Exergy Analysis: Process Engineering Thermodynamics

Process Engineering Thermodynamics
course # 424304.0 v. 2015
Exergy Analysis
Commented / edited by
Ron Zevenhoven Prof. Özer Arnas,
visiting ÅA VST May/June 2014
from the US Military Academy
Åbo Akademi University
Thermal and Flow Engineering Laboratory / Värme- och strömningsteknik
tel. 3223 ; ron.zevenhoven@abo.fi
course material: http://users.abo.fi/rzevenho/kursRZ.html
ÅA 424304
1.1 Exergy vs. Energy
Åbo Akademi Univ - Thermal and Flow Engineering, Piispankatu 8, 20500 Turku 11 jan 15 2/102
Energy Conversion /1
 In a hydraulic power
plant, the potential
energy difference can
be completely
converted into work
 For a thermal plant
Carnot (C1824)
discovered that only
a portion of heat Q
at temperature T1
can be converted
Pic: S05
into work, with cold T  T  T 
W  Q   Q     
sink temperature T2 : T  T 
11 jan 15 Åbo Akademi Univ - Thermal and Flow Engineering, Piispankatu 8, 20500 Turku 3/102
Energy Conversion /2
 The preferable way
to convert heat Q at
T1 into work is to
use a natural,
unlimited cold sink,
such as the natural
environment at
temperature T0.
 With T2 > T0 no full

use of Q is made; Pic: S05
for T2 < T0 a cooling T  T  T 
Wmax  Q   Q     
effort is needed. T  T 
Exergy /1
 EXERGY quantifies how much of a certain
amount of energy contained in an energy
source can be extracted as useful work.
Picture:http://cpcclibraries.files.wordpress.com/2008/04/earth.jpg
 The potential of (natural) energy resources for driving a
mechanical, thermal, chemical or biological process depends
on the deviation from thermodynamic equilibrium with the
surrounding environment.
 This allows evaluation of the ability to
perform maximum work under certain
environmental conditions.
 This involves quality assessments,
for example for heat Q its temperature
T, relating it to temperature T0 of the
surrounding environment.
Picture: http://upload.wikimedia.org/wikipedia/commons/thumb/b/b1/Dead_possum.jpg/800px-Dead_possum.jpg
Exergy /2
 Note that work is a path function:
W = ƒ(initial state, path, final state)
 For maximising the work output:
– The process should be reversible
– The end of the process should be at a dead state which
is in equilbrium with the surrounding environment:
temperature T0 and pressure p0 as the environment; no
kinetic or potential energy relative to the environment;
no chemical reactivity with the environment.
(And no electrical, magnetic etc. effects.)
 This requires a description of the state and, if
chemistry is involved, the composition of the local
environment for the prevailing chemical species.
Exergy /3
 While the quantities of energy allow for ”bookkeeping”
with the help of the First Law of Thermodynamics (”energy
cannot be produced or destroyed”); the exergy concept
follows from the Second Law of Thermodynamics, which
involves the quality of energy and its degradation during
energy conversion.
 A few useful definitions: Exergy expresses the maximum work output
attainable in the natural environment, or the minimum work input necessary to
realise the reverse process (Rant, 1956);
Exergy expresses the amount of mechanical work necessary to produce a
material in its specified state from components in the natural environment, in a
reversible way, heat being exchanged only with the environment (Rickert, 1974)
 During the 1940s, the term ”availability” had been introduced for
a similar purpose (Keenan, 1941, K41) – see p. 9
Surroundings - Environment
 Some care should be considered with respect to ”the
surroundings”, which is everything outside the system’s
boundaries. Part of the surroundings, referred to as the
”immediate surroundings” are affected by the process,
the ”environment” refers to the region beyond that.
 ”Normal conditions” for the reference environment:
T° = 298.15 K, p°= 101.325 kPa, relative humidity 70%,
atmospheric CO2 concentration 330 - 380 ppm, sea water
salinity 3.5 %-wt, etc. etc. etc.
 Some data for air: N2 = 75.78 kPa; O2 = 20.39 kPa, Ar = 906
Pa, CO2 = 33.5 Pa , H2O = 2200 Pa, He = 1.77 Pa, and Ne,
D2O, Kr, Xe < 1 Pa (SAKS04)
39.7 Pa would be better – see co2now.org
Notation For Exergy
 In the literature, symbols like Ex, or X for exergy, or ex
or x for specific exergy (i.e. exergy per mass, Ex/m = X/m =
ex = x) are most common; but
 Also the symbols B and b are used, especially in (and by
followers of) the very important work by Szargut et al.
 And, in some (U.S.) literature,
availability, B, is defined as
BAV = H - T°·S, which can be
related to exergy by
Ex = BAV (T, p) – BAV (T°, p°),
where BAV (T°,p°) = (H - T°·S)T°, p°
= GT°,p° which ≠ 0 necessarily (depends on UT°,p° in HT°,p° )
Ex (T,p) = (H - T°·S)T,p - (H - T°·S)T°,p° (SAKS04)
ÅA 424304
1.2 Reversible Work-Irreversibility
Exergy and Work Potential
 Thus: a system will deliver the maximum possible work in a
reversible process from a specified initial state to the state
of its environment, i.e. the dead state.
 This useful work potential is called exergy. It is also the
upper limit of work from a device without violating the Laws
of Thermodynamics. The part of the energy that cannot be
converted into work is called unavailable energy or anergy:
energy = exergy + anergy
 Since exergy depends on the surrounding environment, it is
not a state variable like U, H, S, V, p, G.
 In some special cases a changing environment can be
considered, for example when analysing air flight, or large
seasonal or daily changes (day/night).
 Unlike energy, exergy is consumed or destroyed.
2
Surroundings Work
 During the expansion of a work W producing closed system,
with volume change ΔV = Vfinal – Vstart > 0, work Ws is done
on the surroundings at pressure p°:
Ws = p°·ΔV Note: here W > 0 defined
as work done by the system
 Similarly, ΔV < 0 is possible. In many cases this surroundings

work cannot be recovered, reducing the useful work Wu of
the process:
Wu = W - Ws = W - p°·ΔV
 This has no significance for 1) cyclic processes and 2)

systems with fixed boundaries, but is important for
constant pressure processes with large volume changes
(for example: combustion furnaces, engines)
Reversible Work
 Reversible work Wrev is the maximum amount of work that
can be obtained from a process; it is equal to exergy if the
final state is the dead state (which usually is not so!)
 The difference between Wrev and Wu
is referred to as the irreversibibility:
I = Wrev - Wu
which is equal to the amount of
exergy that is destroyed.
 The irreversibility represents ”lost
opportunity” to do work.
 If I = 0, no entropy is generated.
 For work consuming devices, Wrev ≤ Wu
Pic: ÇB98
Example: Irreversibility 1/1

 A heat engine (HE) receives Qin = 500
kW heat at TH = 1200 K and rejects
waste heat at TL = 300 K. The power
output of the engine is 180 kW.
Calculate the reversible power Wrev
and irreversibility rate I, in kW.
 Wrev follows from the Carnot efficiency

ηcarnot = 1-TL/TH = 0.75
 Wrev = ηcarnot · Qin = 375 kW.
 The actual power output Wu = 180 kW,
thus I = Wrev - Wu = 195 kW
 Note that the 500 kW - 375 kW = 125 kW Pic: ÇB98

rejected to the sink was not available for work
 The 125 kW rejected to
the sink follows from 
Q 500 kW
Carnot efficiency; this is 
T in 1200 K
the anergy part of the
 417 J/(K  s)
input energy:
energy = anergy + exergy
500 kW = 125 kW + 375 kW

