Section 4 :

Second Law of
Thermodynamics
 Second Law of Thermodynamics
The First Law is concerned with energy quantities
- conservation of energy.
The Second Law is concerned with energy quality
-what proportion of internal energy can be converted into useful work?
-determining the best theoretical performance of cycles, engines, and other
devices

1. Kelvin-Planck Statement
"It is impossible to convert all the energy supplied by heating from a single
source into useful work, in a continuous manner"
 Second Law of Thermodynamics
2. Clausius Statement
"Energy transfer by heating will not occur naturally from a low temperature to
a high temperature"

These two statements result from observation of actual phenomena. They

represent the practical consequences of an underlying natural tendency for
matter and energy to become more disorganised. (The complementary natural
tendency is for matter to seek a minimum energy level).

Energy transfer by heating is transfer of disorganised energy.

Energy transfer by working is transfer of organised energy,
Video; 8.physics animations – Entropy.flv
 Ex 1.The Heat Engine

Qsupplied - energy transfer by

heating from the high
temperature source to the
working fluid.

Part of the heat

Qrejected - energy transfer by received by a heat
heating from the working fluid to engine is converted
the low temperature sink. to work, while the
rest is rejected to a
sink.
Wout - useful work done by the
system on its surroundings.

According to the Kelvin-Planck

Statement of the Second Law.
Qrejected > O
Ex 2.Steam Power Plant
 Ex 3.Reciprocating Engine

expansion (power)

compression
spark/start of
injection

exhaust

intake
V

TDC BDC
 Thermal Efficiency of Any Heat Engine

Source of Internal
By the First Law, Q – W = U
Energy At T
A
However, the working fluid undergoes a
Q
complete cycle, so there is no net change in
supplied
System boundary internal energy of the system.
- contains the working fluid. Thus, Q - W = O or Q = W
Heat Engine W
Where Q represents the net energy supply to
out
Cycle the system by heating and W represents the
net work done by the system
Q Thus, Q = Qsupplied – Qrejected = Wout
rejected

Sink of Internal
Energy at T
B
Useful Work Output Wout
ThermalEfficiency  
Energy Supplied Qsupplied
Qsup plied-Qrejected
TH 
Qsup plied
Q rejected
TH  1 
Qsupplied
 Kelvin-Planck Statement of the Second Law

It is impossible to convert all the energy supplied by heating

from a single source into useful work, in a continuous manner

A heat engine will always have thermal efficiency less than

100%
Wout
Thermal Efficiency 
Qsupplied
 Heat engine in reverse - Refrigerator

Sink of Internal energy rejected

Energy At T by heating
A 3
2
Q
rejected condensor
System boundary

throttle
Refrigeration W valve compressor
in
Cycle
evaporator
(in cold space)

1
Q
supplied 4
Source of Internal energy supplied
by heating
Energy at T
B

Clausius Statement of the Second Law

Energy transfer by heating will not occur naturally from a low
temperature body to a high temperature body - work must be
done to make the transfer happen.
 Thermodynamic Equilibrium and Reversibility

A system is in thermodynamic equilibrium if its thermodynamic

properties do not change (spontaneously) when the system is isolated
from its surroundings.

The system must remain in thermodynamic equilibrium throughout -

process slow enough to maintain uniform pressure and temperature

General rules like the equation of state for a perfect gas only apply to
systems in thermodynamic equilibrium.

Relaxation Time
When a system is disturbed and a process occurs, the ‘slowness’ of the
process depends on the speed at which the system can regain equilibrium
within itself. A system undergoes a relaxation process in response to a
sudden impressed change in any property.
Ex: For air at room temperature in a cylinder 8 cm long, this is about
2x10-4 seconds.
 Reversibility
When a system undergoes a reversible process, both the system
and its surroundings can be returned to their original state by
retracing the process exactly
Reversible process: A process that can be reversed without
leaving any trace on the surroundings.
Irreversible process: A process that is not reversible.
• All the processes occurring in nature are irreversible.
• Why are we interested in reversible processes?
• (1) they are easy to analyze and (2) they serve as idealized models
(theoretical limits) to which actual processes can be compared.

Reversible processes deliver the most and consume the least work.
 Expansion of a gas
Very slow expansion (reversible)
- resisting force only infinitesimally less than gas
pressure force
- gas pressure at piston same as in rest of gas
- maximum possible work produced net force resisting force

due to system
pressure

Very fast expansion

- resisting force less than gas pressure force
- gas pressure at piston lower than in rest of
gas
- Turbulence in the gas leads to frictional
losses.
- less work produced than slow expansion
 Irreversible Processes
The factors that cause a process to be irreversible are called
irreversibilities.

