process can only take place such that Sgen 0 where Sgen = 0
for a reversible process only and Sgen can never be less than zero.
 Increase disorder increase entropy
The motto of this contractor—“Increasing entropy is our business”—is appropriate
because by knocking down the building, the contractor increases the disorder of
the structure.
 Order Tends to Disorder
Push a heavy crate across a rough floor and all your work will go into heating the floor
and crate. Work against friction turns into disorganized energy.

Organized energy in the form of electricity that goes into electric lights in homes and office
buildings degenerates to heat energy. This heat energy is lost to the environment and has no
further use.
 Order Tends to Disorder
Imagine that in a corner of a room sits a closed jar filled with argon gas atoms. When the lid
is removed, the argon atoms move in haphazard directions, eventually mixing with the air
molecules in the room.

The system moves from a more ordered state (argon atoms

concentrated in the jar) to a more disordered state (argon atoms
spread evenly throughout the room).

The argon atoms do not spontaneously move back into the jar to
return to the more ordered containment state.
With the number of ways the argon atoms can randomly move, the
chance of returning to an ordered state is practically zero.

We see that the quality of energy is lowered with each transformation

indicating that;
Organized energy tends to disorganized forms.
 Order Tends to Disorder
This abandon house demonstrates entropy. Without continual maintenance, the
house will eventually fall apart. An abandoned or parked car for a very long time
will eventually start depreciating if not maintained again.
 Order Tends to Disorder
What happens to the orderly state of any natural system?
According to the second law of thermodynamics, in the long run, the entropy of
a system always increases for natural processes.

Gas molecules escaping from a bottle move from a relatively orderly state to a
disorderly state.

Organized structures in time become disorganized messes. Things left to

themselves run down.

When a physical system can distribute its energy freely, entropy increases and
energy of the system available for work decreases.

Another way to say this is that organized, usable energy degenerates into
disorganized, non-usable energy. It is then unavailable for doing the same work
again.
 Implications of Increase of Entropy Principle
• Entropy, unlike energy, is non-conservative since it is always increasing.

• The entropy of the universe is continuously increasing, in other words, it is

becoming disorganized and is approaching chaotic.

• The entropy generation is due to the presence of irreversibilities.

• Therefore, the higher irreversibilities lead to the higher the entropy generation
and the lower the efficiency of a device.

• Note that this does not mean that the entropy of a system cannot be reduced, it can.
However, total entropy of a system + surroundings cannot be reduced.
 Disorder to Order

Disordered energy can be changed to ordered energy only at the expense of

work input.

Plants can assemble sugar molecules from less organized carbon dioxide and
water molecules only by using energy from sunlight.

It takes an input of energy to change your messy room into a clean room.

In the broadest sense, the message of the second law is that the tendency
of the universe, and all that is in it, tends to disorder.
 Entropy and Physical Systems
Entropy normally increases in physical systems. However, when there is work input, as in
living organisms, entropy decreases.

All living things extract energy from their surroundings and use it to increase their own
organization. This order is maintained by increasing entropy elsewhere.

Energy must be transformed into the living system to support life. When it is not, the
organism soon dies and tends toward disorder (increase entropy)

The first law of thermodynamics is a universal law of nature for which no exceptions have
been observed.

The second law, however, is a probability statement. Disordered states are much more
probable than ordered states.
 Some improbable States (Decrease in Entropy)
Even the most improbable states may occur, and entropy spontaneously
decrease:

• haphazard motions of air molecules could momentarily become

harmonious in a corner of the room (Fresh air or breeze)

• a barrel of pennies dumped on the floor could show all heads

• a breeze might come into a messy room and make it organized

The chances of these things occurring are infinitesimally small compare to

the occurrence of probable states (disordered states)
 Irreversibility or Unavailability of Energy; Heat Death