Q 125 kW

T out 300 K
 The entropy part of the
 417 J/(K  s)
energy cannot be
converted into useful
work.
Pic: ÇB98
11 jan 15 Åbo Akademi Univ - Thermal and Flow Engineering, Piispankatu 8, 20500 15/102
Turku

 A block of iron (m = 500 kg) is cooled
from TH = T1 = 200°C to TL = 27°C by
transferring heat to the surrounding air
(T0 = 27°C). Calculate reversible work
Wrev and irreversibility I, in kJ
 The maximum work equals (assuming a
series of reversible heat engines):
TL T
δWrev  ηc  δQin  (  )  δQin  (   )  δQin
TH T
where δQin   m  c avg  dT which gives
T
 T
Wrev   δWrev  m  c avg   (T  T )  T  ln    8191 kJ
T   T 
Pic: ÇB98
 Here, cavg is an average value for the
specific heat of iron, ~ 450 J/(kg·K)
 In the result, the first part (m·cavg·ΔT) is
the heat transferred from the iron
block which equals 38925 kJ.
 The 8191 kJ calculated as Wrev could have
been converted into useful work
 Since no work was obtained, Wu = 0 and
the irreversibility therefore equals
I = Wrev = 8191 kJ (21% of Qin) .
 The remaining 38925 - 8191 = 30734 kJ
(79% of Qin) is rejected also to the surroundings.
Pic: ÇB98
Irreversiblities and Exergy Loss

 Typical examples of irreversibilities that result in exergy
destruction, or exergy losses:
– Friction, including friction in fluid flows
which results in pressure drop
– Mixing (which increases entropy)
– Chemical reactions
– Heat transfer, especially through Rule of thumb:
large temperature differences irreversible processes are
– Unrestrained expansion; throttling processes that look absurd
when run backwards
– Fast compression
– Electric resistance
– Adiabatic processes are often more reversible
 Note that fast processes can be more reversible than slow
processes; for example discharging a battery
 Slower does not automatically mean more reversible !
Second-Law Efficiency, η2, Revisited
 Second-law efficiency is defined as:
actual thermal efficiency η
η  
maximum possible thermal efficiency ηcarnot
 Equally, it can be defined as (for work producing devices):

useful work W I
η   u 
maximum possible useful work Wrev Wrev
for work done (for work -power- consumed η2 = Wrev / Wu, input )
with irreversibility, I, or, expressed as exergies:
exergy recovered, i.e. made use of exergy destroyed
η  
exergy supplied exergy supplied
Turku
Example: Efficiency
 A house, like many in Finland, is electrically
heated, using an electric resistance heating
element that converts electricity for 100%
into heat at room temperature.
For indoor T = 21°C and outdoor T = 10°C,
determine the Second-law efficiency.
 The performance can be described by the so-called coefficient of

performance, COP, defined as
heat output which here is equal to COP = 1.
COP 
heater
work input
Thigh
 For the most efficient, Carnot, process: COPheater 
Thigh  Tlow
with result COPrev = 294/(294-283) = 26.7.
 Thus, the Second-law efficiency η2 = COP/COPrev = 0.037 = 3.7%
ÅA 424304
1.3 Physical Exergy
Exergy of ”Non-Heat” Energy

 Kinetic energy Ek = ½m(v-vref)2 can* be completely and
reversibly converted into work  Ex(Ek) = Ek
 Potential energy Ep = mg(z-zref) can* be completely and
reversibly converted into work  Ex(Ep) = Ep
 Electric energy Eelec = i·V·t (current × voltage × time) can**
be completely and reversibly converted into work 
Ex(Eelec) = Eelec
 Similar for energy streams Ė (J/s, W) or specific energy
(streams) e = E/m = Ė/ṁ, ė = Ė/m, with mass stream ṁ
(kg/s) or mass m (kg)
* if frictional losses (giving heat) can be avoided

** if Ohmic losses (giving heat) can be avoided
Exergy of Heat
 The exergy of heat follows directly from Carnot’s
analysis (C1824): the maximum amount of reversible
work that can be obtained from conversion of heat Q
at temperature T, with temperature T° of the
surroundings, equals
T0
Ex( Q )  ( 1  )  Q  Carnot factor  Q
T
with of course T’s in K!!
 As noted above: the entropy part Sadi Carnot

of energy (anergy), for heat Q equal 1796-1832
to Q/T, cannot be converted into work. see C1824
Exergy of Internal Energy

 Internal energy U is composed of sensible heat (∫cvdT), latent
heat (ΔUphase transitions), chemical energy and nuclear energy.
Chemical (reaction) exergy will be addressed separately (sections 1.8 and
1.9), nuclear (reaction) exergy will not be addressed here.
 Remember that for internal energy, ΔU = Q + W or

dU = δQ + δW, where, as shown above,
- Ex(δW) = δWu = -(p-p°)dV = -pdV + p°dV = δW + p°dV,
with useful work Wu> 0, gained by the system (!!) and
- with Ex(δQ) = (1 - T°/T)· δQ and δQ = dS/T it follows that
Ex(δQ) = (1 - T°/T)·TdS = δQ -T°dS
- Ex(dU) = Ex(δWu) + Ex(δQ) = dU + p°dV - T°dS
This gives finally:
!!!  Ex(U)=T°,V°,p°∫T,p,VdU+p°dV-T°dS=(U-U°)+p°(V-V°)-T°(S-S°)
Exergy of Enthalpy
 For enthalpy, H = U + pV
Thus, Ex(H) = Ex(U) + Ex(pV)
 As shown above, for internal energy:
Ex(U) = (U-U°) + p°(V-V°) - T°(S-S°)
and since Ex(pV) = (p-p°)V (see above: surroundings work p°ΔV)
for work done by the system the result is:
!!  Ex(H) = U+pV - (U°+p°V°) - T°(S-S°) = (H-H°) - T°(S-S°)
 Combined with Ek + Ep for kinetic and potential energy this is

also known as ”flow exergy”,
with symbol ψ typically used for Ex(H) + Ek + Ep,
 Similarly, symbol Φ is often used for Ex(U) + Ek + Ep
Exergy of a Flow / Non-flow System

 The exergy of a moving or non-moving (or flow or non-
flow) system is a combination of the kinetic, potential and
thermo-mechanical exergy
 see Figures below for non-flowing and flowing systems:
Pics:
ÇB98
Example: Internal Energy Exergy /1
 Calculate the maximum amount of

work to be obtained from expanding
200 m3 compressed air at p1=10 bar,
T1 = 300 K to ambient conditions
(T° = 300K, p° = 1 bar).
 The maximum work is equal to the exergy of the closed

system of compressed gas: Ex = Ex(U) = m·ex(u), where m
can be found using ideal gas law (temperature and pressure
are far from Tcrit, pcrit);
 m = Mp1V1/RT1 ≈ 2323 kg.
Pic:
ÇB98
Example: Internal Energy Exergy /2

 No kinetic energy, no potential energy
to be considered.
 Ex(U) = (U-U°) + p°(V-V°) - T°(S-S°)
 T1=T°  ΔT=0  U1 - U0 = 0
 Note: s1 = s° + cp·ln(T1/T°) - R·ln(p1/p°)
using δq = du - δw  Tds = du + pdV = dh - Vdp = cpdT - (RT/p)dp
 p°(v1-v°) = p°·R(T1/p1-T°/p°) = RT°(p°/p1-1); (T1=T° !)

