19.

2nd Law of Thermodynamics

1.
2.
3.
4.

Reversibility & Irreversibility

The 2nd Law of Thermodynamics
Applications of the 2nd Law
Entropy & Energy Quality

Most energy extracted from the

fuel in power plants is dumped to
the environment as waste heat,
here using a large cooling tower.
Why is so much energy wasted?

2nd law: no Q W
with 100% efficiency

Efficiencies
Engine

Efficiency

Gasoline

18~20%

Diesel

up to 40%

Steam

~8%

Gas Turbine

~ Diesel

Power Plant

Efficiency

Coal

36%

Nuclear

30%

19.1. Reversibility & Irreversibility

Bouncing ball:

Block slowed down by friction:

reversible

irreversible

Examples of irreversible processes:

Beating an egg, blending yolk & white
Cups of cold & hot water in contact

Spontaneous process:
order disorder
( statistically more probable )

GOT IT? 19.1.

Which of these processes is irreversible:
(a) stirring sugar into coffee.
(b) building a house.
(c) demolishing a house with a wrecking ball,
(d) demolishing a house by taking it apart piece by piece,
(e) harnessing the energy of falling water to drive machinery,
(f) harnessing the energy of falling water to heat a house?

19.2. The 2nd Law of Thermodynamics

Heat engine extracts work from heat reservoirs.
gasoline & diesel engines
fossil-fueled & nuclear power plants
jet engines
Perfect heat engine: coverts heat to work directly.

2nd law of thermodynamics ( Kelvin-Planck version ):

There is no perfect heat engine.

No process is possible in which the sole result is the absorption

of heat from a reservoir and its complete conversion into work.
Heat dumped

 cylinder compressed adiabatically

( T rises to Th adiabatically )
gas in contact with Th , expands isothermally
to do work; heat Qh = Wh absorbed
cylinder expands adiabatically
( T drops to Tc )
cylinder in contact with Tc , gas compressed
isothermally heat Qc = Wc dumped

simple heat engine

Efficiency

Net Work
Heat Input

(any engine)

U 0 W Q

(any cycle)

Qh Qc
Qh

(Simple engine)

Qc
Qh

Carnot Engine
Ideal gas:
AB:
Heat abs.

Qh Q AB

B C:
Work done

3
V
n R Th ln B
2
VA

WBC U BC nR Tc Th

C D:
Heat rejected:

Qc QCD n R Tc ln

VD
VC

D A:
WDA U DA
Work done
Adiabatic processes:
1. isothermal expansion: T = Th , W1 = Qh > 0
2. Adiabatic expansion: Th Tc, W2 > 0

3
nR Th Tc
2

Th VB 1 Tc VC 1
1
D

Tc V

Th V

1
A

VC VB

VD VA

3. isothermal compression: T = Tc , W3 = Qc < 0

Adiabatic compression : Tc Th , W4 = W2 < 0

ecarnot 1

Qc
T
1 c
Qh
Th

Example 19.1. Carnot Engine

A Carnot engine extracts 240 J from its high T reservoir during each cycle,
& rejects 100 J to the environment at 15C.
How much work does the engine do in each cycle?
Whats its efficiency?
Whats the T of the hot reservoir?

work done
efficiency

W Qh Qc 240 J 100 J
e 1

Qc
100 J
1
Qh
240 J

e 1

288 K
Th

140 J

58.3 %

Th

288K
691 K 418 C
1 e

Engines, Refrigerators, & the 2nd Law

Carnots theorem:
1.All Carnot engines operating between temperatures Th & Tc have the same efficiency.
2.No other engine operating between Th & Tc can have a greater efficiency.
Refrigerator: extracts heat from cool reservoir into a hot one.

work
required

perfect refrigerator: moves heat from cool to hot reservoir without work being done on it.
2nd law of thermodynamics ( Clausius version ):
There is no perfect refrigerator.

No process is possible whose sole result is the transfer of heat from a body of
lower temperature to a body of higher temperature.

