ME6101 Entropy

Entropy
Consequences of Second Law of Thermodynamics

Entropy
Dr. Md. Zahurul Haq If a system is taken through a cycle and produces work, it must be
exchanging heat with at least two reservoirs at 2 different
Professor temperatures.
Department of Mechanical Engineering
Bangladesh University of Engineering & Technology (BUET) If a system is taken through a cycle while exchanging heat with a
Dhaka-1000, Bangladesh
single reservoir, work must be zero or negative.
http://zahurul.buet.ac.bd/
Heat can never be converted continuously and completely into
work, but work can always be converted continuously and
completely into heat.
Work is a more valuable form of energy than heat.
For a cycle and single reservoir, Wnet ≤ 0.
ME 6101: Classical Thermodynamics
http://zahurul.buet.ac.bd/ME6101/
c Dr. Md. Zahurul Haq (BUET) Entropy ME6101 (2019) 1 / 32 c Dr. Md. Zahurul Haq (BUET) Entropy ME6101 (2019) 2 / 32
Entropy Entropy
Example: ⊲ Clausius Inequality: Steam Power Plant:

Clausius Inequity
Clausius Inequality
I
δQ
≤0
T
⇒ δWnet ≡ (δWrev +δWsys ) = δQR −dU

δQR TR
⇒ δQ = T
⇒ δWnet = TR δQ − dU T037
⇒ Wnet = TR δQ
HT
At 0.7 MPa T = T = 164.95 C
sat H
o
At 15 kPa T = T = 53.97 C
T
H
=⇒ δQ ≤ 0 as Wnet ≤ 0 sat L
o
Q = Q = h − h = 2.066 MJ/kg
T

H δQ = 0 reversible process H 12 2 1
T < 0 irreversible process QH = Q = h − h = −1.898 MJ/kg
L 34 4 3
δQ QH QL
T141
⇒ T = TH + TL = −1.086 kJ/kg ⊳
Entropy Entropy
Entropy (S): A Thermodynamic Property

Entropy is a property, hence change in
entropy between two end states is same
H
For reversible process: δQ for all processes, both reversible and
T =0
⇒ δq
H R2 δq
T = 1 T A+
R 1 δq
=0 1
2 T B irreversible.
If no irreversibilities occur within the
H R2 δq R1 δq

⇒ δq T = 1 T C + 2 T B =0
2 system boundaries of the system during
R2 δq R 2 δq the process, the system is internally

1 − 2 :⇛ 1 T = 1 T = ··· reversible.
A C T187
T038 R
Since δq/T is same for all reversible processes/paths between state 1
For an internally reversible process, the change in the entropy is due
& 2, this quantity is independent of path and is a function of end
solely for heat transfer. So, heat transfer across a boundary associated
states only. This property is called Entropy, S.
R2 with it the transfer of entropy as well.
ds ≡ δq T =⇒ ∆s = s2 − s1 = 1 δq T Z2
rev rev
δq
δqrev = Tds ≡ Entropy transfer (or flux)
1 T rev
Entropy Entropy
Moran Ex. 6.1: ⊲ Internally reversible heating in a piston-cylinder system.

Example: ⊲ Steam generation in Boiler.
s R2 δq R2
δq
2 − s1 = 1 T = 1
Tsat
rev
q12 h2 −h1 hfg
⇒ s2 − s1 = Tsat = Tsat = Tsat
⇒ hfg = sfg Tsat
q 23 =
R3
2
δq =
R3
2
Tds
T152
q12 = Tsat (s2 − s1 ) = area (1 − 2 − b − a) T169
q23
R3
= 2 Tds = area (2 − 3 − c − b) ⇒ w=
Rg
f Pdv = P(vg − vf ) = 101.325(1.673 − 0.001044) = 170 kJ/kg ⊳
qnet = q12 + q23 = area (1 − 2 − 3 − c − a) ⇒ q=
Rg
f Tds = T (sg − sf ) = Tsfg = 373.15 · 6.0486 = 2256.8 kJ/kg ⊳
Also note that, hfg = 2257 kJ/kg ⊳
Entropy Entropy
Carnot Cycle
δqrev = Tds
T154
T156
q23 = R23 Tds = TH R23 Tds = TH (s3 − s2) = TH ∆s