 T°(s1-s°) = T°·[cp·ln(T1/T°)-R·ln(p1/p°)] = - R·T°·ln(p1/p°)
=0
 Ex(u1) = 120.76 kJ/kg; Ex(U1) = m· ex(u1) = 280.53 MJ

Pic: ÇB98
Open System Exergy, h-s diagram /1
 As for an alternative derivation: Consider an open
system that produces work w, which is maximal, wmax,
for a reversible process. Neglect kinetic and potential
energy effects.
 For reversible heat exchange q, this must occur at a
temperature T°  q = T°·Δs = T°·(s2 - s1)
 Also, the outflow 2 must be at equilibrium with the
surroundings: h2 = h°, T2 = T°, p2 = p°, s2 = s°
For those
who use
h,s diagrams
Pic: B01
Open System Exergy, h-s diagram /2

 The energy balance for this system gives:
wmax = h1 – h2 + q = h1 – h2 - T°·(s2 – s1) , and thus
for the maximum work, wmax = ex, in general:
ex = h – h° - T°·(s – s°)
 This can be conviniently plotted in h-s diagrams, with
reference line dh/ds = T°
T0
Pics: B01
ÅA 424304
1.4 Exergy Destruction;

Isolated-Closed-Open Systems
Exergy Destruction /1
 Consider an isolated system: no energy or mass
transfer across the system boundaries is possible
 The energy and entropy balance equations give, for time
t1  t2: ΔU = U2 - U1 = 0, Sgen = S2 - S1.
 Combined, and ×T°  T°·Sgen= T°·(S2 - S1)
 For the total exergy of this system:
Ex2 - Ex1 = (U2 -U1) + p°·(V2 - V1) - T°·(S2 - S1)
= - T°·(S2-S1) = -T°·Sgen  ΔEx = -T°·Sgen ≤ 0
with exergy destruction –ΔEx = T°·Sgen ≥ 0
 For systems in general, this is known as the
Gouy-Stodola relation referring to work reported by Gouy
(1889) and by Stodola (1910)
 Considering again an open
system as in the figure  ,
for a reversible process
wrev = h1 - h2 + q°, where q°= T°(s2-s1),
Pic: B01
while for an irreversible process
wirrev = h1 - h2 + q with q < q°, indicating a
net entropy production Δs = s2-s1 – q°/T° >0
Thus, Δex = wrev – wirrev = T°·Δs (Gouy – Stodola)
 Similar to the principle of increasing entropy, this is
known as the principle of decreasing exergy
 For an entropy production rate the exergy destruction
rate is equal to -ΔĖx = T°·Ṡgen ≥ 0
 For a closed system, which does not involve mass
flows a general balance equation reads: Picture: http://www.mikecurtis.org.uk/images/radiation.jpg
Exheat + Exwork – Exdestroyed = ΔExsystem,

where Exdestroyed = T°·Sgen ≥ 0
which gives, for several heat (streams) Qi :
 T0 
 1  T   Qi  (W  p0 (V2  V1))  T0  Sgen  Ex2  Ex1
i  i 
 T0  
or as rate :   1    Qi  (W  p0 dV )  T0  S gen  dEx
 Ti  dt dt
i 
or with non  constant Ti for Qi :
2
 T0 
  1  T   Qi  (W  p0 (V2  V1))  T0  Sgen  Ex2  Ex1
i 1 i 
 For an open system, which does involve mass flows a
general balance equation reads:
Exheat + Exwork + Exin - Exout - Exdestroyed = ΔExsystem,
where Exdestroyed = T°·Sgen ≥ 0
which gives, for several heat (streams) Qi and incoming and
outgoing enthalpy streams with exergy ψj, ψk:
 T0 
 1  T   Qi  (W  p0 (V2  V1))   m j  j  mk  k  T0  Sgen  Ex2  Ex1
i  i  j k
 T0  
or as rate :   1    Qi  (W  p0 dV )   m  k  k  T0  S gen  dEx
 j  j   m
 
Ti  dt dt
i  j k
or with non  constant Ti for Qi :
2
 T0 
  1  T   Qi  (W  p0 (V2  V1))   m j  j  mk  k  T0  Sgen  Ex2  Ex1
i 1 i  j k
Example: Exergy Analysis-Open System /1

 A 200 m3 storage tank for air, at
p1=100 kPa, T1= 300K is to be used for
air storage at p2 =1 MPa, T2 =300 K.
Air is supplied by a compressor that
takes in air at p° =100 kPa, T°= 300 K.
Calculate the minimum work Pic:
ÇB98
requirement for this process.
 Ideal gas behaviour can be assumed; no kinetic or potential

energy effects.
 Note that for the incoming air, ψ1=ψ°=Φ°= 0
 Final mass follows from ideal gas law  m2 ≈ 2323kg.
Example: Exergy Analysis-Open System /2
 For the final state, Ex(U2) = m2·Φ2 is
to be calculated, where u2 - u° = 0
since ΔT = 0
 p°(v2-v0) = RT°(p°/p2 -1) and

Pic:
 T°(s2-s1) = -RT°(ln(p°/p2)) ÇB98
 Thus, Φ2 = ex(u) = (u2-u°) + p°(v2-v°) - T°(s2-s°)

= 0 + RT°(p°/p2 -1) + RT°(ln(p°/p2))
= 120.76 kJ/kg
 Wrev = m2·Φ2 = 280.53 MJ see also

slides 27 – 28...
ÅA 424304
1.5 Physical Exergy:

Applications
heat exchangers, tube flow, combustion,
endoreversibility
Heat Transfer and Exergy Losses
 During the transfer of heat Q
from medium 1 to medium 2,
with temperatures T1 > T2, the
entropy of the heat Q increases Q
from Q to Q . T
T T
 The entropy increase ΔS = Sgen
is equal to
Q Q   Pic:
S gen    Q   ÇB98
T T  T T 
 And the exergy losses are equal

to –ΔEx = T°·Sgen
Turku
Heat Transfer Efficiency (PTG course)

 A simple steady-state heat  Thermodynamic analysis
transfer process; heat is Energy balance
transported from medium 1  Q
Q 
 
to medium 2 by conduction
Entropy balance
through a material that
Q 
Q
separates them. 
 S gen   
T T
 Temperature T1 > T2
       Q
S gen  Q  T  T  
  
 T T  . TT
 This shows that Sgen is
large for large temperature
. .
Q1 Q2 differences (T1-T2) and low
T = T1 T = T2 See also temperatures T1 and T2
vS91
Quality Diagram : 1/T versus Q
 Heat exchange: hot side T1  T2, cold side T3  T4
 Exergy loss = T0  the surface between lines in the
quality diagram
Q Source:
1/T0 TUD92
3 4
4 2 2
1/T 1 1
3
1/T = 0
Heat Exchanger Exergy Losses /1