Perfect refrigerator Perfect heat engine

Clausius Kelvin-Planck

Hypothetical
engine,
e = 70%

Carnot
refrigerator,
e = 60%

Carnot engine is most efficient

eCarnot = thermodynamic efficiency
eCarnot erev > eirrev

19.3. Applications of the 2nd Law

Power plant

Turbine
Generator
Electricity

Boiler
Condenser

fossil-fuel : Th = 650 K
Nuclear :

Th = 570 K
Tc = 310 K

Heat source
Cooling
water

Waste
water

Actual values:
efossil ~ 40 %

enuclear ~ 34 %
Prob 54 & 55

ecar ~ 20 %

e fossil 1

310 K
650 K

enuclear 1

310 K
46 %
570 K

52 %

Application: Combined-Cycle Power Plant

Turbine engines: high Th ( 1000K 2000K ) & Tc ( 800 K ) not efficient.
Steam engines : Tc ~ ambient 300K.
Combined-cycle : Th ( 1000K 2000K ) & Tc ( 300 K ) e ~ 60%

Example 19.2. Combined-Cycle Power Plant

The gas turbine in a combined-cycle power plant operates at 1450 C.
Its waste heat at 500 C is the input for a conventional steam cycle, with its condenser at 8 C.
Find e of the combined-cycle, & compare it with those of the individual components.

ecombined 1

273 8
84 %
273 1450

eturbine 1

273 500
273 1450

55 %

esteam 1

273 8
273 500

64 %

Refrigerators

Coefficient of performance (COP) for refrigerators :

COP

Qc
W

Qc
Qh Qc

Tc
Th Tc

1st law

Max. theoretical value (Carnot)

COP is high if Th Tc .

W = 0 ( COP = ) for moving Q when Th = Tc .

Example 19.3. Home Freezer

A typical home freezer operates between Tc = 18C to Th = 30 C.
Whats its maximum possible COP?
With this COP, how much electrical energy would it take to freeze 500 g of water initially at 0
C?

COP

Tc
Th Tc

273 18
30 18

5.31

Q L m 334 kJ / kg 0.5 kg 167 kJ

W

167 kJ
Q

5.31
COP

Table 17.1

31 kJ

2nd law: only a fraction of Q can become W in heat engines.

a little W can move a lot of Q in refrigerators.

Heat Pumps
Heat pump: moves heat from Tc to Th .

Heat pump as AC :

COPcooling

Heat pump as heater : COPheating

Qc Qc Tin

W Qh Qc Tout Tin

Qh
Tin
Qh

Tin Tout
W
Qh Qc

Ground temp ~ 10C year round (US)

GOT IT? 19.2.

A clever engineer decides to increase the efficiency of a Carnot
engine by cooling the low-T reservoir using a refrigerator with the
maximum possible COP.
Will the overall efficiency of this system
(a) exceed.
(b) be less than.
(c) equal that of
the original engine alone?

see Prob 32 for proof

19.4. Entropy & Energy Quality

2nd law:
Energy of higher quality can be converted
completely into lower quality form.
But not vice versa.

Energy quality measures the

versatility of different energy forms.

Conceptual Example 19.1. Energy Quality, End Use, & Cogeneration

You need a new water heater, & youre trying to decide between gas & electric.
The gas heater is 85% efficient, meaning 85% of the fuel energy goes into heating water.
The electric heater is essentially 100% efficient.
Thermodynamically, which heater makes the most sense?

Ans.
Only 1/3 of fuel energy is converted to electricity at a power plant.
With this in mind, the gas heater is a better choice.

Cogeneration:
Waste heat from electricity generation used for low needs.

Making the Connection

If the electricity comes from a more efficient gas-fired power plant with e = 48%,
compare the gas consumption of your two heater choices.

Gas heater:

1 unit of fuel energy becomes 0.85 unit of heat.

Electric heater:

1 unit of fuel energy becomes 0.48 unit of electric energy,

then becomes 0.48 unit of heat.

Electric heater consumes 0.85/0.48 = 1.8 times the fuel consumed by gas heater.