q41 = R41 Tds = TL R41 Tds = TL(s1 − s4) = −TC ∆s
wnet = qnet = q23 + q41 = (TH − TC )∆s
T153
1-2 : Isentropic compression.

2-3 : Isothermal heat addition and expansion. qin = q23
3-4 : Isentropic expansion. wnet (TH −TC )∆s TC
ηCarnot ≡ qin = TH ∆s =1− TH
4-1 : Isothermal heat rejection and compression.
Entropy Entropy
Entropy Change for Irreversible CM Process

For reversible H
process: δq
T =0
H δq R2 R1

δq δq
⇒ T = 1 T + 2 T =0 1
A B
For irreversible process:
H δq
T
<0
H δq R2 R1

T170
δq δq
⇒ T = 1 T C
+ 2 T B
<0 2
For irreversible process:
T041
1 − 2 :⇛ R2 δq
1 T >
R 2 δq
1 T Z2 Z2
Since path A is reversible, and since entropy is a property
A C
w12 6= Pdv : q12 6= Tds
1 1
Z2 Z2 Z2 Z2 Z2
δq δq So, the area underneath the path does not represent work and
= dsA = dsC =⇒ dsC >
1 T A 1 1 1 1 T C heat on the P − v and T − s diagrams, respectively.
Since path C is arbitrary, for irreversibleprocess In irreversible processes, the exact states through which a system
δq
R2 δq undergoes are not defined. So, irreversible processes are shown as
ds > T =⇒ s2 − s1 > 1 T irrev dashed lines and reversible processes as solid lines.
Entropy Entropy
Entropy Generation
Change in entropy of any CM system is due to only 2 physical
effects:
δQ δQ
dS ≧ T =⇒ δσ ≡ dS − T ≧0 1 Heat transfer to/from the system as measured by entropy
σ , Entropy produced (generated) by internal irreversibilities. transfer/flux, δQ/T .
2 Presence of irreversibilities within the system & its contribution is
 measured by entropy production, σ ≥ 0.
Only way to decrease the entropy of a closed system is to transfer

> 0 irreversible process

σ : = 0 internally reversible process

 of heat from it. In this case, heat transfer contribution must be
< 0 impossible process
T173 more -ve that the +ve contribution of any internal irreversibility/
For CM system: dSCM = δQT + δσ Reversible process: ds = δq/T & adiabatic process: δq = 0
CM system, with heat transfer occurring at several boundaries, if δq/T = 0 ⇒ s = constant: for reversible adiabatic process.
Ti is the temperature at point where δQi takes place, then All isentropic processes are not necessarily reversible & adiabatic.
dSCM P δQ_ i Entropy can remain constant during a process if heat removal
dt = T i + δσ
_
balances the contribution due to irreversibility.
Entropy Entropy
Moran Ex. 6.2: ⊲ Irreversible process of water.

Principle of Increase of Entropy
δq
ds ≧ T
Adiabatic or isolated system For control mass:

δw ⇒ dsCM ≧ δq
T.
Control Mass, For the surroundings at To , δq < 0,
temperature = T and reversible heat transfer:
T172
du + dKE + dPE = δq − δw ⇒ du = −δw δq −δq