 A heat exchanger involves two media at temperatures TCin
and TCout on the cold side, THin and THout on the hot side.
(Note: TCin = TCout or THin = THout is possible!)
 For a heat exchanger transferring a heat stream Q, to a cold
mass stream ṁC from hot mass stream ṁH:
>0 <0
TCout
T
TCout
T0  TCout 
E xC   (1  0 )Q   T c pC
(1  )  
m c dT  
m c 
C pC 
 (TCout  TCin )  T0 ln 
TCin
T TCin  TCin 
<0 >0
THout
T
THout
T  T 
E xH   (1  0 )Q   (1  0 )  m c c pH dT  m H c pH   (THout  THin )  T0 ln Hout 
THin
T THin
T  THin 
 and the exergy losses are then equal to <0 >0
T T
 ΔE x  ( ΔE x C  ΔE x H )  T  (m
 Hc pH  ln Hout  m
 Cc pC  ln Cout )
THin TCin
with specific heats cpH, cpC for the hot and cold streams.
Turku
http://oldtacomamarine.files.wordpress.com/2008/01/straight-tube_heat_exchanger_1-pass.png
 ! Also, -ΔEx = T°∙ [ṁH· (sHout-sHin) + ṁC· (sCout-sCin)]
 The efficiency of a heat exchanger, ηHX, can then be
defined as
Q Q
ηHX   (%)
Q  T  ΔS Q  ΔE x
 In cases where electric
power Pelec is (for example)
used on the hot side:
 ΔE x  Pelec 
 T 
 Cc pC   T  ln Cout  (TCout  TCin ) 
m
 TCin 

 Heat exhanger exergy analysis shows that the temperature
difference between the flows (or with the flow, for only on
medium flow) should be as small as possible (but too small
ΔT requires much surface A!).
 This shows that counter-current heat exchangers perform
much better than co-current heat exchangers.
 Ideally, the flows aquire each others temperature: the
exergy losses will then be zero. For this, the heat capacities
ṁ·cp for the streams should be equal:
ṁC·cpC = ṁH·cpH.
 This is anyhow a requirement for a high ”effectiveness” of
the heat exchanger, which depends on the ratio
(ṁC·cpC) / (ṁH·cpH) (see course PTG 424101 # 4.3)
Example: Heat Exchanger
 Consider heat flow Q through a 5m×6m
wall with thickness dwall = 0.3 m and heat
conductivity λ = 0.69 W/(m·K), from an
indoor temperature of 27°C to an
outside temperature of 0°C. The inside
and outside wall temperatures are 20°C
and 5°C, respectively.
Calculate the heat flow Q and the exergy
destruction rate –ΔEx in W.
 Q = -λ(ΔTwall/dwall) = 1035 W Pic:
ÇB98
 - ΔEx = Ex(Qinside) – Ex(Qoutside)
= Q·[(1-T°/Twall,in) – (1-T°/Twall,out)] = 52.0 W in the wall,
and = Q·[(1-T°/Tinside) – (1-T°/Toutside)] = 93.2 W in total
A Process Example
 Bilge water (waste
oil/water mixtures) Cold
storage
Heated
heat Hot water
storage
processing for recycled
fuel oil (in Turku) Raw
material
 Significant savings could heat
Hot water Fuel
be obtained by Water
oil
disposal heat
– Replacing the heating
Heating
centre and, more center
importantly the electric Electricity
heat
heating (!) by heat from Product
the local district heat Surfactant
network Product
Separator
storage
– Making use of hot raw Source:
heat
Sludge
material deliveries Hot water ZHPSS07
Heat Exchange and Driving Force
 Heat transfer theory states that heat transfer is driven by a
temperature difference ΔT = TH-TL :
Q ~ A·(TH-TL), for heat flow Q through a surface A from
higher temperature TH to lower temperature TL.
   
 Exergy analysis shows that  ΔEx loss  Q  T    
which suggests a thermodynamic  TL TH 
driving force equal to Δ(1/T) instead, and
 the exergy losses are the product of three factors, being
1) surroundings temperature T0, 2) the heat flow Q, and
3) the driving force Δ(1/T).
 As irreversible, or non-equilibrium thermodynamics
See later
part
of this shows: Ṡgen = ∑ Ji·Xi for flows Ji and driving forces Xi
course
Exergy Losses and Tube Flow /1

 For fluid flow V (m³/s) through a tube, viscous friction results
in pressure drop Δp (Pa), which must be compensated for by
pumping power W  p  V . This energy is converted to heat
at fluid flow temperature T (so not all is lost!)
 Thus the exergy losses can be calculated as:
 ΔĖx = Δp· V - Δp· V ·(1-T°/T) = Δp· V ·T°/T = mechanical
dissipation × loss factor T°/T; or Δėx = (Δp/ρ)·T°/T
 Note that ΔĖx > Δp· V if T < T°. (No cooling for free!)
Note: 4ƒ = ζ = Blasius, Darcy friction factor
-τw
ƒ = Fanning friction factor
p1 R p2
r For pressure drop Δp:
A (p1 - p2 ) = -Δp = τw∙L·(4 /Dh)
x = 4ƒ∙½∙ρ∙<v>2 ∙L/Dh
S with hydraulic diameter Dh = 4·A/S
L
1 2 A = ”wet” area, S = ”wet” perimeter
Turku
 The pressure drop can be related to the fluid flow with cross
sectional averaged velocity <v> = V /A, with friction factor ƒ,
where 4ƒ = 64/Re for laminar circular tube flow, or for
turbulent flow in smooth tubes with hydraulic diameter Dh :
4ƒ= 0.316·Re-0.25 (2500 < Re < 105) (Blasius).
 This gives dissipation losses for turbulent flow along round tube
length x: δ w /dx = (δW /ṁ)/dx = (-dp/dx)/ρ = cp·dT/dx, which is
equal to
w 1.79   0,25  m 1,75 for fluid density ρ,
 1,75 2 4,75 dynamic viscosity η,
dx   D mass flow ṁ.
-τw
p1 R p2
r
A
x
S
L
1 2

 For a round tube with diameter D, with insulation material, giving
overall heat transfer coefficient U (W/m2·K), carrying turbulent
flow at temperature T (for example a heat exchanger
tube) the heat exchange per meter with the environment is:
q U(T  T 0 )D
Q
 
dx m  dx
 m
which gives for the total exergy losses per length section dx:
dex 1.79 0,25m

 1,75 T 0 U(T  T 0 )2D
 1,75 2 4,75 
dx   D T T
m
which shows that losses due to pressure drop decrease with
diameter, while those for heat losses increase with diameter !
Turku
For a given optimal value for the diameter,

Doptimal , the exergy losses are minimal:
η,   m
 .  T 
Doptimal
, 
 .
U  ρ   (T  T  )
Turku
Energy Conversion Stages in

“conventional” Electricity
Production, i.e. condensing power plant
 Energy in chemical bonds of fuel  Sources of exergy loss:
 Furnace  Friction in flow lines,
pressurising and de-
 Thermal energy of hot flue gas
pressurising
 Heat transfer to steam cycle  Heat transfer at low
 Thermal energy of water / steam temperatures and/or
across large temperature
 Steam cycle generator
differences
 Electrical energy  Conversion of chemical
(potential) energy into
thermal energy (heat)
Exergy Loss in Expansion Turbine
 p1, T1, S1  p2, T2, S2 is non-isotropic Pic:vL77
due to friction
 frictional heat Q = surface 1-2’-S2’-S1-1
in T,S diagram
 frictional heat to fluid = surface 1-2’-4-3-1
= (1-T0/Tav) Q
 exergy loss Ex = surface 3-4-S2’-S1-3
= (T0/Tav)Q
  loss factor T0/Tav i.e. less serious at
increasing average temperature Tav
Transformation
of Work into Heat 2
Exergy Losses in Combustion /1

