Advanced Thermodynamics

Note 4
The Second Law of Thermodynamics

Lecturer: 郭修伯
 Differences between heat and work
• A conversion efficiency of 100% by elimination of
friction, a dissipative process that transforms work into
heat.
• All efforts to devise a process for the continuous
conversion of heat completely into work or into
mechanical or electrical energy has failed. Conversion
efficiencies do not exceed about 40%.
• The flow of heat between two bodies always takes place
from the hotter to the cooler body, and never in the
reverse direction.
 The second law
• No apparatus can operate in such a way that its
only effect is to convert heat absorbed by a system
completely into work done by the system.
– It is impossible by a cyclic process to convert the heat
absorbed by a system completely into work done by the
system.
• No process is possible which consists solely into
the transfer of heat from one temperature level to a
higher one.
 • Heat engine: devices or machines that produce
work from heat in a cyclic process.
– Essential to all heat-engine cycles are absorption of heat
into the system at a high temperature, rejection of heat
to the surroundings at a lower temperature, and
production of work.
– In operation, the working fluid of a heat engine absorbs
heat |QH| from a hot reservoir, produces a net amount of
work |W|, discard heat |QC| to a cold reservoir, and
returns to its initial state.

The first law: W = QH − QC

W QH − QC QC
The thermal efficiency of the engine: η ≡ = = 1−
QH QH QH
• If a thermal efficiency of 100% is not possible for heat engines, what determines
the upper limits?
• A heat engine operating in a completely reversible manner is called a Carnot
engine (N.L.S. Carnot, 1824):
– Step 1: A system at the temperature of a cold reservoir TC undergoes a reversible adiabatic
process that causes its temperature to rise to that of a hot reservoir at TH.
– Step 2: The system maintains contact with the hot reservoir at TH, and undergoes a reversible
isothermal process during which heat |QH| is absorbed from the heat reservoir.
– Step 3: The system undergoes a reversible adiabatic process in the opposite direction of step
1 that brings its temperature back to that of the cold reservoir at TC.
– Step 4: The system maintains contacts with the reservoir at TC, and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns to its initial state with
rejection of heat |QC| to the cold reservoir.
The cycle traversed by an ideal gas serving as the working fluid in a Carnot engine
is shown by a PV diagram.
a → b adiabatic compression
b → c isothermal expansion
TH c → d adiabatic expansion
d → a isothermal compression
P b |QH|
For the isothermal steps b → c and d → a
c Vc Vd
QH = RTH ln and QC = RTC ln
TC Vb Va
For adiabatic processes a → b and c → d
a
d TH CV dT Va TH CV dT Vd
|QC|
∫TC R T
= ln
Vb
and ∫
TC R T
= ln
Vc
V
QH TH ln(Vc / Vb ) TH W QC TC 300
= = η= = 1− = 1− η = 1− = 0.5
QC TC ln(Vd / Va ) TC QH QH TH 600
Rough practical limits for ηof a Carnot engine; actual heat engines are irreversible
and ηrarely exceed 0.35.
A central power plant, rated at 800,000 kW, generates steam at 585K and discards
heat to a river at 295 K. If the thermal efficiency of the plant is 70% of the
maximum possible value, how much heat is discarded to the river at rated power?

295
η max = 1 − = 0.4957 η = 0.7 × 0.4957 = 0.347
585

W QC TC
η= = 1− = 1−
QH QH TH

η = 0.347 W = 800000 kW
QC = 1505500 kW
 QH QC QH QC
• A Carnot engine: = + =0
TH TC TH TC

dQH dQC
+ =0
TH TC

dQrev dQrev dQrev

∆S t = ∫ dS t = ∫ =0
T
• There exists a property called entropy S,T which is an intrinsic
T property of a system,
functionally related to the measurable coordinates which characterize the system.
– If a process is reversible and adiabatic, dQrev = 0, dS = 0. The entropy of a system is constant
t

during a reversible adiabatic process and the process is isentropic.

– When a system undergoes an irreversible process between two equilibrium states, the entropy
change of the system ΔSt is evaluated by an arbitrarily chosen reversible process. Since entropy is
a state function, the entropy changes of the irreversible and reversible processes are identical.
 Entropy changes of an ideal gas
• For one mole of fluid undergoing a mechanically
reversible process in a closed system:
dU = dQrev − PdV

dH = dU + PdV + VdP

dQrev = dH − VdP
dH = C Pig dT V = RT / P
dQrev dT dP
dS = = C Pig −R
T T P

∆S T C
ig
P dT P
=∫ − ln
R T0 R T P0
For an ideal gas with constant heat capacities undergoing a reversible
adiabatic process:
∆S T C
ig
dT P
=∫ P − ln
R T0 R T P0
∆S = 0
C Pig T2 P
0= ln − ln 2
R T1 P1

R / C Pig
T2  P2 
=  
T1  P1 
ig
C
C =C +R γ = P
ig ig
P V
CVig
( γ −1) / γ
T2  P2 
=  
T1  P1 
The 2nd law mathematical statement
• Let a quantity of heat |Q| be transferred from the hotter (TH) to
the cooler (TC) reservoir. The entropy changes of the two
reservoirs are: −|Q| −|Q|
∆S H =
t t
∆SC =
TH TC

 TH − TC 
∆Stotal = ∆S + ∆S =| Q | 
t
H
t
H

 TH TC 

• For the process of irreversible heat transfer, ΔStotal is always

positive, approaching zero as the process becomes reversible.

