Second Law of Thermodynamics

Three Statements of the second law

Heat engines (Kelvin-Planck Law)
Second Law of Thermodynamics.
9.1 Refrigerators (Claussius Statement)

Second Law of Thermodynamics Entropy Principle

Carnot cycle efficiency
-Heat engines
- Refrigerators

Kelvin-Planck Statement of
Heat Engines the second law of thermodynamics

Perfect heat engine

A heat engine takes in heat
at a high temperature and
exhausts heat at a low
temperature.

In the process of heat flow

some of the input heat is
converted to work
Tc
It is impossible to construct a heat engine operating in a cycle that
extracts heat from a reservoir and delivers an equal amount of work.
First Law (for a cycle)
Q = Qh + Qc = W No perfect heat engine

Second Law ( puts limits on Qh and QC)

Efficiency of a heat engine Carnot Cycle

The efficiency is the
Sadi Carnot, a French engineer (1796-1832) proposed a
fraction of the heat input
cycle set the limits to the efficiency of a heat engine operating
at high temperature converted
between two temperatures.
to work. Th

W Qh − Q c The cycle consists of 4 reversible steps. Tc

e= = 1
Qh
Qh Qh P
1. Isothermal expansion at Th 4
Qc 2. Adiabatic expansion from Th to Tc 2
e = 1− 3. Isothermal compression at Tc Qc
Qh
4. Adiabatic compression from Tc to Th. 3
In calculating efficiencies Qh and Qc are taken as positive quantities. V
(i.e. the magnitude of the heat)

The second law says that a heat engine cannot be 100% efficient.

1
 Heat engine undergoing the Carnot
Heat engine.
cycle.

Work is done by the gas in expansion

Work must be done on the gas to compress it to the initial state

Efficiency of the Carnot cycle

Heat transfer in the Carnot cycle Th
In the Carnot cycle the magnitude of the heat Th
Qc Tc
transferred at T is proportional to the absolute
temperature T. Tc
e = 1− A1
Qh
A1 Qh P
B
Qh 4
Qh Th P becomes
= (here Q is
4
B
D
2
Qc Tc always positive) Tc
D
2
e = 1− Qc
3
C

From the relations

Qc
3
C Th V
Isothermal expansion and compression The efficiency only depends on the ratio of the absolute
V
V V temperatures.
Qh = RTh ln B Qc = RTc ln C
VA VD
Adiabatic expansion and compression The efficiency would be 100% if Qc =0.

ThVBγ-1 = TcVcγ-1 This is only possible if Tc = 0 K (i.e absolute Zero)

VB VC Qh Qc
γ-1 =
= =
Th VA Tc VDγ-1 VA VD Th Tc A temperature of absolute zero cannot be attained.
(Third law of thermodynamics)

Carnot’s Theorem Stirling Engine

Maximum efficiency is less
All Carot engines operating between temperatures Th and Tc than the Carnot efficiency.
have the same efficiency.
Isothermal Th
w2 =w4 =0 Q2 = Q 4 Q4 Q1
T P
e = 1− c
Th then Qin − Qout Q1 − Q3
e= =
Qin Q1 + Q 4 Q2
No other heat engine operating between these temperatures Q3
can have a greater efficiency For isothermal Q1 Q3 Isothermal Tc
processes same =
Th Tc
volume change
⎛ ⎞
V
⎜ ⎟
e = ecarnot ⎜ ⎟
1
then ⎜ Q4 ⎟ Efficiency lower due to extra heat added.
⎜ 1+ Q ⎟
⎝ 1 ⎠

2
 Clausius Statement of the Second Law
Refrigerator and heat pump
of Thermodynamics.
Th

Tc
A1
Qh It is impossible to construct a refrigerator
P
B operating in a cycle whose sole effect is to
4
2 transfer heat from a cooler object to a hotter
D one.
Qc C
3
V Heat always flows from high temperature
to low temperature.
A heat engine run in reverse is a refrigerator and heat pump.

Work is done to move heat from a cold temperature source to a

hot sink.
This device and be used for cooling or heating.

Equivalence of the Kelvin-Planck and

Clausius statements.
Proof of the Carnot Principle
higher efficiency Carnot engine
engine reversed

If a perfect refrigerator were possible (Clausius) then a perfect If a heat engine with a higher efficiency than a Carnot engine
heat engine could be constructed (Kelvin-Planck). Thus, the could exist. Then it could convert heat to work with 100% efficiency.
impossibility one implies the impossibility of the other.
The Carnot engine has the highest efficiency for any heat engine
acting between two temperatures.

Real Heat Engines Example

work done in expansion
In a wood burning power plant the steam in the turbine operates
between the high temperature of 810 K and a low temperature of
366 K. What is the Carnot efficiency for this plant.

Tc 366
e = 1− = 1− = 0.55
Th 810
Compare this to the efficiency calculated from the electrical power
output of 59 MW and heat power input of 165 MW (see prob. 60)
Qh Qc W P 59MW
e= = = = 0.35
heat must be removed Qh H 165MW
to condense the gas
The actual efficiency is less than the Carnot efficiency.
Power Plant

3
 How to improve the efficiency Cogeneration
of a heat engine. Use of waste heat

Increase Th This requires high temperature materials

Decrease Tc This requires efficient heat transfer.

This power plant in Denmark uses the waste heat to heat green
houses nearby.

Refrigerators Refrigerator
The refrigerator uses a liquid with a low
Coefficient of performance
boiling point. The evaporation takes up heat
COP- the heat removed from the
from the refrigerator and the condensation of
4
cold source divided by the work
the gas releases the heat outside the refrigerator.
done.
1 Compressor – gas is compresses and heated
Qc Qc
COP = =
w Qh − Qc 2 Heat exchange coils - the heat is released
from the gas and exhausted outside of the
1
The maximum Carnot COP
refrigerator.
Tc
COP = 3 Expansion valve – The pressure is decreased 2
Th − Tc 3
after going through the valve. The gas is cooled
since Qh Qc
= 4 Cooling coils- Heat is absorbed from within the
Th Tc refrigerator. The gas is heated.

Refrigerator Summary
A freezer is kept at a temperature of 0o F. What is the maximum
COP for a Carnot refrigerator with output temperature of 85o F. If the • The second law of thermodynamics limits the efficiency
electrical energy use is 500kWh/year how much heat is removed in of heat engines to less than 100%
one year, assume 90% conversion of electrical energy to work. • The Carnot cycle is a reversible cycle taking in heat at
COP high T and exhausting heat at low T.
Tc Tc = ( 0 -32)(5/9) +273=255 K
COP = =
255
= 5 .4 • The maximum efficiency of a heat engine working
Th − Tc 302 − 255
Th =(85-32)(5/9)+273=302 K between two temperatures is the Carnot efficiency that
depends only on the ratio of the absolute temperatures.
Work • Refrigerators and heat pumps are heat engines run in
⎛ 60min ⎞ ⎛ 60s ⎞ reverse.
W = 0.9(500 x103 W ⋅ hr ) ⎜ ⎟⎜ ⎟ = 1.62 x10 J
9

⎝ hr ⎠ ⎝ min ⎠
• The maximum coefficient of performance is determined
Heat
Q by a Carnot cycle.
COP = c
w
Qc = COP (w ) = 5.4 x1.62 x109 = 8.7 x109 J Heat removed