 Combustion = Oxidation, i.e. transfer of electrons
from fuel to oxygen  Two “extreme” options :
1. “Conventional electric power generation”
 Mix fuel and oxygen at (adiabatic) temperature
T, and produce heat Q at temperature T.
 Fuel exergy Ex 
exergy of hot gas + exergy loss
 Exergy of hot gas = (1-T0/T) Q
2. “Electric power generation” using fuel cells
 Separate the release of electrons from the fuel from the take-up of
electrons by oxygen, connect this, allow for the positive ions from the
fuel to combine with the negative oxygen ions.
 Fuel exergy Ex  Electrical energy We + exergy losses
 Exergy loss due to heat production Qp : Ex = We + (1-T0/T) Qp
Quality Diagram for Furnace
 Fuel: area = exergy / T0
 Product gases: calculate exergy from Tfurnace to T0
Q
0
1/Tfurnace
 1/T Pic:
TUD92
Fuel 1/Tstack
1/T0
Ex flue gases
Flue gases Ex fuel

Quality Diagram for Total System
 Exergy input (fuel) = Exergy loss in combustion + Stack
losses + Heat transfer loss to steam
cycle + Exergy taken up by steam cycle
Fuel Q
0
1/Tfurnace
Combustion
losses
Pic:
 1/T TUD92
Exergy to 1/Tstack
steam cycle
1/T0
Ex flue gases
Stack losses Ex fuel
ÅA 424304
Energy and Exergy Analysis-PFBC

(Pressurised Fluidised Bed Combustion) : Sub-systems
Pic: ACA95
ÅA 424304
Energy and Exergy Analysis PFBC
Pics: ACA95
Endoreversibility /1 Qin
 The maximum work output
from a Carnot engine Carnot TH
engine
operating on heat input Qin, operating W
between T=TH and T=T° is between
equal to Wmax = Qin(1-TH/TL), TH and T°
T°
with isothermal transfer of
Qout
heat Qin·T°/TH to the
environment at T=T°.
Endo- TH Qin
 However, isothermal heat reversible
transfer cannot exist; a Carnot THc
driving force ΔT or, more engine W
operating
correctly, Δ(1/T) is needed, between T
Lc
which then gives losses THc and TLc
Qout
Qin·T°·Δ(1/T) Pics: SAKS04 T°
Endoreversibility /2 See also Curzon & Ahlhorn

Am. J. Phys. 43 (1975) 22
 If these are the only losses, Endo- TH Qin

reversible
the process is referred to as THc
Carnot
endoreversible. engine W
 If Qin→0, W→0, the endore- operating
versible process → reversible between TLc
THc and TLc
with THC≈TH , TLC≈T°, W = 0 Qout
 If Qin→Qin,max, temperatures THC T°
≈ TLC and W → 0.
 Maximum power Wmax is ηcarnot
achieved for optimum
TLC o
T
 W ηcycle
THCoptimum TH
at efficiency TLCoptimum To
Wmax
η    optimum   
Pics: SAKS04 THC TH Qin
Qin,max
Turku
ÅA 424304
1.6 Mixing Exergy
See SAKS04 §7.2, §6.3
Exergy of Mixing /1
 Assuming two gases, each at temperature and pressure T0
and p0, separated by a barrier;
 Removing the barrier results in (diffusive) mixing, giving a
homogeneous mixture in which the chemical potential
(i.e. Gibbs energy) of each of the components decreases.
 The exergy change is given by µ(x) = µpure + RT ln (γ∙x)
ΔEx mix  ΔHmix  T  ΔSmix  ΔGmix (p  , T )
 For ideal mixing (no changes in p, T, total V, and activity

coefficients γi = 1), which means also ΔHmix=0:
ΔSmix  R x i  ln x i  ΔEx mix  RT  x i  ln x i
i i
 This is important for separation processes (e.g. distillation!)

Turku
Exergy of Mixing /2
 Consider adiabatic
mixing of cold and hot 1
water, at T°=25°C,
p=p° =1 atm 2 3
 Ėxi = ṁi·((hi-h°) - T°(si-s°)),

with enthalpy h°, entropy
s° for liquid water at T°, p°
 p=constant; si-s°=cp· ln(Ti/T°)
 Water/steam table data
give the results as in the
so-called Grassmann
exergy flow diagram
η = Ėxout / Ėxin = 0.216
 Ėxlost=T°· (ṁ3s3 - ṁ2s2 - ṁ1s1) Ėxlost = 78.4 %!
Pics: SAKS04
Turku
Exergy of Mixing /3 Source: S05
 More general, for mixing of two molar streams n1, n2 with

molar fractions xi in the original streams and molar fractions xj
in the final stream:
ΔEx mix  RT  (n  n  ) x j  ln x j  n  x i  ln x i  n   x i   ln x i  

 j i i 
Turku
Exergy of Mixing /4 Source: S05
 For example: oxygen-rich (x=30%-vol O2) gas for a blast furnace is

produced by mixing technical oxygen (x=95%-vol O2) and
atmospheric air (x=21%-vol O2).
 The consumption of technical oxygen per mole of product gas,

nto/npg, follows from:
0.3 = 0.95·nto/npg + 0.21·(1- nto/npg)  nto/npg= 0.122 mol/mol (= m3/m3)
  for the exergy loss per mole of product gas
 .  ln .  . ln . 

 
Δex mix  .      .  (.  ln .  .  ln .)   . J/mol
  .  (.  ln .  .  ln .) 
 
Turku
ÅA 424304
1.7 Heat Radiation Exergy
See S05 §1.4.6; §2.7
and P10
Thermal Radiation /1
 The radiation Q. R (W) from a
surface with emissivity ε (-) surface A
(m2) and temperature T(K) equals
.
QR = ε· σ·A·T4
with Stefan-Boltzmann coefficient
σ = 5.67×10-8 W/m2K4
 For a blackbody surface
– ε =1 in the Stefan-Boltzmann Law
– all incident radiation is absorbed
– radiation is maximum for its temperature at
each wavelength, λ (m)
– the intensity of the emitted radiation is
independent of direction: it is a diffuse
emitter
Pictures: T06
 For a blackbody, the entropy flux associated with
. thermal
radiation is not, as might be expected, ṠR,BB= QR/T = σ·A·T3, but
.
ṠR,BB= (4/3)·σ·A·T3 = (4/3)· QR/T
 For emitting and absorbing blackbody surfaces with equal surface

Ae = Aa that can ”see” each other completely (i.e. view factors Fa→e =
Fe→a = 1) the entropy generation during heat radiation equals
  Te  Ta 
S gen,BB  σ  Ta  Te  
 
 Ta 
 T 
 σ  Ta  Te e  
 Ta  
See also Petela, R., J. of Heat & Mass. Transf.
Ser. C, 86 (1964) 187-192; and S05 section 2.7 Pic: WRSH02
 For gray surfaces, emissivity ε =
ε(λ,T,θ), absorptivity α = α(λ,T,θ),
reflectivity ρ = ρ(λ,T,θ),
transmissivity τ = τ(λ,T,θ), are all Incident angle
θ with respect
0 < .. < 1. to normal
 Energy balance α + ρ + τ = 1, and Pic: after