⇒ dssurr = To .
h i
1 1
⇒ W
=−
Rg
du = −(ug − uf ) = −2087.56 kJ/kg ⊳ ⇒ dsnet = dssys + dssurr ≧ δq T − To
If T > To ⇒ δq < 0 ⇛ dsnet ≧ 0
m f Surroundings,
Note that, the work input by stirring is greater in magnitude than the temperature = To
work done by the water as it expands (170 kJ/kg). If T < To ⇒ δq > 0 ⇛ dsnet ≧ 0
δ(σ/m) = ds − δq
T = ds − 0 = ds
T171
dsnet ≧ 0
σ
⇒ m = sg − sf = 6.048 kJ/kg.K ⊳ Entropy change for an isolated system cannot be negative.
Entropy Entropy
Example: ⊲ Suppose that 1 kg of saturated water vapor at 100o C is to a

saturated liquid at 100o C in a constant-pressure process by heat transfer to
the surrounding air, which is at 25o C. What is the net increase in entropy of
the water plus surroundings?
∆snet = ∆ssys + ∆ssurr
∆s sys = −sfg = −6.048 kJ/kg.K
T188
∆s surr = q
To =
hfg
To = 2257
298 = 7.574 kJ/kg.K
T189
⇒ ∆snet = 1.533 kJ/kg.K⊳
Entropy change of an isolated A system and its surroundings form
system is the sum of the entropy So, increase in net entropy.
an isolated system.
changes of its components, and is
never less than zero. dsisolated > 0
Second-Law of Thermodynamics for CV Systems Second-Law of Thermodynamics for CV Systems
Second Law Analysis for CV System
T320 at t at t + ∆t
CM (time t) : region A + CV CM (t + ∆t) : CV + region B
SCM ,t = SA + SCV ,t SCM ,t +∆t = SB + SCV ,t +∆t

T042
SCM ,t +∆t −SCM ,t
∆t = SCV ,t +∆t
∆t
−SCV ,t
+ SB −SA
∆t :⇛ dSCM
dt =
dSCV
dt + m _ B sB − m _ A sA
dSCM
dt =
P Q_ i
Ti + σ
_
dSCV P Q_ i P P
dt = Ti + i (ms)
_ i − e (ms)
_ e + σ_ CV
T175
dSCV P Q_ j P P
dt = j Tj + (ms)
_ i − (ms)
_ e +σ
_ CV
For CM systems: mi = 0, me = 0 =⇒ dSdt = Pj QT + σ

_ _
CM
_
j
j
_
For steady-state steady-flow (SSSF) process: dSdv /dt = 0.

For 1-inlet & 1-outlet SSSF process: mi = me . _ _
P q_j σ_ CV
⇒ (se − si ) = j Tj + m_
For adiabatic 1-inlet & 1-outlet SSSF process:

σ_ CV
⇒ (se − si ) = m_
=⇒ se ≧ si
T757
(a) Energy balance (b) Entropy balance.

Moran Ex. 6-6 ⊲ Determine the rate at which entropy is produced within Principle of Increase of Entropy
the turbine per kg of steam flowing, in kJ/kgK.
SSSF: dSCV
dt = 0,
m
_ i = m_ e = m_
system dSCV
dt =
P Q_ i
Ti +
P
i (m
_ s)i −
P
e (ms)
_ e + σ_ CV
P Q_ i Q_
Ti = Tb : Tb = 350 K.
P
ṁe se
⇒ dSCV
=
P Q_ i
+
P
i (m
_ s)i −
P
e (ms)
_ e + σ_ CV
z =z
δQcv dt Ti

T P
ṁi si P Q_ i P P
i e dSsurr
= + i (ms)
_ − e (ms)
_ + σ_ surr
States 1 & 2 : defined.
surrunding dt Ti i e
T0 _ P P ✿0
T1082
⇒ dSsurr
dt = − QTCV
o
− i (ms)
_ e+ e (ms)
_ e +✘
σ_ surr
✘✘
T321

