Lecture note for general thermodynamics, 2003

Chapter 10 Irreversibility and availability

• potential for providing USEFUL work from some energy sources

reversible – real work = irreversibility i

lost-work = ToSgen

T Carnot T Isobaric process

T T
Available
energy Available
To To
unavailable unavailable
S S
⎛ T ⎞ ⎛δQ ⎞ Q
WrevH . E . = Q − Qo = Q ⎜ 1 − o ⎟ ∆S = ∫ ⎜ ⎟ = o
⎝ T⎠ ⎝ T ⎠ rev To
WrevH . E . = Q − To ∆S

•Definitions

•Availability (exergy): maximum reversible work without the additional heat

transfers
•Irreversibility = reversible work – actual work

• Descriptions of reversible work and irreversibility (three processes)

A. STEADY PROCESS(power plants or refrigerators), no KE and PE

TH
q q = ( he − hi ) + w (1st law)
inlet cv exit From 2nd law, irreversible process such
w that
1 dS q
= ( se − si ) − = s gen > 0
 dt
m TH
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Title
 Lecture note for general thermodynamics, 2003

1 dS q qorev
= ( se − si ) − − =0
 dt
m TH To TH
To
qorev = To ( se − si ) − q q
TH
inlet cv exit
w rev
=q+q rev
o − ( he − hi )
qrev
⎛ T ⎞
w rev = To ( se − si ) − ( he − hi ) + q ⎜ 1 − o ⎟ T0
wrev
⎝ TH ⎠

• irreversibility i
Comments
i=w rev
−w 1. without k.E.and P.E.
To 2. for nozzles and diffusers, these terms should be
= To ( se − si ) − q
TH involved
⎡ q ⎤
3. for these cases, total enthalpy should be used
= To ⎢( se − si ) − ⎥
⎣ TH ⎦
⎡ 1 dS net / real ⎤
= To ⎢ = To s gen
⎣m dt ⎥⎦
c.m.
1Q2 1W2
B. Control mass process TH U2-U1
S2-S1
•No k.E.and P.E. changes assumed
•1st law of thermodynamics

1 Q2 = U 2 − U 1 + 1 W2
Q2
∆S net / real = ∆Scm + ∆S surr = ( S 2 − S1 ) − 1
=1 S2, gen > 0
TH
TO
•Any necessary heat engines and pumps QOrev
Q2 QOrev
∆Snet / real = ( S2 − S1 ) − 1
− =0 c.m.
TH TO 1Q2 1W2
TO
TH U2-U1
QOrev = TO ( S2 − S1 ) −1 Q2 S2-S1
TH
1 W2rev =1 Q2 + QOrev − (U 2 − U 1 ) 1 I 2 =1 W2rev −1 W2
TO
= TO ( S2 − S1 ) −1 Q2
TO
+ 1 Q2 − (U 2 − U 1 ) = TO ( S2 − S1 ) −1 Q2
TH TH
⎛ T ⎞ ⎡ T ⎤
= TO ( S2 − S1 ) − (U 2 − U 1 ) + 1 Q2 ⎜ 1 − O ⎟ = TO ⎢( S2 − S1 ) − O ⎥ = TO 1 S 2, gen
⎝ TH ⎠ ⎣ TH ⎦

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Title
 Lecture note for general thermodynamics, 2003

C. Transient process

. v = TO ( m 2 s2 − m1 s1 ) − ( m 2 u2 − m1 u1 ) + TO ( me se − m i si )
Wcrev
⎛ T ⎞
− ( me he − mi hi ) + Q cv ⎜ 1 − O ⎟
⎝ TH ⎠
⎛ T ⎞
= mi ( hi − TO si ) − me ( he − TO se ) + m1 ( u1 − TO s1 ) − m2 ( u2 − TO s2 ) + Q cv ⎜ 1 − O ⎟
⎝ TH ⎠
T
= mi hi − miTO si − me he + meTO se + m1u1 − m2 u2 − m1TO s1 + m2TO s2 + Q cv − Q cv O
TH

Wc .v = Q cv + ( m1u1 − m2 u2 ) + ( mi hi − me he )

I cv = Wcrev
. v − Wcv

⎡ Q ⎤
= TO ⎢( m2 s2 − m1 s1 ) + ( me se − mi si ) − cv ⎥ = T0 S gen
⎣ TH ⎦

•AVAILABILITY and 2nd Law Efficiency

•What is the maximum reversible work that can be done by a given mass in a
given state ?

•Availability (exergy): maximum reversible work without the additional heat

transfers
•Irreversibility = reversible work – actual work
•Equilibrium
•pressure and temperature equilibrium with the surroundings
•chemical equilibrium implying no further chemical reactions
•Zero velocities and minimum P.E.