Kirchhoff’s law (from Second law) KJ05
gives ε = α for gray bodies and not- λ = wavelength; here of interest
too-large temperature differences. is the range 0.1 < λ < 100 µm
 The exergy of (blackbody) radiation, exBB, with respect to its

energy content, eBB:
ex BB T  T
     (  )
eBB T  T See also Petela, R., J. of
Heat & Mass. Transf. Ser.
which does not depend on ε°= εenvironment, C, 86 (1964) 187-192
and S05 section 2.7
and can be used for gray bodies if ε ≠ ε(λ)
 Recently (see e.g. W07) it was shown that for the entropy of
gray radiation
Q      
S R,GB  R ,BB
 I(ε )  SR,BR  I(ε )  σεT     ( .  .ε )  ln( ε ) ;
 T π 
π 
  π


Q    
or in general S R,GB  n(ε )  ε  R,BB , where n(ε )     ( .  .ε )  ln( ε ) 
T   π 

Net radiation from a black- Net radiation from a BB Net radiation for incident
body (BB) with incident with incident BR, with GR on a blackbody
blackbody radiation (BR) gray-body radiation (GR)
To be continued in Part 2 Heat Radiation, Solar Energy Pics, source: W07
ÅA 424304
1.8 Chemical Exergy
Exergy of Chemical Substances /1

 Chemical exergy gives the exergy of a substance
with respect to a reference environment.
Note, again, that the environment is not a dead state at thermodynamic
equilibrium, due to a constant influx of solar energy.
 For each chemical element a reference species that
contains, it is chosen, which gives the lowest exergy
level in nature (yet indeed appearing!), i.e. the most
common component of the environment (which can
be the air, seawater, the earth’s crust)
”Normal conditions” for the reference environment (see also slide 8):
T° = 298.15 K, p°= 101.325 kPa, relative humidity 70%, atmospheric
CO2 concentration 330 - 380 ppm, sea water salinity 3.5 %-wt, etc.
Some data for air: N2 = 75.78 kPa; O2 = 20.39 kPa, Ar = 906 Pa,
CO2 = 33.5 Pa, H2O = 2.2 kPa, He = 1.77 Pa, Ne, D2O, Kr, Xe < 1 Pa
(SAKS04)
 Examples for reference species are atmospheric O2 and CO2
for oxygen and carbon, CaCO3 for calcium, Fe2O3 for iron,
etc. at 298.15 K, 101.325 kPa
 The standard chemical exergy ex°chem = b°chem

of a compound or element follows from an exergy balance
of a reversible standard reference reaction, where :
b ochem  Δ r Go   b ochem,product   b ochem,reac tan t

product reac tan t
 For example, for Ca+½O2+CO2  CaCO3,

with -ΔrG° = 738.6 kJ/mol;
for the elements (see Tables on following pages)
the normal standard values for the chemical exergy for the references
species are
16.3 kJ/mol for CaCO3, 19.87 kJ/mol for CO2 and 3.97 kJ/mol for O2.
 This gives for calcium, Ca:
ex°chem = b°chem =-738.6 + 16.3 - 19.87 - 1½×3.97 = 729.1 kJ/mol
 For chemical compounds, the standard chemical
exergy can be more easily calculated from the reversible
standard formation reaction, with ΔG = ΔfG°
b ochem  ex ochem  Δ f Go   nelement  ex ochem,element

elements
where nelement is the number of moles of the element per

mole of compound, and ex°chem, element = b°ch from tables.

 For the constituents of air (N2, O2, Ar, CO2, ...),
at T° = 298.15 K and the average pressure p°avg = 99.31 kPa
the exergy value = 0.
 Note that ideal gas law usually applies.
 Thus, for a pure component at T°,p°,

since ΔExseparate = ΔHseparate -T°·ΔSseparate = -T°·ΔSseparate
= T°·ΔSmix,
and ΔS1,2 = -Rln(p2/p1)
gives
 E°chem,i = RT°ln(p°/pi) for these.
Standard Chemical Exergy of the
Elements 1/5 Source: S05
γ = activity coefficient in seawater, m = molarity in seawater, p = %-vol, x = molar fraction


ÅA 424304

ÅA 424304

ÅA 424304

Remember the meaning of chemical exergy:

it gives the maximum amount of work that can be made available
from a mole of the species in a given environmental surroundings
Standard exergies
for solids
based on
reference
species
dissolved in
seawater
Source: S05
Chemical Exergies of Fuels
Ratio of the standard chemical exergy to the
lower and higher heating value for several
hydrocarbon fuels (HL = LHV; HH = HHV)
Source: S05
Example: Standard Chemical Exergy

 Calculate the standard chemical exergy of larnite, Ca2SiO4,
for which the energy of formation is -ΔfG° = 2191.6 kJ/mol.
 b°chem = -2191.6 + 2×b°chem,elCa + 2×b°chem,elO2 + b°chem,elSi

= - 2191.6 + 2×729.1 + 2×3.97 + 854.9 = 129.4 kJ/mol
Picture: http://webmineral.com/data/Larnite.shtml
 Tabelised data in S05 give b°chem = 95.7 kJ/mol .......
(mixing exergy cannot explain this)
Larnite
Example: Mineral Carbonation /1
 (1) xMgO.ySiO2.zH2O(s) + (x-z)H2O  ….  xMg(OH)2(s) + ySiO2(s)
(2) Mg(OH)2 (s) + CO2  MgCO3 (s) + H2O
 Chemical exergies of the chemical species are calculated

using exchem(T, p) = exchem + exchem (T,pT,p) where
exchem(T,pT,p) = h(T,pT,p) - Ts(T,p  T,p)
For liquids and solids: exchem(T,pT,p) = exchem(TT)
= h(TT) - Ts(TT); and exchem(T, p) = exchem(T)
 Standard exergies of formation are calculated using:
o
exchem   f Go   nelement  exchem
o
,element
elements
where nelement is the number of moles of the element in a
mole of a certain compound, and e°chem, element from Tables

 The exergy of CO2 as a function of temperature and pressure can
be calculated, with h = h(T) and s = s(T) (for ideal gas) as
exChem,CO2 (p,T) = ex°Chem,CO2+(h(T)-h°)- T°·(s(T)-s°)+RT ·ln(p/p°)
with reference ex°Chem,CO2 = RT° ln (p°/p°°) = 19.587 kJ/mol
using a reference concentration of 0.0375 %-vol of CO2 in the dry
atmosphere (p°° = 0.000375·p°)*.
 R = 8.314 J/(mol·K), T = 298.15 K, p = 101.325 kPa.
 For all compounds “reaction exergies” can be calculated as
exergy differences between reactant and product exergies
 With entropy difference ΔS(T) for the carbonation reaction at
temperature T, the irreversibility or exergy loss is defined as
ΔExloss(T) = -ΔEx(T) = T°·ΔS(T)
* In 2014, atmospheric CO2 concentration has risen to 0.0397 %-vol
ÅA 424304
Example: Mineral
Carbonation /3
Calculated
results
using
data from
SMS88 and
K95
taken from ZK04
ÅA 424304

-20
MgO + CO2(g) <=> MgCO3
Mg(OH)2 + CO2(g) <=> MgCO3 + H2O(g)
½ Mg2SiO4 + CO2(g) <=> MgCO3 + ½ SiO2
-30 1/3 Mg3Si2O5(OH)4 + CO2(g) <=> MgCO3 + 2/3 SiO2 + 2/3 H2O
Irreversibility kJ/mol CO2
-40
-50
Chemical exergies of MgO,
Mg(OH)2, Mg2SiO4,
-60
Mg3Si2O5(OH)4 and MgCO3,
0 100 200 300 400 500 per mol Mg.
Temperature °C 100
MgO
Irreversibility of the reaction Mg(OH)2
80 Mg2SiO4
of CO2 with several MgO-
Chemical exergy of substance
Mg3Si2O5(OH)4
MgCO3
containing species, per mol 60
kJ/mol Mg
CO2. (1 bar) 40
20
-20
0 100 200 300 400 500
taken from ZK04 Temperature °C
ÅA 424304
1.9 Simplified Exergy Analysis With

