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Fire preceded the harnessing of fuels to achieve work. The

heat of fire the tumbling of out of energy as the chaotic

motion of atoms is easily contrived for the tumbling is

unconstrained.

Work is energy tamed, and requires greater sophistication

to contrive.

Thus humanity stumbled easily on to fire but needed

millennia to arrive at the sophistication of the steam

engine, the internal combustion engine and the jet engine.

Peter Atkins (The Four Laws)

Thermodynamics

Michele Hastie

Process Engineering and Applied Science

Dalhousie University

Fall 2016

Slide 23: Area inside the Pv diagram should be the work input

to the refrigeration cycle, not the work output.

Outline

7.1.2 Equivalence of the Kelvin and Clausius Statements

7.3 Heat Engines

7.4 The Carnot Cycle

7.5 The Thermodynamic Temperature Scale

7.6 Refrigerators and Heat Pumps

Thermodynamics

7.7.2 The Molecular Interpretation of Entropy

Outline

7.8.2 The Tds Relations

7.8.3 Entropy Changes of Incompressible Substances

7.8.4 Entropy Changes of Ideal Gases

7.10.2 Entropy Balance for Open Systems

7.11.2 Second Law Efficiency

7.11.3 Lost Work

Introduction

below:

Laws of

Thermodynamics

Concept

Property

Defined

Zeroth Law

Thermal equilibrium

Temperature

First Law

Energy conservation

Energy

Second Law

Direction of processes

Entropy

It does not give any information about:

(page 153)

The quality or usefulness of that energy

the ambient surroundings, but the reverse process will not occur

floor and the reverse (impossible) process

A heat engine is a

system that converts

thermal energy

(transferred as heat)

into mechanical energy

(transferred as

work).

Examples: Otto cycle,

Diesel cycle, Rankine

steam cycle (Chapter 8).

Hot Reservoir

QH

A Cyclic

Process

(Heat Engine)

W = QH QL

QL

Cold Reservoir

Thermal reservoir:

constant temperature.

Source or sink.

Fig. 7.3: Sketch of a system that violates the Kelvin form of the Second Law of Thermodynamics

equivalent ways.

Kelvin statement:

from a hot source completely into work.

Clausius statement:

It is impossible for a

cyclic process to

transfer the heat

absorbed from a

body at a low

temperature to a

body at a higher

temperature

without producing

any other effects.

form of the Second Law of Thermodynamics

Heat does not naturally (spontaneously) flow from a cold

object/system to a hot object/system.

In thermodynamics, spontaneity refers to the tendency

for a process to occur (no information about time/rate).

Some examples of spontaneous processes:

https://en.wikipedia.org/wiki/Combustion

http://www.theguardian.com/science/2011/apr/28/wellcome-science-writing-prize

https://physics.aps.org/story/v22/st5

http://phys.org/news/2013-03-unusual-recrystallization-behavior-one-dimensional-electron.html

Process A is a

contradiction of

the Kelvin form of

the Second Law.

The work from

Process A is used

to drive Process B.

system is that heat

(QL) is transferred

from the cold

reservoir to the hot

reservoir with no

change to the

surroundings.

This is a

contradiction of the

Clausius form of the

Second Law.

Fig. 7.5: Sketch of a system showing that failure of the Kelvin statement implies failure

of the Clausius statement

the Clausius form of the

Second Law.

If it were possible, it

would be in contradiction

of the Kelvin form of the

Second Law.

Fig. 7.6: Sketch of a system showing that failure of the Clausius statement implies

failure of the Kelvin statement

without causing any net change in the surroundings.

Example: Reversible expansion of a gas.

Pexternal

Pexternal

Pile of

sand

Forward

Process

Pexternal

Reverse

Process

P1

P1

P2

P1

(page 159)

P1 > P > P2

P2

P2

Pexternal

Pexternal

Forward

Process

Pexternal

Weight

Reverse

Process

P1

P1

P2

P1

P2

P2

P2

because there are always some irreversible losses.