dECV V2i V2e
dSdt = dSdt
_ −W
=Q _
dt cv + m
_ i hi + 2 + gzi − m
_ e he + 2 + gze P Q_ i _
dSsurr Q CV
net CV
+ dt = Ti − To + σ_ tot
σtot ≥ 0, so
_
√
⇒ Q=
_
dSCV
dt =
P Q_ i
Ti + (m
_ s)i − (ms)
_ e +σ
_ CV
dSnet
dt = dSCV
dt + dSsurr
dt ≥0
√
⇒ σ_ CV =
Second-Law of Thermodynamics for CV Systems Entropy of a Pure Substance
Observations: Principle of Increase of Entropy Entropy of a Pure Substance
The increase-in-entropy principles are directional statements. A

decrease in entropy is not possible for closed, adiabatic systems or
for composite systems which interact among themselves.
The entropy function is a non-conserved property, and the
increase-in-entropy principles are non-conservation laws.
Irreversible effects create entropy. The greater the magnitude of
the irreversibilities, the greater the entropy change.
The second law states that a state of equilibrium is attained when
the entropy function reaches the maximum possible value,
consistent with the constraints on the systems.
T1080
T-s and h-s diagrams for steam.

Entropy of a Pure Substance Entropy of a Pure Substance
Entropy of Ideal Gas Isentropic Process: s = constant ⇒ ∆s = 0

First Law: δq − δw = du s2 − s1 = cP ln
Reversible process: δw = Pdv :

T2
+ R ln vv12
δq = Tds T1
Ideal gas: Pv = RT : du = cv dT : dh = cP dT
⇒ ln

T2

= − cRV
(k −1)
ln vv21 = −(k − 1) ln vv12 = ln vv12
T1
⇒ du = −Pdv + Tds ⇒ Tds = du + Pdv : 1st Tds Equation.
⇒ ds = cV dT P dT dv
T + T dv = cV T + R v : For ideal gas. T2
(k −1)
v1
RT =⇒ T1 = (ideal gas, s1 = s2 , constant k )
v2
v2
=⇒ s(T2 , v2 ) − s(T1 , v1 ) = T12 cV dT + R ln
T v1

T2 P2
s2 − s1 = cP ln T1
− R ln P 1
=⇒ s2 − s1 = cV ln T 2 v2
T1 + R ln v1 : Ideal gas with cV = constant. (k −1)
T2 R P2 (k −1) P2 P2 k
⇒ h = u + Pv ⇒ dh = du + Pdv + vdP = δqrev + vdP = Tds + vdP ⇒ ln T1 = cP ln P1 = k ln P1 = ln P1
⇒ dh = Tds + vdP ⇒ Tds = dh − vdP : 2nd Tds Equation. (k −1)
T2 P2 k
RT
P2 =⇒ = (ideal gas, s1 = s2 , constant k )
=⇒ s(T2 , P2 ) − s(T1 , P1 ) = T12 cP dT
T − R ln P1
T1 P1
=⇒ Pv k = constant (ideal gas, s1 = s2 , constant k )

=⇒ s2 − s1 = cP ln T P2
T1 − R ln P1 : Ideal gas with cP = constant.
2
Cengel Ex. 7.2: ⊲ Air is compressed in a car engine from 22o C and 95 kPa
in a reversible and adiabatic manner. If the compression ratio, rc = V1 /V2 of
this engine is 8, determine the final temperature of the air.
T1081
T190
Polytropic processes on P-v and T-s diagrams
(k −1) (k −1)
T2 v1 v1
= ⇒ T2 = T1 = 295(8)1.4−1 = 677.7 K ⊳
T1 v2 v2
Example: ⊲ Air is contained in one half of an insulated tank. The other side
is completely evacuated. The membrane is punctured and air quickly fills the
entire volume. Calculate the specific entropy change of the isolated system.
Example: ⊲ Determine the change in specific entropy, in KJ/kg-K, of air as
an ideal gas undergoing a process from 300 K, 1 bar to 400 K, 5 bar. Because
of the relatively small temperature range, we assume a constant value of cP =
1.008 KJ/kg-K.
T2 P2
∆s = cP ln − R ln T022
T1 P
=