•A. STEADY PROCESS (control volume analysis)

⎛ T ⎞
w rev = To ( se − si ) − ( hTOTe − hTOTi ) + q ⎜ 1 − o ⎟
⎝ TH ⎠
⎛ T ⎞ Contribution to the net reversible work
= ( hTOTi − To si ) − ( hTOTe − To se ) + q ⎜ 1 − o ⎟ from the heat transfers
⎝ TH ⎠

For steady state, flow reversible work will be maximum when the mass leaving the c.v. is
in equilibrium
h = ho , s = so ,Ve = 0, Z e = Z o

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 Lecture note for general thermodynamics, 2003

•Flow availability (EXERGY)

•Maximum reversible work per unit mass flow without the additional heat
transfers

⎛ 1 ⎞
ψ = ⎜ h − TO s + V 2 + gZ ⎟ − ( ho − TO so + gZ o )
⎝ 2 ⎠
TH
•For steady state,
q
⎛ T ⎞ inlet cv exit
w rev = ψ i − ψ e + q ⎜ 1 − o ⎟
⎝ TH ⎠
qrev
wrev
T0
•Irreversibility

•Difference between the reversible work and the actual work

⎛ T ⎞
Icv = ( ∑ m
 iψ i − ∑ m eψ e ) − ∑ ⎜ 1 − o ⎟Q cv , j − W cv = Φ
 cv − W cv
⎜ T ⎟
⎝ j ⎠

•1st term : decrease in the availability of the mass flows

•2nd term : decrease of availability of each heat transfer rate j at reservoir Tj
•3rd term : increase in availability of the surroundings that receive the actual work
•Rate of irreversibility means the destruction rate of availability – proportional to
the net rate of entropy increase

•B. CONTROL MASS ANALYSIS (non-flow analysis)

•Volume may change, and some work is exchanged with the ambient

⎛ T ⎞
W2rev = TO ( S 2 − S1 ) − (U 2 − U 1 ) + 1 Q2 ⎜ 1 − O ⎟
1
⎝ TH ⎠
⎛ T ⎞
∴1 w2rev = ( e1 − TO s1 ) − ( e2 − TO s2 ) + 1 q2 ⎜ 1 − O ⎟
⎝ TH ⎠
•Maximum if the final state is in equilibrium with the surroundings

e2 = eo = u∂ + gZ o
w surr = Po ( vo − v1 ) = − Po ( v1 − vo )

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 Lecture note for general thermodynamics, 2003

•Maximum available work

max
wavail = wrev
max
− w surr
⎛ T ⎞
= ( e − TO s ) − ( eo − TO so ) + Po (v − vo ) + 1 q2 ⎜ 1 − O ⎟
⎝ TH ⎠
•Nonflow availability φ: maximum available work from as a state without the heat
transfers

φ = ( e − To s ) − ( eo − To so ) + Po (v − vo )
= ( e + Po v − To s ) − ( eo + Po vo − To so )

•Irreversibility I: maximum available work from as a state without the heat transfers

⎛ To ⎞
I
1 2 = m (φ1 − φ 2 ) + (
∑ ⎜⎜ 1 − T ⎟⎟ Q j − 1W2act − ( PoV2 − V1 ) )
⎝ j ⎠

Decrease in availability of the Availability increase of the

control mass surroundings that received the
Decrease in availability of the
actual work
heat transfers at reservoirs Tj

NET DESTRUCTION OF AVAILABILITY OF THE CONTROL MASS AND

SURROUNDINGS : proportional to the net increase of entropy

if c.m receives the work – increase of availability

for the work done by the c.m – decrease of availability
other irreversible factors that decrease availablity
- heat transfer (combustion or frictions etc.)
- expansion work e.g. turbine shaft work

NOTES
•The less the irreversibility associated with a given change of state,
state, the greater the
amount of work will be done (the smaller the amount of work will be required)
•Availability is one of our natural sources – for effective use of these
•From an economic point of view, exergy analysis can be applied to the optimum
design of a variety of engineering systems

Here defines the second-

second-law efficiency ---- > NEXT TALK

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 Lecture note for general thermodynamics, 2003

•Second Law Efficiency

•Comparisons of the desired output of a process with the cost, or input, in terms of
the thermodynamics availability
•As previously, for example, the turbine efficiency is defined as

η turb = wa / w s

•This compares two energy quantities -> first law efficiency

•BUT, here actual work is divided by the decrease in availability from
the same inlet state ot the same exit state

η 2 nd = wa / (ψ i − ψ e )