Common causes of irreversibilities in real systems are:

(page 159)

frictional effects

unrestrained expansion

mixing of fluids

electric resistance

chemical reactions

heat transfer across a finite temperature difference

provide efficiency targets for real processes

http://www.learnthermo.com/T1-tutorial/ch06/lesson-D/pg07.php

absorb or supply large quantities of heat

at constant temperature.

Examples of typical heat sources include:

(page 159)

reactors in nuclear power stations

http://www.industrialboiler.com/boilers/watertube-boilers.aspx

http://www.power-eng.com/articles/print/volume-117/issue-10/features/converting-once-through-cooling-to-closed-loop.html

http://peakoil.com/consumption/watering-down-the-energy-debate

using a working fluid (often steam)

in a cyclic manner to partially

convert heat into work.

The general operation can be

divided into the following steps:

1.

2.

3.

4.

(page 160)

Hot Reservoir

QH

A Cyclic

Process

(Heat Engine)

W = QH QL

fluid from a high-temperature source

QL

(furnaces, nuclear reactors, etc.).

Cold Reservoir

Part of the absorbed heat is

converted into work (typically the

First Law Energy Balance:

working fluid is used to drive a

W QH QL

rotating shaft).

The remaining heat is rejected to a

low-temperature sink (atmosphere,

Thermal efficiency:

ocean, lakes, etc.)

net work output W

heat input

QH

(7.1)

(7.2)

(page 161)

QH QL

QH

QL

QH

Therefore a thermal efficiency of 100% is impossible.

What is the theoretical upper efficiency level of a heat

engine?

(7.3)

1.

(page 162)

Reversible Isothermal

Expansion at TH (1-2):

reversible isothermal

expansion while in contact

with the hot reservoir.

The expansion is reversible

because the temperature of

the system never drops more

than an infinitesimal amount

dT below the temperature of

the hot reservoir.

During the process, the system

absorbs heat, QH, from the hot

reservoir.

2. Reversible

during which the temperature drops from TH to TL.

3. Reversible

reservoir.

The system then undergoes isothermal compression, which is

reversible since the temperature of the system is never more

than an infinitesimal amount dT greater than the temperature

of the cold reservoir.

4. Reversible Adiabatic

(page 162)

Compression (4-1):

during which the temperature changes from TL to TH.

This returns the system to its original state, thereby completing

the cycle.

(page 162)

2

1

P

1

QH

QH

2

TH

Wnet,out

TH

Wnet,out

4

3

TL

4

QL

Green area:

Work done by gas (Steps 1-3)

TH

Wnet,out

4

QL

QH

QL

TL

TL

v

Purple area:

Work done on gas (Steps 3-1)

Blue area:

Work done by cycle

(page 162)

also be operated in

reverse

the cold reservoir and

rejected to the hot

reservoir.

This process is

necessarily associated

with a net work input.

in

refrigeration cycle

(page 163)

Carnots Theorem:

No heat engine operating between two heat reservoirs can

have a higher thermal efficiency than that of a Carnot engine.

Have a lower thermal efficiency than a Carnot engine

operating between the same two temperatures.

(page 163)

consider the situation shown

in Fig. 7.10

In contradiction with Carnots

theorem we assume that a

heat engine, E, with a higher

efficiency than a Carnot

engine drives a Carnot

refrigerator, C.

From the definition of thermal

efficiency we can write that:

W

W

QH

QH

drives a Carnot refrigerator, C. If the

efficiency of engine E is higher than

that of the Carnot refrigerator, the

Second Law is violated.

QH QH

QL QL

(page 163)

the hot reservoir.

This is in direct contradiction to Clausiuss statement of the

Second Law. Thus, Carnots theorem is proved.

Using the same logic it can be shown that all Carnot engines

operating between heat reservoirs at the same two

temperatures must operate with the same thermal efficiency.

Thus, a direct result of Carnots theorem is that:

The thermal efficiency of a Carnot engine only depends on the

temperature levels of the hot and cold reservoirs.

working substance and only depends on the temperature of

the hot and cold reservoirs.

engines with engine A

operating between TH and

TL and engine B operating

between TL and an even

colder temperature TF.

Together, engines A and B

constitute a third Carnot

engine C operating

between TH and TF.