 When a physical system can distribute its energy freely, entropy

increases and energy of the system available for work decreases.
 Another consequence of the second law is that in any natural process,
some energy becomes unavailable to do useful work.
 If we look at the universe as a whole, it seems inevitable that, as more
and more energy is converted to unavailable forms, the ability to do
work anywhere will gradually vanish. This is called the heat death of the
universe.
 The excess heat exhausted during an irreversible process cannot be
recovered; doing that would require a decrease in entropy, which is not
possible because entropy continue to increase
 Entropy at a glance
• The total entropy of the universe increases whenever an irreversible process
occurs. The total entropy of the universe remains constant whenever a
reversible process occurs.
•Since all real processes are irreversible, the entropy of the universe
continually increases. If entropy decreases in a system due to work being
done on it, a greater increase in entropy occurs outside the system.
•As the total entropy of the universe increases, its ability to do work
decreases. The excess heat exhausted during an irreversible process cannot
be recovered; doing that would require a decrease in entropy, which is not
possible because total entropy of a system + surroundings cannot be reduced.
•The second law is not a conservation principle (as in the 1 st Law), but rather
is a law defining the direction of flow of energy in relation to entropy
 Some other ways of stating thermodynamics law
The laws of thermodynamics are sometimes put this way:
Version 1
First Law: You can’t win (because you can’t get any more energy out of
a system than you put in).
Second Law: You can’t break even (because you can’t even get as much
energy out as you put in).
Third Law: You can’t get out of the game (entropy in the universe is
always increasing).

Version 2
Zeroth Law: You must play the game.
First Law: You can't win the game, you can only break even.
Second Law: You can only break even at absolute zero.
Third Law: You can't reach absolute zero.
 Version 3
Zeroth Law: You must play the game.
First Law: You can't win the game.
Second Law: You can't break even except on a very cold day.
Third Law: It never gets that cold!

Version 4
Zeroth Law: There is a game.
First Law: You can't win the game.
Second Law: You must lose the game.
Third Law: You can't quit the game.
 Assessment Questions
1. The lowest possible temperature is absolute zero, at
a. 0 on the Kelvin scale and 0 degrees on the Celsius scale.
b. 0 on the Kelvin scale and -100 degrees on the Celsius scale.
c. 0 on the Kelvin scale and -273 degrees on the Celsius scale.
d. 373 on the Kelvin scale and -273 degrees on the Celsius scale.
Answer: C

2. When heat is added to a system, the amount of heat added can

a. decrease the temperature, decrease internal energy, and do no external work.
b. increase the temperature, increase internal energy, and do external work.
c. increase the temperature, decrease internal energy, and do external work.
d. decrease the temperature, increase internal energy, and do no external work.

Answer: B
3. When you breathe on your hand, the temperature of the exhaled air reaching your
hand
a. always increases.
b. always decreases.
c. remains unchanged.
d. depends on how you blow.

Answer: D

4. The second law of thermodynamics tells us that heat cannot flow from
a. hot to cold ever.
b. cold to hot ever.
c. hot to cold without external energy.
d. cold to hot without external energy.

Answer: D
 5. Heat engines such as jet engines are more efficient when run at
a. high temperatures.
b. constant temperatures.
c. low temperatures.
d. a constant rate.

Answer: A
6. The direction of natural processes is from states of
a. higher order to lower order.
b. lower order to higher order.
c. disorganization to organization. 7. As entropy in a system increases, energy in the
d. disorder to equilibrium. system
a. becomes more ordered.
b. becomes less ordered.
Answer: A c. reaches equilibrium.
d. moves toward destruction.

Answer: B
 Further Assement
1. A gas stored in an insulated cylinder with a movable piston is compressed adiabatically and 100 J
of work is done in the process. The gas is then allowed to expand adiabatically while doing 10 J
of work. What is the net change in internal energy? [Ans: 90 J]

2. Three moles of a gas expand Isothermally. If the initial temperature of the gas is 300 K and its
final volume is twice the initial volume is twice the initial volume. Calculate the work done by the
gas. Take universal gas constant = 8.314). [Ans: 5186.5 J]

3. 3. 50 g of ice is melted at the same temperature. Calculate the change in internal energy if the
latent heat of fusion of ice is 3.35 x 105 J/Kg. [Ans: 1.68 x 104 J]

4. What is the maximum efficiency of an engine which operates between two reservoirs at
temperatures of (a) 25oC and 40oC(b) 25oC and 100oC? [Ans : (a) 4.7%, (b) 20.11%]

5. A carnot engine operating between two reservors at temperatures 0oC and 100oC receives 10 kg
of heat from the high- temperature reservoir. Calculate (a) the heat rejected to the low
temperature reservoir, (b) the work done by the engine, and (c) the thermal efficiency. [ Ans:(a)
7319 J, (b) 2681 J, (c) 26.81%].

6. What is the change in entropy when 1 kg of water at 20oC is mixed with 1 kg of water at 100oC?
(For water c = 4186 J/kg.oC) [Ans: 60.8 J/K].