Chapter 20 Second law

of Thermodynamics

Topics:
-2nd law
-heat engines
-entropy
-3rd law
 20-1 Second law of
Thermodynamics -
introduction
ocesses can be imagined for which energy is conserved,
se are not observed to occur in nature, e.g.

process “heat from colder object to hotter object” energy ca

ed, but it does not happen spontaneously

law of thermodynamics is about which processes occur in natur

ch do not
 20-1 Second law of
Thermodynamics -
f thermodynamics introduction
according to Clausius:

flow spontaneously from a hot object to a cold object, heat

ntaneously from a cold object to a hot object

tage of this formulation:

to one particular process, not obvious how it applies to othe

l statement of 2nd law of thermodynamics based partly on the s

ngines, which are devices that change thermal energy into mec
e.g. steam engine, automobile engine)
 20-2 Heat Engines
operating
temperature
Mechanical energy can be
obtained from thermal energy
only when heat is allowed to
flow from a high to a low
temperature. Some of the
heat can then be transformed
to work.

engines that run in a

repeated cycle
E  0
exhaust (then system returnsint
repeatedly to
QH and
its starting point) W  QL
thus can run continuously :

operating
temperature conservation of energy:
 20-2 Heat Engines
steam engines
working substance:
material that is
heated and cooled

gas on exhaust side is cooled,

hence pressure on backside of
the blade is less and the turbine
runs!

Why a temperature difference is needed:

suppose steam is at the same temperature throughout the system (no
condenser or pump), then pressure of the gas being exhausted is the
same as that on intake, i.e. work is done by the gas on the piston
during expansion and an equal amount of be
should work hasthan
less to bethedone
workbydone
the
piston to force the steam out thebyexhaust no net intake
the gas during work!
 20-2 Heat Engines
internal combustion
engine
(see also Otto cycle)
 20-2 Heat Engines
efficiency
output
(what you get from the engine)

W QH  QL QL
e   1
QH QH QH
input
(what you pay for in burned fuel)

e = 1 (100 %) only if QL = 0
(i.e. when no heat is exhausted to environment)
 20-2 Heat Engines
Exercise A: a violation of the 2nd
law?

ideal gas expands adiabatically (Q =

then
W
e 
Q

no violation of the 2nd law, as

W efficiency makes no sense for
a single process, it is only defined
for cyclic processes that return
to the initial state
 20-2 Heat Engines
QL
e  1
QH
it is NOT possible to reduce QL
to zero, i.e. a perfect engine
(100 % efficiency) is NOT possible

Planck statement of 2nd law of thermodynamics according:

ce is possible whose sole effect is to transform a given amou

mpletely into work

he Clausius and Kelvin-Planck statements equivalent?

 20-3 Reversible and
Irreversible processes -
Carnot cycle
ible process:
ied out infinitely slowly
ess can be considered a series
quilibrium states
be done in reverse with no change
magnitude of work done or heat
hanged

al processes are irreversible

W
nnot be done precisely in reverse
are not done infinitely slowly
here is friction, turbulence in the gas, etc.)
cannot be plotted on a PV diagram

Carnot’s idealized engine (reversible cycle)

working substance = ideal gas
ible processes are conceptually
etically) important -ab: isothermal expansion at TH, heat QH added
-bc: adiabatic expansion, Q = 0, temp lowered
-cd: isothermal compression at TL, heat QL flow
-da: adiabatic compression, Q = 0, temp back t
hs of the Carnot cycle are reversible !
20-3 Reversible and
Irreversible processes -
Carnot
Carnot’s cycle
theorem:

All reversible engines operating between the same two

constant temperatures TH and TL have the same efficienc
Any irreversible engine operating between the same two
fixed temperatures will have an efficiency less than th

The maximum possible efficiency for a real (irreversibl

engine is:
TL
eideal  1
TH
(derivation see book of Giancoli)
practice: 60-80 % of the Carnot efficiency is reached

e = 1 (100 %) only if TL = 0, which is practically (but

theoretically) impossible (see Kelvin-Planck statement
2nd law)
20-3 Reversible and
Irreversible processes –
Otto cycle (self study)
(automobile internal combustion
engine)
1
burning of the gas:
 V 
e  1 a  
heat QH added at
constant V power stroke  Vb 
(adiabatic expansion)
compression ratio

compression stroke
(adiabatic) exhaust stroke
heat QL ejected to
environment
start
 20-4 Refrigerators and
basis: Air Conditioners
QL  W  QHreverse of heat engine: transfer heat out
cool environment into a warm one
note: QH > QL and work W is needed for thi

environment According to the Clausius statement of th

2nd law, a perfect refrigerator (W = 0) is
exhaust NOT possible, i.e. work must be done.