∆Stotal ≥ 0
A 40 kg steel casting (CP= 0.5 kJ/kgK) at a temperature of 450°C is quenched in
150 kg of oil (CP= 2.5 kJ/kgK) at 25°C. If there are no heat losses, what is the
change in entropy of (a) the casting, (b) the oil, and (c) both considered together?

No heat losses: ( 40)(0.5)(T − 450) + (150)(2.5)(T − 25) = 0 T = 46.25 C

dQ C dT T kJ
(a) the casting ∆S = ∫ = m∫ P = mC P ln 2 = −16.33
t

T T T1 K
dQ C dT T kJ
(b) the oil ∆S t = ∫ = m∫ P = mCP ln 2 = 26.13
T T T1 K
kJ
(c) total entropy change ∆Stotal = ∆S cast + ∆S oil = 9.80
t t

K
 Entropy balance for open systems

Net rate of change Time rate of Time rate of Total rate

in entropy of change entropy in change entropy of entropy
flowing streams control volume in surroundings generation

t
d (mS ) cv dS surr
∆ ( Sm ) fs + + = S G ≥ 0
dt dt

d (mS ) cv Q j
∆( Sm ) fs + −∑ = S G ≥ 0
dt j Tσ , j
 In a steady-state flow process, 1 mol/s of air at 600 K and 1 atm is continuously
mixed with 2 mol/s of air at 450K and 1 atm. The product stream is at 400K and 1
atm. Determine the rate of heat transfer and the rate of entropy generation for the
process. Assume that air is an ideal gas with CP = (7/2)R, that the surroundings are
at 300K, and that kinetic- and potential-energy changes are negligible.
mol
n = 3 Q
s 
S G = n S − n A S A − n B S B −
mol Tσ
n A = 1 T = 400 K
s Q
= n A ( S − S A ) + n B ( S − S B ) −
TA = 600 K Tσ
C.V.
mol T T Q
n B = 2 = n AC P ln + n B C P ln −
s TA TB Tσ
TB = 450 K 7  400 400  8729.7
Q = ( )(8.314) (1) ln + (2) ln  +
2  600 500  300
J
= 10.446
Ks

Q = n H − n A H A − n B H B = n AC P (T − TA ) + n B C P (T − TB ) = −8729.7 J / s
 An inventor claims to have devised a process which takes in only saturated steam
at 100 °C and which by a complicated series of steps makes heat continuously
available at a temperature level of 200°C. The inventor claims further that, for
every kilogram of steam taken into the process, 2000 kJ of energy as heat is
liberated at the temperature level of 200°C. Show whether or not this is possible. In
order to give the inventor the benefit of any doubt, assume cooling water available
in unlimited quantity at a temperature of 0°C.
∆H = Q + Ws
T’ = 200°C
Q = Q′ + Qσ = −2000 + Qσ
Q′ = −2000kJ
∆H = 0.0 − 2676 = −2000 + Qσ
Saturated steam Liquid water
at 0 °C Qσ = −676.0 kJ
at 100 °C
apparatus kJ
kJ ∆S = 0.0 − 7.3554 = −7.3554
H 1 = 2676 H 2 = 0.0 K
kg
S 2 = 0.0 2000 kJ
kJ ∆S t = = 4.227
S1 = 7.3554 Qσ 200 + 273.15 K
kgK
676.0 kJ
∆S t = = 2.4748
Tσ = 0°C 0 + 273.15 K
kJ
∆S total = −7.3554 + 4.227 + 2.4748 = −0.6536
K
 Calculation of ideal work
• In a process producing work, there is an absolute
maximum amount which may be accomplished as the
result of a given change of state of the fluid flowing
through the control volume.
• The limiting value obtains when change of state associated
with the process is accomplished completely reversibly.
• The entropy generation is zero:

Q  1  
∆( Sm ) fs − =0 Q = Tσ ∆( Sm ) fs ∆  H + u 2 + zg m  = Tσ ∆( Sm ) fs + W s (rev)
Tσ  2   fs

 1  
Wideal = ∆H − Tσ ∆S W ideal = ∆( Hm ) fs − Tσ ∆( Sm ) fs W ideal = ∆  H + u 2 + zg m  − Tσ ∆( Sm ) fs
 2   fs

W ideal W s
ηt ( work required ) =  ηt ( work produced ) = 
Ws Wideal
 What is the maximum work that can be obtained in a steady-state flow process
from 1 mol of nitrogen (assumed an ideal gas) at 800 K and 50 bar? Take the
temperature and pressure of the surroundings as 300 K and 1.0133 bar?