Common sources of irreversibility are free expansion, friction,

energy transfer by heating through finite temperature
gradients, free expansion and combustion. No real process is
fully reversible
(a) Free Expansion -
gas
expansion without gas vacuum

useful work
initial state final state
Irreversible Processes

(b) Friction - relative motion of matter in

contact
- surfaces
- turbulence - conversion of bulk kinetic
energy into random molecular motion
(internal energy)

(c) Heat transfer - naturally from

high temperature to low temp
- reverse requires work (refrigerator)
 Irreversible Processes

(d) Combustion (irreversible)

- when a fuel and oxidant react directly, the chemical potential
energy becomes random molecular motion (internal energy)
- only a portion can be converted into useful work (heat engine)

Hydrogen oxygen fuel cell (theoretically reversible)

- theoretically possible to convert all chemical potential energy
into electricity and for the electrical energy to be used to
reverse the process by electrolysis
 Entropy
Entropy is the thermodynamic property associated with the
Second Law.

It is represented by the symbols: S (kJ/K) and s (kJ/kgK)

As the energy of a system becomes more disorganised, the

system's entropy increases.

Energy cannot be created or destroyed.

Entropy cannot be destroyed.
Entropy is created by irreversible processes.
Entropy is “transferred” by heating processes.
Disorganized energy
does not create much
useful effect, no
matter how large it is.
Entropy and Energy Quality
• As mass falls, it rotates the
paddle, hence PE of mass is
transferred to the IE of fluids.
• However, the reverse process by
transferring heat to a paddle
wheel will not raise the weight.
• Stored energy is high quality can
all be recovered as work
• low entropy process

• Stirring the gas creates disorder

• stored energy is low quality
(internal energy)
• only part of the energy can be
recovered as work (heat engine)
• high entropy process
 Entropy

1. A system's entropy increases when irreversible

processes occur within the system. (Entropy production)

Examples of irreversible processes are: unresisted

expansion, mechanical or fluid friction, combustion, mixing
of separated gases.

2. A system's entropy increases when energy is transfered

to the system by heating.(Entropy “transfer”)
(and decreases when the system is cooled)
 Isentropic Process
For adiabatic processes, there is no energy transfer by heating
so there is no entropy “transfer”.

For reversible processes, there is no entropy created.

i.e., For reversible + adiabatic processes, there is no change in

the entropy of the system

ie. adiabatic and reversible = isentropic (constant entropy)

During an internally
reversible, adiabatic
(isentropic) process,
the entropy remains
constant.
 Entropy Equation

Entropy is a system property and it is defined in terms of the

way it changes during a process:
2 dQ 2
For a reversible process S   Q   TdS
1 T 1
For an irreversible process 2 dQ 2
S   Q   TdS
1 T 1

Q
S = Entropy change for reversible isothermal heating
T
 Reversible Heat Engine
 Reversible expansion produces Source of Internal
most work Energy At T
A
Q
supplied
 Reversible compression requires T
System boundary
A
least work Reversible
Heat Engine W
out
 Reversible heat engine cycles are Cycle

TB
the most efficient Q
rejected
i.e. If there are no irreversible
Sink of Internal
processes within the system, then Energy at T
B
there is no entropy production within
the system.
No entropy production within … entropy inflow = entropy outflow

Q Qsupplied Qrejected Qrejected T

S =  TH  1  ηTH  1  B
T TA TB Qsupplied TA
 Reversible Heat Engine

 The higher the temperature at which energy is supplied by

heating to the heat engine cycle, the greater the proportion
of this energy which can be converted into useful work.

 The lower the temperature at which the unconverted

energy is rejected from the heat engine cycle, the greater
the proportion of supplied energy which can be converted
into useful work.

 Even a fully reversible heat engine cycle has thermal

efficiency less than 100% because it is impossible to
completely convert disorganised energy (internal energy)
into organised energy (work).
 Combined First and Second Laws

dq - dw = du - non flow energy equation in differential form (First Law)

dwrev = pdv - for compression/expansion work
dqrev = Tds - Second Law

Tds = du+ pdv

h = u + pv
dh = du + pdv + vdp
du + pdv = dh - vdp

Tds = dh - vdp
 Combined First and Second Laws for a Perfect Gas
Tds = du + pdv for any reversible process
or for a perfect gas,
du p p R
ds   dv du = cvdT and 
T T T v
dT dv
 ds  c v R
T v
2 2 dT 2 dv
 s 2  s1   ds   c v  R
1 1 T 1 v
Involves properties at end states
T2 v2
s 2 - s1 = c v ln  R ln only and so applies to reversible
T1 v1 and irrreversible processes
v2 T2 p
Substituting for  s 2 - s1 = cp ln  R ln 2
v1 T1 p1
T2 p2 v
Substituting for  s2 - s1 = cv ln  c p ln 2
T1 p1 v1
Temperature-entropy diagram for steam
Temperature-entropy diagram for a gas

Solid line = Const pressure

Dashed line = Const volume
 PROCESS Q (kJ)  W (kJ) = U (kJ)

1 300 75
2 (adiabatic) 175
3 -50 -150
4 (adiabatic)

For the cycle 0