Chemical Reactions
Simplified Process Analysis /1

 Exergy optimisation of processes with many heat streams
(in / out), giving an overall excess output:
T
j Ex(Qout,j )  i Ex(Qin,i )  max , with Ex(Q)  (   )Q
T
 From this it can be assessed if  Qout , j   Qin ,i  0
j i
indeed gives an exergy output (or if <0 : minimal losses...)
 For processes with chemical conversions (if exotherm, ΔH < 0
 Qout > 0, if endotherm ΔH > 0  Qin > 0), these typically will
give the largest exergy losses due to entropy changes ΔS
 ΔExloss = T°·ΔS, or = T°·∑ΔSi
 The optimisation becomes, for a process with k chemical
conversion steps:  T 
and calculate the values for
k   (  ΔHk )  max
 Tk 
ΔSk and from that ΔExloss
 This is very effective for finding the optimum
temperature combinations for a process with several
reactions/reactors at different temperatures.
 Example: the ÅA route for serpentinite carbonation
1. Magnesium extraction solid/solid ~ 400-450°C
– Mg3Si2O5(OH)4 + 3(NH4)2SO4 + heat ↔
3MgSO4 + 2SiO2 + 5H2O(g) + 6NH3(g)
2. Mg(OH)2 production aqueous solution
– MgSO4 + 2NH4OH(aq) ↔
(NH4)2SO4(aq) + Mg(OH)2
3. Mg(OH)2 carbonation gas/solid, 20-30 bar, ~500°C
– Mg(OH)2 (s) + CO2 (g) ↔
MgCO3 (s) + H2O (g) + heat
ZFNRBH12
Simplified Process Analysis /3 B10
 Example: the ÅA route for serpentinite carbonation

Grassman diagram
Exergy consumption
5.54 GJ (~1.5 MWh)/ton CO2
ÅA VST
DI thesis
T Björklöf
2010
 Another approach: various temperatures and electrolysis.
NaOH
HCl ③ Cl2, H2 Electrolysis

production ②
CO2 CO2 ⑤ NaHCO3

capture NaCl
HCl
MgCl2 CO2
Serpentine Pre‐ ① “Serpentine” Extraction Carbonation
treatment ④ ⑥
Mg5(OH)2(CO3)4∙4H2O
Side prods. BZ12
T ΔH ΔG ΔEx
(°C) (kJ/mol) (kJ/mol) (kJ/mol)
R1 2 3 2 5 4 → 3 2 4 2 4 2 650 279.411 ‐248.034 267.3
R2 2 2 2 →2 2 2 85 426.608 412.834 423.2
R3 2 2 →2 25 ‐351.935 ‐254.468 ‐263.4

4 2 4 →2 2 2 2 2 ‐236.137 ‐195.95 ‐15.0

R4 or
6 → 3 2 5 70
3 2 5 4 2 2 2 ‐280.632 ‐252.296 ‐12.0
R5 2 → 3 25 ‐68.865 ‐36.586 0.4
5 2 10 3
R6 55 488.753 ‐104.527 ‐6.7
→ 5 2 3 4 ∙4 2 10 6 2

ÅA 424304
1.10 Exergy Analysis vs. Pinch

Analysis
Process Integration, Pinch /1
 Process integration deals primarily with process energy
and efficient design of heat exchanger networks
(HENs)
 Important for the system is the so-called pinch point;
heat should not be ”transferred across the pinch”
 Combining the hot streams
and cold streams of a system
into two composite curves
(temperature versus
enthalpy) shows the
Example process with two hot streams to
minimum temperature: the be cooled and two cold streams to be
pinch heated up. .
 The pinch divides the system CP = stream heat capacity = m·cp (W/°C)
in two ”regions” with cp averaged between Tin and Tout
Picture: CR93
Process Integration, Pinch /2
For the
example
on previous
slide
↑ Hot stream temperatures versus enthalphy Hot and cold stream composite curves ↑
↑ Grid for the four-stream network Proposed heat exchanger network for ΔTmin = 10 K ↑
Pictures: CR93
Exergy Analysis vs. Pinch Analysis
 It has been argued by Linnhoff (1987) that pinch analysis
is superior to exergy analysis.
 A study (1991) on the process integration of a new
nitric acid plant, however, showed that exergy analysis
allowed for energy savings 3× higher than what pinch
analysis suggested.
 Note, however, that pinch analysis is limited to heat
exchanger network (HEN) optimisation, and then with
certain restrictions, such as
– so-called threshold problems (no pinch!)
– integrating with heat pumps (where heat is transported
to higher temperatures) Source: S08
ÅA 424304
1.11 Final Remarks
Common-sense 2nd Law Guidelines
1 Do not use excessively large or excessively small thermodynamic driving forces in
process operations.
2 Minimize the mixing of streams with differences in temperature, pressure or chemical
composition.
3 Do not discard heat at high temperatures to the ambient, or to cooling water.
4 Do not heat refrigerated streams with hot streams or with cooling water.
5 When choosing streams for heat exchange, try to match streams where the final
temperature of one is close to the initial temperature of the other.
6 When exchanging heat between two streams, the exchange is more efficient if the flow
heat capacities of the streams are similar. If there is a big difference between the two,
consider splitting the stream with the larger flow heat capacity.
7 Minimize the use of intermediate heat transfer fluids when exchanging heat between two
streams.
8 Heat (or refrigeration) is more valuable, the further its temperature is from the ambient
9 The economic optimal ΔT at a heat exchanger decreases as the temperature decreases,
and vice versa,
10 Minimize the throttling of steam, or other gases.
11 The larger the mass flow, the larger the opportunity to save (or to waste) energy.
12 Use simplified exergy (or availability) consumption calculations as a guide to process
modifications.
13 Some second law inefficiencies cannot be avoided; others can. Concentrate on those
which can. Taken from: Sama, 2008 (S08)
Closing Remarks
 The First and Second laws of thermodynamics as
formulated by Baehr (B88):
– 1. The sum of anergy and exergy is always
constant
– 2. Anergy can never be converted into exergy
 ”Accepting exergy losses should always have some

