Irreversibility and exergy (availability)

Subhransu Roy
April 19, 2020

1 Exergy
Exergy is the maximum useful work from a system during a thermodynamic process. An
irreversible real thermodynamic system that exchanges work Ẇcv and heat Q̇0 with the
surrounding at temperature T0 is shown in figure 1. The 1st and 2nd law of thermody-
namics applied to such a system is given below.
d 1 1 1
 
mcv (u + v 2 + gz)cv = Q̇0 + Q̇j − Ẇcv + ṁi (hi + Vi2 + gzi ) − ṁe (he + Ve2 + gze )
dt 2 2 2
d Q̇0 Q̇j
Ṡcv = [mcv scv ] = ṁi si − ṁe se + + + (Ṡgen )cv
dt T0 Tj
Q̇0
Ṡsurr = − − (ṁi si − ṁe se )
T0
1 1
Ẇcv ṁi (hi + Vi2 + gzi ) − ṁe (he + Ve2 + gze ) − T0 (ṁi si − ṁe se )
2 2
d 1 2 d
 
− mcv (u + V + gz)cv + T0 [mcv scv ]
dt 2 dt
Q̇j
+Q̇j − T0 − T0 (Ṡgen )cv where Ṡgen ≥ 0
Tj
1 1
Ẇcv = ṁi (hi − T0 si + Vi2 + gzi ) − ṁe (he − T0 se + Ve2 + gze )
2 2
!
d 1 T0
 
− mcv (u − T0 s + V 2 + gz)cv + 1 − Q̇j − T0 (Ṡgen )cv
dt 2 Tj

The equivalent thermodynamic system undergoing same change of state in a reversible

manner is shown in figure 2. This requires work exchange Ẇrev and the heat exchange
Q̇rev
0 with the surrounding at temperature T0 . The 1st and 2nd law of thermodynamics

1
 Environment (p0 , T0 )

Tj _ cv
W T0 control volume
boundary
Q_ j Q_ cv

Tj

_ i (hi + 12 vi2 + gzi )

m d _ o (ho + 21 vo2 + gzo )
m
[mcv (u + 12 v 2 + gz)cv ]
dt
_ i si
m d _ o so
m
[mcv scv ]
dt

S_ gen

Figure 1: irreversible (real) thermodynamic system

Tj _ rev
W T0
Environment (p0 , T0 )
Q_ rev
Q_ j 0

_c
W Reversible control volume
Heat Engine boundary
_ rev
W Q_ rev
cv cv

Tj

_ i (hi + 21 vi2 + gzi )

m d _ o (ho + 21 vo2 + gzo )
m
[mcv (u + 12 v 2 + gz)cv ]
dt
_ i si
m d _ o so
m
[mcv scv ]
dt

Figure 2: reversible (ideal) thermodynamic system

2
applied to such a reversible system is given below.
d 1 1 1
 
mcv (u + v 2 + gz)cv = Q̇rev 0 + Q̇j − Ẇ
rev
+ ṁi (hi + Vi2 + gzi ) − ṁe (he + Ve2 + gze )
dt 2 2 2
rev
d Q̇ Q̇j
[mcv scv ] = ṁi si − ṁe se + 0 +
dt T0 Tj
1 1
Ẇ rev = ṁi (hi + Vi2 + gzi ) − ṁe (he + Ve2 + gze ) − T0 (ṁi si − ṁe se )
2 2
d 1 2 d
 
− mcv (u + V + gz)cv + T0 [mcv scv ]
dt 2 dt
Q̇j
+Q̇j − T0
Tj
1 1
Ẇ rev = ṁi (hi − T0 si + Vi2 + gzi ) − ṁe (he − T0 se + Ve2 + gze )
2 2
!
d 1 2 T0
 
− mcv (u − T0 s + V + gz)cv + 1 − Q̇j
dt 2 Tj
I˙ = Ẇ rev − Ẇcv = T0 (Ṡgen )cv
Q̇j
= T0 (Ṡcv + Ṡsurr − )
Tj
Ẇ rev − Ẇcv = Q̇rev
0 − Q̇0

The useful work for a flexible control volume having volume Vcv is given below.

dVcv
Ẇusef ul = Ẇcv − Ẇsurr = Ẇcv − p0
dt
rev rev dVcv
Ẇusef ul = Ẇ − p0
dt
rev 1 2 1 2
Ẇusef ul = ṁi (hi − T0 si + Vi + gzi ) − ṁe (he − T0 se + Ve + gze )
2 2 !
d 1 2 T0
 
− mcv (u − T0 s + p0 v + V + gz)cv + 1 − Q̇j
dt 2 Tj

The concept of exergy is used to calculate the reversible work output.

1
 
non-flow exergy φ = u − T0 s + p0 v + V 2 + gz − (u0 − T0 s0 + p0 v0 )
2 | {z }
dead state
1
 
flow exergy ψ = h − T0 s + V 2 + gz − (h0 − T0 s0 )
2 | {z }
dead state

!
rev d T0
Ẇusef ul = ṁi ψi − ṁe ψe − [mcv φcv ] + 1 − Q̇j
|dt {z Tj
| {z }
flow exergy
} | {z }
non-flow exergy heat exergy
!
d T0
Ẇusef ul = ṁi ψi − ṁe ψe − [mcv φcv ] + 1 − Q̇j − T0 Ṡgen
|dt {z Tj
| {z } | {z }
flow exergy
} | {z } exergy destroyed
non-flow exergy heat exergy
3
 Figure 3: Variation of G with T at constant P

Concept of exergy balance is as follows

" ! #
d T0 h i
[mcv φcv ] = ṁi ψi + 1 − Q̇j − ṁe ψe + Ẇusef ul − T0 Ṡgen
|dt {z } Tj | {z } | {z }
| {z } exergy out exergy destroyed
system exergy increase exergy in
" ! #
d T0 h
rev
i
[mcv φcv ] = ṁi ψi + 1 − Q̇j − ṁe ψe + Ẇusef ul
|dt {z } Tj | {z }
system exergy increase
| {z } exergy out
exergy in

2 Gibbs free energy

For a system maintained at p and T undergoing a spontaneous process

dU = δQ − pdV
δQ
dS = + δSgen
T
dU = T dS − T δSgen − pdV
dU + pdV − T dS = −T δSgen where δSgen ≥ 0
Therfore, dH − T dS ≤ 0
dG ≤ 0

Let us look at the value of G when liquid water evaporates i.e., find ∆Gf g at a constant
Psat and Tsat as shown below

Gg − Gf = ∆Gf g
= ∆Hf g − Tg ∆Sf g = 0

So, we see that during phase change ∆G=0. The figure 3 shows that at constant pressure
P if the temperature T is varied then the phase that has the minimum value of G at the
particular temperature is the equillibrium phase.