The thermal efficiency of

engine A depends only on

the temperature levels of

the two reservoirs:

QL

QH

f TL , TH

(7.4)

QH

QL

g TL , TH

1 f TL , TH

Engine B:

QL

QF

g TF , TL

Engine C:

QH

QF

g TF , TH

Dividing:

QH

QL

(7.6c)

QH

QL

g TF , TH

g TF , TL

1

g TL , TH

1 f TL , TH

QH

TH

QL

TL

(7.5)

(7.7)

working fluid is an

ideal gas.

For the isothermal

processes, 1-2 and 3-4:

QH

V2

RTH ln

V1

V3

QL RTL ln

V4

(7.8a)

(7.8b)

QH

QL

TH lnV2 V1

TL lnV3 V4

(7.9)

processes, 2-3 and 4-1:

TH

TH

TL

TL

c v dT

V3

ln

R T

V2

(7.10a)

c v dT

V4

ln

R T

V1

(7.10b)

side of these two

equations is the same:

V3

V4

ln ln

V2

V1

V3

V2

ln ln

V4

V1

(7.11)

From (7.9):

QH

QL

TH lnV2 V1

TL lnV3 V4

QH

QL

TH

TL

(7.12)

rev 1

QL

QH

TL

1

TH

(7.13)

rev 1

QL

QH

TL

1

TH

(7.13)

which it is operating.

defines the maximum efficiency that a real heat engine can

operate between two temperatures.

will only be 100% if the cold reservoir has a temperature of

absolute zero or if the hot reservoir has a temperature of

infinity ().

Engine A

Engine B

Thermal efficiency

300 K = 27C

300 K = 27C

25%

62.5%

Heat engines operating with a higher-temperature heat

source can produce more work.

We usually say that thermal energy available at a higher

temperature has a higher quality.

Example 7.1: A power

plant produces 500

MW of electricity.

Steam is generated in

the boiler at 650 K and

discharged to a river at

300 K.

If the thermal

efficiency of the power

plant is 60% of the

maximum theoretical

efficiency, how much

heat is discharged to

the river?

Hot Reservoir

QH

A Cyclic

Process

(Heat Engine)

QL

Cold Reservoir

W = QH QL

Example 7.2: An engine operating

with 80% of the maximum

theoretical efficiency operates

between a hot reservoir at 900 K and

a cold reservoir at 300 K. The engine

is used to drive a Carnot refrigerator.

The Carnot refrigerator is to be used

to freeze 5 kg/h of water at 10C.

If the Carnot refrigerator rejects heat

to a hot reservoir at 300 K, what is

the quantity of heat drawn from the

900 K reservoir by the engine? The

latent heat of fusion of water is

334 kJ/kg.

cycle used by a steam power plant.

Hot Reservoir (i.e. Heat Source), TH

Hot Reservoir

QH

QH

Boiler, T<TH

A Cyclic

Process

(Heat Engine)

W = QH QL

Wnet ,in

Wnet,out

Pump

Turbine

Condenser, T>TL

QL

3

QL

Cold Reservoir

(page 171)

reservoir and reject it to one at a higher-temperature.

Two devices are commonly used to accomplish this:

Both typically operate using a vapour compression cycle.

QH

Boiler, T<TH

Wnet ,in

Wnet,out

Pump

Turbine

Condenser, T>TL

3

QL

(page 171)

(page 172)

typically defined using a coefficient of performance

(COP):

Desired Output

COP

Required Input

Refrigerator

(7.14)

Heat Pump

COPR

QL

Wnet ,in

COPHP

QH

Wnet ,in

COPR

QL

QH QL

COPHP

QH

QH QL

COPR

1

QH / QL 1

COPHP

1

1 QL / QH

(page 172)

pumps will be when these are operated using a reversed

Carnot cycle.

Refrigerators and heat pumps operating on such a cycle

are called Carnot refrigerators or Carnot heat pumps.