economic justification. If such a justification does not
exist, it indicates that the exergy loss results only from
an error in the art of engineering” (S05)
Sources
 ACA95: Pressurised Fluidised Bed Combustion, M. Alvarez Cuenca, E.J. Anthony, Black Acad. & Profess.,
Glasgow (1995)
 B88: Baehr, H.D. Thermodynamik Springer Verlag, Berlin (1988)
 B01: Bart, G.C.J. Advanced Thermodynamics (in Dutch) course compendium Delft Univ. of Technol., Delft
(2001)
 B97: Bejan, A. Advanced Engineering Thermodynamics John Wiley & Sons (1997) Chapter 3
 B10: Björklöf, T. An energy efficiency study of carbon dioxide mineralization . MSc (Eng) thesis, ÅA (2010)
 BZ12: Björklöf, T., Zevenhoven, R. “Energy efficiency analysis of CO2 mineral sequestration in magnesium
silicate rock using electrochemical steps” Chem. Eng. Res. and Design 90 (2012) 1467-1472
 C1824: Carnot, S., Reflections on the motive power of fire. Paris, 1824; Dover Publ. Mineola (NY) 1980
 CB98: Çengel, Y.A., Boles, M.A. Thermodynamics. An Engineering Approach, McGraw-Hill (1998)
 CR93: Sinnott, R.K. ”Coulson & Richardson’s Chemical Engineering”, vol. 6, 2nd ed., Pergamon Press
(1993)
 dWetal08: DeWulf, J. et al., ”Exergy: its potential and limitations in environmental science and technology”
Env. Sci. & Technol. 42(7) (2008) 2221-2232
 FÖ97: Finnveden, G., Östlund, P. ”Exergies of natural resources in life-cycle assessment and other
applications” Energy - The International Journal 22(9) (1997) 923-931
 H84: Hoogendoorn, C.J. Advanced Thermodynamics (in Dutch) course compendium Delft Univ. of
Technol., Delft (1984)
 K41: Keenan, J.H. Thermodynamics, MIT press (1941) Chapter 17
 KJ05: D. Kaminski, M. Jensen ”Introduction to Thermal and Fluids Engineering”, Wiley (2005)
 K95: Kotas, T.J. The Exergy Method of Thermal Plant Analysis. Krieger Publ. Co., Malabar (FL) (1995)
 P03: Petela, R. ”Exergy of undiluted thermal radiation” Solar energy 74 (2003) 469-488
 P10: Petela, R. Engineering Thermodynamics of Thermal Radiation” McGraw-Hill (2010)
 RG06: Rivero, R., Garfias, M. ”Standard chemical exergy of elements updated” Energy - The International
Journal 31 (2006) 3310-3326

Sources (cont’d)
S08: Sama, D. ”Thermodynamic insights; an unusually stubborn attempt to think clearly”, Proc. of
ECOS2008, Kraków-Gliwice, Poland, June 2008, 19-40
 SAKS04: de Swaan Arons, J., van der Kooi, H., Sankarana-rayanan, K. Efficiency and
Sustainability in the Efficiency and Chemical Industries. Marcel Dekker, New York 2004
 S05: Szargut, J. Exergy Method. WIT Press (2005)
 SMS88: Szargut, J., Morris, D., Steward, F.R. Exergy Analysis of Thermal, Chemical and
Metallurgical Processes. Hemisphere Publishing Co, New York, (1988)
 SW07: Sciubba, E., Wall G. ”A brief commented history of exergy from the beginnings to 2004”. Int. J.
Thermodyn., 10(1) (2007), 1-26.
 T06: S.R. Turns ”Thermal – Fluid Sciences”, Cambridge Univ. Press (2006)
 vL77: Van Lier, J.J.C. Thermodynamic processes in the power plant and possiblities to improve these
processes, (in Dutch) course compendium Delft Univ. of Technol., Delft (1977)
 vS91: von Schalien R. Teknisk termodynamik och modellering, 6. ed, Åbo Akademi Univ. (1991)
 TUD92: Energy and exergy, Symposium Delft Univ. of Technol., Delft, Nov. 3,1992 (in Dutch)
 WRSH02: Wright, S.E., Rosen, M.A., Scott, D.C., Haddow, J.B. ”The exergy flux of radiative heat transfer
for the special case of heat radiation”, Exergy 2 (2002) 24-33
 W07: Wright, S. ”Comparative analysis of entropy of radiative heat transfer” Int. J. Thermodyn., 10(1)
(2007), 27-35
 Z99: Zevenhoven, R. ”Advanced combustion and gasification technology” course material ENY-47.210
Helsinki Univ. of Technol., Espoo (1999-2004)
 ZK04: Zevenhoven, R., Kavaliauskaite, I. ”Mineral carbonation for long-term CO2 storage: an exergy
analysis” Int. J. Thermodyn., 7(1) (2004), 23-31.
 ZHPSS07: Zevenhoven, R., Helle, H., Pettersson, F., Söderman, J., Saxén H., Heat optimisation of recycled
oil production from waste oils and oily waste waters. Proc. of ECOS'2007, Padova, Italy, June 2007, 839-
846
 ZFNRBH12: “Carbon storage by mineralisation (CSM): serpentinite rock carbonation via Mg(OH)2
reaction intermediate without CO2 pre-separation” Zevenhoven, R., Fagerlund, J., Nduagu, E, Romão, I,
Bu, J, Highfield, J, presented at GHGT-11, Kyoto Japan, Nov. 18-22, 2012

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Process Engineering Thermodynamics

course # 424304.0 v. 2015

1.1 Exergy vs. Energy

 With T2 > T0 no full

1.2 Reversible Work-Irreversibility

 Similarly, ΔV < 0 is possible. In many cases this surroundings

 This has no significance for 1) cyclic processes and 2)

Example: Irreversibility 1/1

 Wrev follows from the Carnot efficiency

 Note that the 500 kW - 375 kW = 125 kW Pic: ÇB98

Example: Irreversibility 2/1

Irreversiblities and Exergy Loss

 Equally, it can be defined as (for work producing devices):

 The performance can be described by the so-called coefficient of

1.3 Physical Exergy

Exergy of ”Non-Heat” Energy

* if frictional losses (giving heat) can be avoided

 As noted above: the entropy part Sadi Carnot

Exergy of Internal Energy

 Remember that for internal energy, ΔU = Q + W or

 Combined with Ek + Ep for kinetic and potential energy this is

Exergy of a Flow / Non-flow System

 Calculate the maximum amount of

 The maximum work is equal to the exergy of the closed

Example: Internal Energy Exergy /2

 p°(v1-v°) = p°·R(T1/p1-T°/p°) = RT°(p°/p1-1); (T1=T° !)

 Ex(u1) = 120.76 kJ/kg; Ex(U1) = m· ex(u1) = 280.53 MJ

Open System Exergy, h-s diagram /2

1.4 Exergy Destruction;

Exheat + Exwork – Exdestroyed = ΔExsystem,

Example: Exergy Analysis-Open System /1

 Ideal gas behaviour can be assumed; no kinetic or potential

 p°(v2-v0) = RT°(p°/p2 -1) and

 Thus, Φ2 = ex(u) = (u2-u°) + p°(v2-v°) - T°(s2-s°)

 Wrev = m2·Φ2 = 280.53 MJ see also

1.5 Physical Exergy:

 And the exergy losses are equal

Heat Transfer Efficiency (PTG course)

Heat Exchanger Exergy Losses /1

Heat Exchanger Exergy Losses /3

Exergy Losses and Tube Flow /1

Exergy Losses and Tube Flow /3

dex 1.79 0,25m

For a given optimal value for the diameter,

Energy Conversion Stages in

Exergy Losses in Combustion /1

Exergy Losses in Combustion /3

Energy and Exergy Analysis-PFBC

Energy and Exergy Analysis PFBC

Endoreversibility /2 See also Curzon & Ahlhorn

 If these are the only losses, Endo- TH Qin

1.6 Mixing Exergy

See SAKS04 §7.2, §6.3

ΔEx mix  ΔHmix  T  ΔSmix  ΔGmix (p  , T )

 For ideal mixing (no changes in p, T, total V, and activity

 This is important for separation processes (e.g. distillation!)

 Ėxi = ṁi·((hi-h°) - T°(si-s°)),