Coefficient of performance:
QL QL
COP  
W QH  QL
Ideal refrigerator:
heat removed from TL T /T
cold area COPideal   L H
TH  TL 1  TL / TH
inside of refrigerator
note: air conditioner works very much
like a refrigerator
 20-4 Refrigerator
system (construction)
20-4 Heat Pump
operating principle of heat pump same as
that of a refrigerator (or air condition
the objective is now to heat (QH) rather
to cool (QL).

hence, the coefficient of performance is

QH QH
COP   1
W QH  QL

ideal heat pump

TH 1
COP heat pump
ideal    1  COPideal
refrigerator

TH  TL 1  TL / TH

note: a heat pump can be ‘turned around’

and used as an air conditioner (in summe
 20-5 Entropy
a general statement of the 2nd law and this can be accomplish
of a quantity called entropy (Clausius)
ntropy is interpreted as a measure of order/disorder of a sys

n entropy of a system when an amount of heat Q is added to it

ersible process at constant T: Q
S 
T
s not constant then
dQ
dS 
T
n entropy of a system taken reversibly from state a to state
b b
dQ
S  Sb  S a   dS  
a a
T
will be shown, this does not depend on the process:
is a state variable

t entropy is a state variable for a Carnot cycle (consider paths abc and adc
 20-5 Entropy is a state
variable dQ  dQ  0 b a


I ,a
T 
II ,b
T

e can show by representing any b b

eversible cycle as a series of dQ dQ
arnot cycles that  T
 
T
with the original sign convention): I , a II , a

i.e. the integral between any two equilibr

dQ states a and b does not depend on the path
 T
0 process
change in entropy between a and b does not
depend on the path, i.e. entropy is state
 20-6 Entropy and the
Second Law of
Thermodynamics - examples
uation for entropy change S can
ly be applied to reversible processes

r real (i.e. irreversible) processes we

ke a reversible process that takes the
stem between the same two states

is S then also holds for the

reversible process, as S only depends
the initial and final states
 20-6 Entropy and the
Second Law of
Thermodynamics
of water at 20 C is mixed with 50 kg of– example
water at 24 C.

20-6
is the change in entropy?

= mcT = 50 x 4186 x 2 = 4.186x105 J flows from hot water (24 C 

d water (20 C  22 C)

entropy change
 20-6 Entropy and the
Second Law of
Thermodynamics
in entropy for adiabatic free expansion –of n example
f ideal gas from volume V to volume V
20-7
1 2

is very quickly, hence irreversible, and further:

versible isothermal process that takes the gas from volume V1 to vol
te S. The first law gives:

ideal gas
 20-6 Entropy and the
Second Law of
Thermodynamics – example
iron (c = 450 J/(kg.K) at T = 880 K is thrown in a huge lake at T =

e approximations (concerning 20-8

1 2
s so huge that its temperature rise is negligible
average T) of example 20-6 cannot be ma

e receives from iron an amount of heat

mc(T2-T1) = 2 x 450 x (880-280) = 540 kJ

total change in entropy
the lake is constantly at T2 = 280 K, hence
1930 J/K – 1030 J/K = 900 J/K
 20-6 Entropy and the
Second Law of
Thermodynamics – exercise
D
ece of ice at 0 C melts slowly to water at 0 C. Ice is in contact w
whose temperature is only infinitesimally greater than 0 C

hange of ice = Q/T = 333x103/273 = 1220 J/K

hange of heat reservoir = -Q/T = -333x103/273 = -1220 J/K

0
 20-6 Entropy and the
Second Law of
Thermodynamics –
r: entropy of system plus that of the environment either stays cons

conclusions
e process (e.g. exercise D): S = S
total + S
syst = 0
env

20-7, 20-8 we found Stotal = Ssyst + Senv > 0

ersible, processes)

atement of the 2nd law of thermodynamics

cesses are observed in nature and which are not? tells us about the
go)

y of an isolated system never decreases. It either stays constant

e process) or increases (irreversible process).

real processes are irreversible)

entropy of any system plus that of its environment increases as a re

ural process: Stotal = Ssyst + Senv > 0
 20-6 Entropy of ideal gas
ideal gas:
(see also problem 51)
PV  nRT P state 2
( P  dP,V  dV , T  dT )
PdV  VdP  nRdT
state 1
CP  CV  R
( P, V , T )