For an ideal gas, enthalpy is independent of pressure, and its change is given:
T J
∆H = ∫ C Pig dT = 8.314 × ICPH (800,300;3.280,0.593E − 3,0.0,0.040 E + 5) = −15060
T0 mol
T2 dT P 1.0133 J
∆S = ∫ C Pig − R ln 2 = −15060 − 8.314 ln = 3.042
T1 T P1 50 mol
J
Wideal = ∆H − Tσ ∆S = −15060 − (300)(3.042) = −15973
mol

Or, Step 1, reversible, adiabatic expansion from initial state to 1.0133 bar, T’
Step 2, cooling to the final temperature
Step 1 Q + WS = ∆H WS = ∆H = ( H ′ − H1 )
T − Tσ T2 dQ
Step 2 dWCarnot = (dQ ) WCarnot = Q − Tσ ∫ = ( H 2 − H ' ) − Tσ ∆S
T T' T

Total Wideal = WS + WCarnot = ∆H − Tσ ∆S

 An inventor claims to have devised a process which takes in only saturated steam
at 100 °C and which by a complicated series of steps makes heat continuously
available at a temperature level of 200°C. The inventor claims further that, for
every kilogram of steam taken into the process, 2000 kJ of energy as heat is
liberated at the temperature level of 200°C. Show whether or not this is possible. In
order to give the inventor the benefit of any doubt, assume cooling water available
in unlimited quantity at a temperature of 0°C.

T’ = 200°C ∆H = 0.0 − 2676 = −2676

kJ
∆S = 0.0 − 7.3554 = −7.3554
Q′ = −2000kJ K
Saturated steam Liquid water Wideal = ∆H − Tσ ∆S
at 100 °C at 0 °C = −2676 − (273.15)(−7.3554)
apparatus
kJ J
H 1 = 2676 H 2 = 0.0 = −666.9
kg mol
S 2 = 0.0
kJ
S1 = 7.3554 Qσ T
kgK | Q |=| W |
Tσ − T
Tσ = 0°C 200 + 273.15
= 666.9 = 1577.7 kJ
200 − 0
 Lost work
• Work that is wasted as the result of irreversibilities
in a process is called lost work: Wlost ≡ WS − Wideal
 1  
W S = ∆  H + u 2 + zg m  = Q
 2   fs
 1  
W ideal = ∆  H + u 2 + zg m  − Tσ ∆( Sm ) fs
 2   fs

W lost = Tσ ∆( Sm ) fs − Q

Surrounding temperature Tσ S = ∆( Sm ) − Q
G fs
Tσ
W lost = Tσ S G ≥ 0
Wlost = Tσ SG ≥ 0
The two basic types of steady-flow heat exchanger are characterized by their flow
patterns: cocurrent and countercurrent. Consider the two cases, for each of which
the following specifications apply:
TH 1 = 400 K TH 2 = 350 K TC1 = 300 K n H = 1 mol
s
The minimum temperature difference between the flowing streams is 10K. Assume
that both streams are ideal gases with CP = (7/2)R. Find the lost work for both
cases. Take Tσ = 300 K.

Fig 5.9
  1  
W S = ∆  H + u 2 + zg m  = Q n H (∆H ) H + n C (∆H ) C = 0
 2   fs

∆( Sn ) fs = n H (∆S ) H + n C (∆S ) C n H C P (TH 2 − TH 1 ) + n C C P (TC 2 − TC1 ) = 0

Negligible pressure change

 TH 2 n C TC 2 
∆( Sn) fs = nH C P  ln
  + ln  W lost = Tσ ∆( Sn ) fs − Q
 TH 1 n H TC1 

Case I, cocurrent: 7  350 340  J

∆( Sn ) fs = (1) (8.314) ln + 1.25 ln  = 0.667
n C 400 − 350 2  400 300  Ks
= = 1.25
n H 340 − 300 J
W lost = Tσ ∆( Sn ) fs = 300 × 0.667 = 200.1
s

Case II, countercurrent: 7  350 390  J

∆( Sn ) fs = (1) (8.314) ln + 0.5556 ln  = 0.356
2  400 300  Ks
n C 400 − 350
= = 0.5556  J
n H 390 − 300 W lost = Tσ ∆ ( S n
 ) fs = 300 × 0 .356 = 106 . 7
s
From thermodynamic point of view, the countercurrent case is much more efficient.
The third law of thermodynamics
• The absolute entropy is zero for all perfect
crystalline substances at absolute zero
temperature.
– When the form is noncrystalline, e.g., amorphous or
glassy, calculations show that the entropy of the more
random form is greater than that of the crystalline form.
– The absolute entropy of a gas at temperature T:
Tf (C P ) S ∆H f Tv (C ) ∆H v T (C P ) g
S=∫ dT + +∫ P l
dT + +∫ dT
0 T Tf T f T Tv Tv T