Entropy
Carnot cycle (reversible
processes):

Qc Tc

Qh Th

Qh = heat absorbed
Qc = heat rejected

Qc Qh

Tc
Th

lukewarm: cant do W,

dQ

C T 0

Qh , Qc = heat absorbed

C = Carnot cycle
C = any closed path

Irreversible processes cant be represented by a path.

Contour = sum of Carnot

cycles.

dQ
T

S = entropy

[S]=J/K

S = 0 over any closed path

S21 + S12= 0
S21 = S21

Entropy change is path-independent.

( S is a thermodynamic variable )

Entropy in Carnot Cycle

Ideal gas

Heat absorbed:
Heat rejected:

Qh Q AB n R Th ln

VB
VA

Qc QCD n R Tc ln

VD
VC

Adiabatic processes

Th VB 1 Tc VC 1
1
D

Tc V

Th V

1
A

Q ABC QAB

V
n R Th ln B
VA

S ABC

Q AB
V
n R ln B
Th
VA

Q ADC QDC

V
n R Tc ln C
VD

S ADC

QDC
V
n R ln C
Tc
VD

VC VB

VD VA

S ABC

Irreversible Heat Transfer

Cold & hot water can be mixed reversibly
using extra heat baths.
T1 = some medium T.

Sc

Tf

Tc

S h

Tf

Th

S Sc Sh

Q Q
c h
T1 T2

S 0

Q Q
c c
T1 T 2

Q
dQ
c
T
T1
Q
dQ
h
T
T2

reversible processes

T2 = some medium T.

1 1
Qc

T1 T2 0

Actual mixing, irreversible processes

T2 T1

Adiabatic Free Expansion

Adiabatic

Qad.exp. = 0

pvacuum 0

Wad . exp. 0

U ad . exp. 0

Tad . exp. 0

S can be calculated by any reversible

process between the same states.

S
p = const.
Cant do work
degraded.

dQ
1
Q
dQ
T
T
T

W
1

T
T
n R ln

V2
V1

V2

V1

n RT
dV
V

isothermal

Entropy & Availability of Work

Before adiabatic expansion, gas can do work isothermally

W Q n R T ln

V2
V1

After adiabatic expansion, gas cannot do work, while its entropy increases by

V
Q
n R ln 2
V1
T

Eunavailable T S

In a general irreversible process

Eunavailable Tmin S

Coolest T in system

Example 19.4. Loss of

A 2.0 L cylinder contains 5.0 mol of compressed gas at 300 K.
If the cylinder is discharged into a 150 L vacuum chamber & its temperature remains at 300 K,
how much energy becomes unavailable to do work?

Eunavailable Tmin S n R T ln

V2
V1
150 L 2 L

2.0
L

5.0 mol 8.314 J / K / mol 300 K ln

54 kJ

A Statistical Interpretation of Entropy

Gas of 2 distinguishable molecules occupying 2 sides of a box

Microstates

Macrostates

probability of
1/4
macrostate

2 =
1/4

Gas of 4 distinguishable molecules occupying 2 sides of a box

Microstates

Macrostates

probability of
macrostate

1/16 = 0.06
4 1/16 = =0.25
6 1/16 = 3/8 = 0.38
4 1/16 = =0.25
1/16 = 0.06

Gas of 1023 molecules

Gas of 100 molecules

Equal distribution of molecules

Statistical definition of entropy :

S k B ln

# of micro states

Entropy & the 2nd Law of Thermodynamics

2nd Law of Thermodynamics :

S 0

in any closed system

S can decrease in an open system by outside work on it.

However, S 0 for combined system.

S 0 in the universe
Universe tends to disorder

Life ?

GOT IT? 19.3.

In each of the following processes, does the entropy of the named system
increase, decrease, or stay the same?

(a) a balloon inflates

(b) cells differentiate in a growing embryo, forming different organs
(c) an animal dies, its remains gradually decays
(d) an earthquake demolishes a building
(e) a plant utilize sunlight, CO2 , & water to manufacture sugar

(f) a power plant burns coal & produces electrical energy

(g) a cars friction based brakes stop the car.