QH

For Carnot engines:

TH

QL

Refrigerator

1

COPR

QH / QL 1

COPR,rev

TH TL 1

(7.12)

TL

Heat Pump

COPHP

1

1 QL / QH

COPHP,rev

1 TL / TH

Example 7.3: All of the work generated

by a Carnot engine is used to drive a

Carnot refrigerator. The refrigerator

extracts heat from a cold reservoir at 0C

at a rate of

35 kW. The energy source for the Carnot

engine is a hot reservoir at 250C. Both

the engine and the refrigerator reject

heat to the surroundings at 25C.

a) How much heat does the Carnot

engine absorb from the hot

reservoir?

b) If the actual COP of the refrigerator is

50% of the maximum value and the

actual efficiency of heat engine is 60%

of the maximum value, how much

heat is absorbed from the hot

reservoir?

(page 173)

QH

QL

QH

TH

(page 175)

TH

TL

QL

TL

(7.12)

(7.22)

heat in (+)

heat out ()

QH QL

TH

TL

(7.23)

QH QL

0

TH TL

(7.24)

(page 175)

differential quantities of heat can be transferred:

dQH dQL

0

TH

TL

(7.25)

transferred for the entire cycle:

dQrev

T 0

(7.26)

State function:

(page 175)

of a system

Does not depend on the way in which the system acquired that

state

its original position upon completion of the cycle. An example

is internal energy:

dQ dW 0

(5.1)

entropy:

dQrev

dQrev

dS

;

(7.27)

T 0

T

(page 175)

2

dS

dQrev

T

dQrev

S

T

1

(7.28)

irreversible process. We do this by choosing an arbitrary

reversible process that has the same initial and final

conditions.

(page 176)

2

S

1

(7.28)

dQrev

T

dQrev = 0 and S = 0

Such a process is called isentropic (constant entropy)

Although such processes cannot exist in reality, they provide a

convenient basis for efficiency calculations.

The change in entropy can be calculated from:

2

dQrev

Qrev

1

S

dQrev

T

Tconstant 1

Tconstant

1

Qrev

S

Tconstant

(7.29)

(page 176)

Thermodynamics

Mathematical statement of the Second Law:

The total entropy change associated with any spontaneous

process is positive:

S 0

system and the surroundings.

(page 177)

Thermodynamics

Consider two heat reservoirs at TH and TL:

Q

S H

TH

Q

S L

TL

Total, Stotal

S total

Q

Q

T TL

Q H

TH T L

T H TL

(page 177)

On the molecular scale, entropy can be regarded as a

measure of disorder

vacuum

irreversible total entropy change is > 0

(page 177)

increasing entropy

http://chemwiki.ucdavis.edu/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3A_Lower's_Chem1/

07%3A_Solids_and_Liquids/7.1%3A_Matter_Under_the_Microscope

7.7.2 The Molecular

Interpretation of Entropy

The entropy of a system can

be calculated from:

S k ln

(7.33)

where

(1.380610-23 J/K)

is the total number of

possible microstates of a

system

http://en.wikipedia.org/wiki/Ludwig_Boltzmann

(page 177)

of the system is fixed.

Review:

The state of a single-phase,

single-species (pure) system

can be fixed by specifying

two (2) intensive variables

Can also specify v (or ), , h, or s

Example: To use the superheated steam table, you must know

two (2) property values.

Review:

The state of a two-phase,

single-species (pure) system

can be fixed by specifying

one (1) intensive variable

Can also specify v (or ), , h, or s

property must be fixed to find the others

This is enough to fix the state of each phase (liquid and vapour). We still

need a second intensive variable to fix the state of the mixture.

7.8.1 Property Diagrams (T-s and h-s)

P

2

P2

Area w12 P dv

1

qrev Tds

dv

Adiabatic

reversible

(7.35)

(7.36)

v1

v2

(7.27)

P1

dQrev

T

dq

ds rev

T

dS

1

h

h'

Adiabatic

irreversible

2

2'

s

s

Example 7.4: Sketch a T-s diagram for the Carnot cycle. Identify the quantities of heat

absorbed and rejected and the net work output.