1.008
kJ
1
ln
400K

−
8.314 kJ

ln
5bar

du = δq − δw
kg.K 300K 28.97 kg.K 1bar
s − s = c ln

T2 v2
2 1 v T1 + R ln v1
= −0.1719 kJ/kg.K ⊳
⇒ w = 0, q = 0 ⇒ du = 0 ⇒ cV dT = 0 ⇒ T2 = T1 .
Note that, for isentropic compression, T2s = T1 (P2 /P1 )(k −1)/k = 475 K.
Hence, entropy change is (-) ve because of cooling of air from 475 K to 400 K. ⇒ s2 − s1 = cv ln T
T1
2
+ R ln v2
v1 = 0 + 287 ln(2) = 198.93 kJ/kg.K ⊳

δq
Note that: s2 − s1 = 198.93 kJ/kg.K > =⇒ ∆s > 0
T
| {z }
0

ME6101 Entropy

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Entropy

Consequences of Second Law of Thermodynamics

Example: ⊲ Clausius Inequality: Steam Power Plant:

⇒ δWnet ≡ (δWrev +δWsys ) = δQR −dU

Entropy (S): A Thermodynamic Property

 R2  δq  R 2  δq  the process, the system is internally

Moran Ex. 6.1: ⊲ Internally reversible heating in a piston-cylinder system.

⇒ hfg = sfg Tsat

q12 = Tsat (s2 − s1 ) = area (1 − 2 − b − a) T169

 q23 = R23 Tds = TH R23 Tds = TH (s3 − s2) = TH ∆s

1-2 : Isentropic compression.

Entropy Change for Irreversible CM Process

Moran Ex. 6.2: ⊲ Irreversible process of water.

Adiabatic or isolated system  For control mass:

 du + dKE + dPE = δq − δw ⇒ du = −δw δq −δq

Example: ⊲ Suppose that 1 kg of saturated water vapor at 100o C is to a

∆snet = ∆ssys + ∆ssurr

 ∆s sys = −sfg = −6.048 kJ/kg.K

Second-Law of Thermodynamics for CV Systems Second-Law of Thermodynamics for CV Systems

Second Law Analysis for CV System

 For CM systems: mi = 0, me = 0 =⇒ dSdt = Pj QT + σ

 For steady-state steady-flow (SSSF) process: dSdv /dt = 0.

 For adiabatic 1-inlet & 1-outlet SSSF process:

(a) Energy balance (b) Entropy balance.

Second-Law of Thermodynamics for CV Systems Second-Law of Thermodynamics for CV Systems

Observations: Principle of Increase of Entropy Entropy of a Pure Substance

 The increase-in-entropy principles are directional statements. A

T-s and h-s diagrams for steam.

Entropy of a Pure Substance Entropy of a Pure Substance

Entropy of Ideal Gas Isentropic Process: s = constant ⇒ ∆s = 0

    =⇒ Pv k = constant (ideal gas, s1 = s2 , constant k )

Entropy of a Pure Substance Entropy of a Pure Substance

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R2 δq R 2 δq the process, the system is internally

q12 = Tsat (s2 − s1 ) = area (1 − 2 − b − a) T169

q23 = R23 Tds = TH R23 Tds = TH (s3 − s2) = TH ∆s

Adiabatic or isolated system For control mass:

du + dKE + dPE = δq − δw ⇒ du = −δw δq −δq

∆s sys = −sfg = −6.048 kJ/kg.K

For CM systems: mi = 0, me = 0 =⇒ dSdt = Pj QT + σ

For steady-state steady-flow (SSSF) process: dSdv /dt = 0.

For adiabatic 1-inlet & 1-outlet SSSF process:

The increase-in-entropy principles are directional statements. A

=⇒ Pv k = constant (ideal gas, s1 = s2 , constant k )