V
PdV  VdP dV
dS  nCV  nR
dQ  dEint  dW  nCV dT  PdV nRT V
 dV dP  dV
dS  nCV     nR
 V P  V
dQ dT P
dS   nCV  dV dP dV
T T T dS  nCV  n CV  R 
P V
dT dV
dS  nCV  nR dP dV
T V dS  nCV  nCP
P V
 20-6 Entropy of ideal gas
(see also problem 51)

deal gas, adiabatic: then show that

PV  nRT
dP dV

PV  constant dS  nCV  nCP 0
P V
CP
= as it should be
CV
20-6 Entropy of ideal gas
integral form
from state 1 (T1,P1,V1) to state 2 (T2
dT dV T  V 
dS  nCV  nR S  nCV ln  2   nR ln  2 
T V  T1   V1 

dP dV P  V 
dS  nCV  nCP S  nCV ln  2   nCP ln  2 
P V  P1   V1 
 20-7 Order to Disorder
stem can be considered a measure of the disorder of the system, i.e.
be stated as:

es tend to move toward a state of greater disorder

e at 0 C: entropy increases:

contact with colder object (example 20-6):

classes of molecules can be distinguished (high and lower average ki

flown: one class with same average kinetic energy (less orderly)

d cold object can serve as the two ‘regions’ of a heat engine and he

jects have reached same temperature, no work can be obtained

t can perform work must have higher order than a system that cannot
 20-8 Unavailability of
Energy; Heat Death
ample 20-6 another aspect of the 2nd law is illustrated:

al process, some energy become unavailable to do useful work

ver lost (it is conserved cf. 1st law), rather it becomes less useful

graded, as it goes from more orderly forms (e.g. mechanical) to leas

s (thermal)

f energy that becomes unavailable to do work is proportional to the

uring any process

e: as time goes on, the universe should approach a state of maximum

se is then at one temperature, no work could be done, as all energy
energy

th of the universe
 20-9 Statistical
Interpretation of
Entropy and
positionthe Second
kes a distinction between ‘macrostate’ and ‘microstate’ of a system
is specified by giving the and velocity of every molecule

Law
is specified by giving macroscopic properties like temperature and
know the macrostate of a system, we assume each microstate is equa

ge number of microstates correspond to the same macrostate.

le:

east probable,
ighest order

ost probable,
owest order

total # of microstates = 1
 20-9 Statistical
Interpretation of
Entropy and the Second
Law
east probable,
ighest order

most probable,
lowest order

total # of microstates = 2100 = 1.3x1030

 20-9 Statistical
Interpretation of
Entropy
probable and
state of a gas: the Second
molecules
very unlikely: orderly arrangement
of all molecules in a corner of the
up whole space and move randomly

Law
ell velocity distribution) space, all moving with same velocity

most probable state = state with greatest entropy

= state with greatest disorder

S  k ln W(with W the number of microstates

corresponding to the given macrostate)
20-9 Statistical
Interpretation of Entropy
and the Second Law
example
of gas, i.e.20-9: free expansion
NA molecules, assume volumeagain
doubles(example 20-7
calculated
umber differently)
of microstates increases by
ch molecule has 2 times as many positions):
W2
 2N A
W1
hange in entropy is:
 W2 
S  S 2  S1  k ln W2  k ln W1  k ln    k ln 2 N A  kN A ln 2  R ln 2
 W1 
same answer as obtained in example 20-7
 20-9 Statistical
Interpretation of
Entropy and the Second
Law
probability, 2nd law states that processes occur whi
does not forbid a decrease in entropy, rather it s
is extremely low
 20-10 Thermodynamic
Temperature; Third Law
of Thermodynamics

law:
is not possible to reach absolute zero in any finit
ber of processes
 20-11 Thermal Pollution,
Global Warming, Energy
Resources
solar energy installation fossil fuel steam plants
cooling towers electric generating p

e energy (80 %) we utilize makes uses of a heat engine

el steam plants, nuclear power plants)

ric (15 %) and solar and wind: no heat engine necessary

orbed by environment), called thermal pollution (unavoidable)

ution (smog) and global warming (CO2) (avoidable)
20-11 Electric
Energy
Resources
 Problem 6
eversible heat engine
orking substance: 1 mol of Ar

oint a: STP
oints b and c: on isotherm at 423 K

a) path of the cycle: clockwise or

counterclockwise?

b) efficiency of the engine?

 Problem 7
Diesel Engine (compare with
Otto cycle)
 Problem 44
al gas of n moles undergoes a reversible
cess shown in the PV diagram

temperature of the gas at points a and b

the same

t is the change in entropy of the gas?

long the isotherm connecting a and b we have

nd

ence
 Problem 58
(see mastering
physics)
 Problem 63
(see mastering
physics)
 Problem 69
(see mastering
physics)
 Problem 72
(see mastering
physics)
 Problem 77
Stirling Cycle (solar
power system)
 Problem 78
Brayton Cycle (gas
turbine)