Solution:

Recall that the Carnot cycle is:

1. Reversible isothermal expansion at TH.

2. Isentropic expansion from TH to TL.

3. Reversible isothermal compression at TL.

4. Isentropic compression from TL to TH.

Note that S = 0

7.8.2 The Tds Relations

The differential form of the First Law for a closed system

undergoing a reversible process is:

dU dQrev PdV

dQrev

dS

T

(7.37)

dQrev TdS

(7.38)

Therefore,

dU TdS PdV

(7.39)

7.8.2 The Tds Relations

Rearranging,

dU PdV

dS

T

T

or

du Pdv

ds

T

T

(7.40)

Substituting dH = dU + d(PV)

dS

T

T

T

T

dH VdP

dS

T

T

or

dh vdP

ds

T

T

(7.41)

7.8.3 Entropy Changes of Incompressible Substances

Solids and liquids are commonly approximated as

incompressible substances:

dv = 0 and c = cv = cp

0

ds

du Pdv c dT

T

T

T

(7.42)

2

c dT

dT

T2

s

cave

cave ln

T

T

T1

1

1

(7.44)

Example 7.5: Liquid water undergoes a process where the

pressure and temperature change from 22 MPa and 25C to

5 MPa and 50C.

a) Determine the change in entropy using the approximation

given by Eq. 7.44 (use an average specific heat of

4.18 kJ/[kg.K]).

b) Estimate the entropy change using the compressed liquid

water table.

c) If water at 20 MPa and 50C undergoes isentropic

expansion to 5 MPa, what is the change in temperature?

Solution:

a) Using Eq. 7.44:

s cave ln

T2

T1

7.8.4 Entropy Changes of Ideal Gases

Recall from Chapter 5, for an ideal gas:

RT

P

v

du cv dT

dh c p dT

du Pdv

ds

T

T

cv dT Rdv

ds

T

v

cv dT

Rdv

s

T

v

1

1

7.8.4 Entropy Changes of Ideal Gases

T2

v2

s cv , ave ln R ln

T1

v1

(7.47b)

ds

dh vdP

T

T

ds

c p dT RdP

T

P

T2

P2

s c p , ave ln R ln

T1

P1

(7.49b)

7.8.4 Entropy Changes of Ideal Gases

Note that when s = 0, these equations reduce to the

isentropic relations we derived in Chapter 5:

cv , ave T2

v2

ln ln

R

T1

v1

cv , ave

T

v

ln 2 ln 2

c p , ave cv , ave T1

v1

1

T2

v2

ln ln

k 1 T1

v1

T2 v1

T1 v2

k 1

(7.50a)

T2

P2

c p , ave ln R ln

T1

P1

T2

P2

c p , ave ln c p , ave cv , ave ln

T1

P1

T

P

k ln 2 k 1 ln 2

T1

P1

T2 P2

T1 P1

k 1

k

(7.50b)

Example 7.6: A closed system containing 0.15 kg of air is initially

at 100 kPa and 303 K. The system undergoes a process that

results in a pressure of 360 kPa and a temperature of 500 K. The

system is in contact with a thermal reservoir at 500 K, from

which 8 kJ of heat is absorbed. Calculate:

a) The change in entropy of the air.

b) The change in entropy of the reservoir.

c) The entropy change in the universe.

Solution:

a) We have: T1 = 303 K; T2 = 500 K; P1 = 100 kPa; P2 = 360 kPa

For air: R = 0.2870 kJ kg1 K1 and cp,ave = 1.01 kJ kg1 K1

The change in entropy of the air is:

(page 186)

is generated during reversible processes

The minimum work input for work consuming systems is

required during reversible processes

From Chapter 6:

= + +

= + +

= + +

= + +

(page 186)

= + +

Integrating,

2

(7.55)

system:

2

(page 186)

can be calculated from:

=

to the Bernoulli equation (incompressible flow with no

work or heat transfer):

22 12

2 1 +

+ 2 1 = 0

2

(page 189)

Mass:

Accumulation = Input Output (no generation/consumption)

Energy: Accumulation = Input Output (no generation/consumption)

Entropy: Accumulation = Input Output + Generation (no consumption)

(page 189)

continuously increasing.