•For compressor or pump η 2 nd = (ψ i − ψ e ) / wa ,input

•For devices without involving the production or the input of workd

4 3
η 2 nd = m 1 (ψ 2 − ψ 1 ) / m 3 (ψ 3 − ψ 4 ) hot
W cv = Φ  cv − TS gen
 cv − Icv = Φ cold
1 2
Total rate of availability
supplied from all sources
 source − Icv
Φ
e.g. flows, heat transfers, and  wanted / Φ
η 2 nd = Φ  source =
work inputs Φ source

•EXERGY BALANCE EQUATION

• flow availability / non-flow availability
• these forms are consistent with one another
• unified formulation for a general control volume Φ = mφ
Φ = mφ = m ( e − eo ) + Po m ( v − vo ) − To m ( s − so )

“o” indicates dead state : ambient state with zero k.E.

k.E.

d Φ dme dm dV dm dms dm
= − eo + Po − Po vo − To + To so
dt dt dt dt dt dt dt
dme dV dms dm
= + Po − To − ( ho − To so )
dt dt dt dt

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 Lecture note for general thermodynamics, 2003

•From continuity equation

dm
= ∑m
 i − ∑m
e
dt

•From energy equation and 2nd law

dE dme
= = ∑ Q cv − ∑ W cv + ∑ m  i hTOTi − ∑ m
 e hTOTe
dt dt
dS dms Q
= = ∑ m i si − ∑ m
 e se + ∑ cv + S gen
dt dt T

• Above three equations are substituted into exergy equation

dΦ dV
= ∑ Q cv − ∑ W cv + ∑ m i hTOTi − ∑ m e hTOTe + Po
dt dt
Q
−To ∑ m
 i si + To ∑ m e se − ∑ To cv − To S gen − ( ho − To so ) ⎡⎣ ∑ m i − ∑ m e ⎤⎦
T

dΦ
dt
⎛ T ⎞
= ∑ ⎜ 1 − o ⎟ Q cv Transfer by heat at T
⎝ T⎠
dV
− ∑ W cv + Po Transfer by shaft/boundary work
dt
+ ∑ m iψ i − ∑ m eψ e Transfer by flow
−To S gen Exergy destruction

where

ψ i = hTOTi − ho − To ( si − so )
ψ e = hTOTe − ho − To ( se − so )

RATE OF EXERGY STORAGE = Transfer by heat + Transfer by shaft/boundary

shaft/boundary work +
Transfer by flow – Exergy destruction(due to entropy generation, irreversibility)

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 Lecture note for general thermodynamics, 2003

•CASE STUDY 1: steady state control volume with a single flow

Steady state : no storage of mass, energy, entropy, and exergy

with constant volume

⎛ T ⎞
0 = ∑ ⎜ 1 − o ⎟ Q cv − W cv + 0 + m  eψ e − To S gen
 iψ i − m
⎝ T⎠
⎛ T ⎞
W cv = ∑ ⎜ 1 − o ⎟ Q cv + m iψ i − m eψ e − To S gen
⎝ T⎠
⎛ T ⎞
w = ∑ ⎜ 1 − o ⎟ qcv + ψ i − ψ e − To s gen
⎝ T⎠

ψ i − ψ e = hTOTi − ho − To ( si − so ) − ⎡⎣ hTOTe − ho − To ( se − so ) ⎤⎦
= hTOTi − hTOTe − To ( si − se )

⎛ T ⎞
w = ∑ ⎜ 1 − o ⎟ qcv + hTOTi − hTOTe − To ( si − se ) − To s gen = w rev − To s gen
⎝ T⎠

Single heat transfer term and no entropy generation

•CASE STUDY 2: no flow steady-state c.v. of heat engine, heat pump, electric
heating element, or refirgerator – no storage and work
-> the work equals the Carnot heat engine work reduced by the exergy
destruction of any irreversible process occurring inside the control volume

⎛ T ⎞
W cv = ∑ ⎜ 1 − o ⎟ Q cv + m iψ i − m eψ e − To S gen
⎝ T⎠
⎛ T ⎞
W cv = ∑ ⎜ 1 − o ⎟ Q cv − To S gen
⎝ T⎠
•CASE STUDY 3: a control mass going through a process (1 – 2)
dΦ ⎛ To ⎞   + P dV − T S
∑
∫ dt ∫ ⎝ T ⎠
= ⎜ 1 − ⎟ Qcv − ∑ W cv o
dt
o gen

⎛ T ⎞
2
Φ 2 − Φ 1 = ∫ ∑ ⎜ 1 − o ⎟ Q cv dt −1 W2 + Po (V2 − V1 ) − To1 S 2, gen
1 ⎝ T⎠
= m (e2 − e1 ) + Po (V2 − V1 ) − To m ( s2 − s1 )
⎛ T ⎞
1 W2 − Po (V2 − V1 ) = ⎜ 1 − o ⎟ 1Q 2 − ( Φ 2 − Φ 1 ) To1 S2, gen
⎝ TH ⎠
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