On a continuous basis:

dSsystem

Sin Sout S gen

dt

(7.59)

(7.60)

(page 189)

Entropy may be transferred into or out of a system due to

heat transfer or mass flow.

Entropy entering the system due to heat transfer at a

constant temperature can be calculated from:

Q

S heat

T

(7.61)

doing work.

Second Law: Heat is the only mechanism for transferring

entropy.

Entropy Generation:

Reversible processes:

Irreversible processes:

Impossible process:

(page 189)

Sgen = 0

Sgen > 0

Sgen < 0

Sgen > 0.

(page 190)

(7.59)

entropy can only be transferred by heat

not have dots on each

term. Each term has

units of J/K or J/(kgK)

Q k

S system

S gen

Tk

into a system and its surroundings,

S gen Ssystem Ssurroundings

(7.66)

(7.67)

Sgen

surroundings

Q

Ssystem

Tsurroundings

(7.68)

(page 190)

uses air as the working fluid. The device produces the following overall

effects:

The air changes states from 250C and 3 bar to 80C and 1 bar.

The system produces 62 kJ/kg of work.

A certain quantity of heat is transferred to a reservoir at 30C.

According to the Second Law of Thermodynamics, is such a process

feasible? Assume that air is an ideal gas with cp = 1.005 kJ kg-1 K-1.

Solution:

We are given:

P1 = 3 bar; P2 = 1 bar; T1 = 250C = 523.15 K; T2 = 80C = 353.15 K

Treating air as an ideal gas, the entropy change of the air is:

sair

T2

P2

cP ln R ln

T1

P1

(page 191)

dSsystem

Sin Sout S gen

dt

At steady-state,

0

dS system

dt

dSsystem

Q k

m i si m e se Sgen

dt

Tk

S gen

Q k

m e se m i si

Tk

(7.70)

(page 192)

Carnot cycle, which has the maximum possible efficiency.

approaches for calculating efficiency related to the

Second Law:

1.

2.

Second law efficiency (general case: adiabatic or nonadiabatic flow processes)

3.

Lost work

(page 192)

Many processes are essentially adiabatic.

Maximum work for these processes is the isentropic (adiabatic

reversible) isentropic work.

efficiency is:

isentropic work intput

(7.71a)

actual work input

actual work output

isentropic net work output

(7.71b)

isentropic work output

Turbine

(page 193)

For processes that are non-adiabatic, the ideal work must

include S for any heat that is transferred

For a reversible process, Sgen = 0:

0

S gen

Q k

m e se m i si

0

Tk

(7.72)

temperature (T):

Q

m e se m i si T 0

Q T m e se m i si

(7.74)

(page 193)

Substituting this expression for Q into our energy balance

equation,

ue2

ui2

m e he gze m i hi gzi T m e se m i si Wideal

2

2

Wideal

reversible process

Wideal is the minimum work for a work-consuming device or

Wideal is the maximum work for a work-producing device

ue2

ui2

T m e se m i si m e he gze m i hi gzi

2

2

(page 193)

If kinetic and potential energy contributions are negligible we

obtain:

e se m

i si m

e he m

i hi

Wideal T m

(7.77)

volume we can write:

Wideal m T s h

(7.78)

efficiency is:

ideal work input

thermodynamic net work input

(7.79a)

actual work input

is:

actual work output

net

work

output

(7.79b)

thermodynamic

g

ideal work output

(page 194)

The amount of work that is lost due to irreversibilities is

often called lost work.

Q W act m e he

W act

(7.80)

m h

Q m h m h

e e

i i

i i

Wideal T

m s m s m h m h

e e

i i

e e

i i

(page 194)

Wlost T m e se m i si Q

Recall that:

S gen

Q k

m e se m i si

Tk

T S gen T m e se m i si Q

Therefore:

Example 7.9

Wlost T S gen

(7.83)

which the entropy is maximum, the more do the occasions

of further change diminish; and supposing this condition to

be at last completely attained, no further change could

evermore take place, and the universe would be in a state of

unchanging death.

Rudolf Clausius (1868)

as quoted by Jed Z. Buchwald, Robert Fox, The Oxford

Handbook of the History of Physics (2013)

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