Energy Conversion and Management xxx (2014) xxx–xxx

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Energy Conversion and Management

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Exergy analysis of zeotropic mixtures as working fluids in Organic

Rankine Cycles
S. Lecompte a,b,⇑, B. Ameel a, D. Ziviani a,b, M. van den Broek b,a, M. De Paepe a
a
Department of Flow, Heat and Combustion Mechanics, Ghent University – UGent, Sint-Pietersnieuwstraat 41, 9000 Gent, Belgium
b
Department of Industrial System and Product Design, Ghent University – UGent, Graaf Karel de Goedelaan 5, 8500 Kortrijk, Belgium

a r t i c l e i n f o a b s t r a c t

Article history: The thermodynamic performance of non-superheated subcritical Organic Rankine Cycles (ORCs) with
Available online xxxx zeotropic mixtures as working fluids is examined based on a second law analysis. In a previous study,
a mixture selection method based on a first law analysis was proposed. However, to assess the perfor-
Keywords: mance potential of zeotropic mixtures as working fluids the irreversibility distributions under different
Organic Rankine Cycle mixtures compositions are calculated. The zeotropic mixtures under study are: R245fa–pentane,
Zeotropic mixtures R245fa–R365mfc, isopentane–isohexane, isopentane–cyclohexane, isopentane–isohexane, isobutane–
Second law
isopentane and pentane–hexane. The second law efficiency, defined as the ratio of shaft power output
Exergy
Working fluids
and input heat carrier exergy, is used as optimization criterion. The results show that the evaporator
accounts for the highest exergy loss. Still, the best performance is achieved when the condenser heat pro-
files are matched. An increase in second law efficiency in the range of 7.1% and 14.2% is obtained com-
pared to pure working fluids. For a heat source of 150 °C, the second law efficiency of the pure fluids
is in the range of 26.7% and 29.1%. The second law efficiency in function of the heat carrier temperature
between 120 °C and 160 °C shows an almost linear behavior for all investigated mixtures. Furthermore,
between optimized ORCs with zeotropic mixtures as working fluid the difference in second law efficiency
varies less than 3 percentage points.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction Because of the simplicity of the technology and the availability

The worldwide electricity demand is still growing. Future
projections assume an increase with 33% by 2020 and 84% by
2035 [1]. Besides growing demand, electricity prices have risen
in the last decade with 12%, both in Europe [2] and in the USA
[3]. Furthermore, environmental aspects, such as global warming,
ozone layer depletion and high-levels of pollution represent a large
concern and heavily influence the global energy policy. Therefore,
in order to reduce the dependency on fossil fuels, it is necessary
to emphasize the use of emerging and well-known renewable en-
ergy approaches. ORCs have the ability to convert low temperature
heat (<300 °C) to electricity. In particular, studies show that low
grade waste heat accounts for more than 50% of the total heat gen-
erated in the industry [4]. Besides waste heat, geothermal and solar
sources are available to provide a clean alternative to fossil fuel
combustion.
⇑ Corresponding author at: Department of Flow, Heat, and Combustion Mechan-
ics, Ghent University – UGent, Sint-Pietersnieuwstraat 41, 9000 Gent, Belgium.
Tel.: +32 470045524; fax: +32 92643289.
E-mail address: steven.lecompte@ugent.be (S. Lecompte).
of components, the ORC has the potential to become an established
technology in the near future. The basic ORC is already well known
in literature and in industry. However, in order to improve the
cycle performance, several modifications to the basic ORC are
proposed [5]. One of these modifications is the use of zeotropic
mixtures as working fluid. Zeotropic mixtures have a non-isother-
mal phase shift. As such, they have the ability to decrease the irre-
versibility associated with heat transfer over a finite temperature
difference across the working fluid and the thermal heat source
or heat sink reservoir. Zeotropic mixtures as working fluids have
been investigated for heat pumps [6–8] and vapor compression
cycles [8–10]. The use of zeotropic mixtures as working fluids for
the ORC has gained interest recently. Still, only a few studies on
this subject have been published. Several studies focus solely on
the first law efficiency with a limited selection of mixtures: Wang
et al. [11] (R245fa–R152a), Garg et al. [12] (R245fa–isopentane)
and Borsukiewiczgozdur and Nowak [13] (propane–ethane). A
systematic and comparative study of zeotropic mixtures as work-
ing fluids based on a first law analysis is given by the authors in
a previous study [14].

http://dx.doi.org/10.1016/j.enconman.2014.02.028
0196-8904/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
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2 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx

Nomenclature

C mole fraction (–) WF working fluid (–)

Cp heat capacity (kJ/(kg K))
e specific exergy (kJ/kg) Greek symbols
E_ exergy flow rate (kW) g efficiency (–)
h specific enthalpy (kJ/kg)
I_ irreversibility rate (kW) Subscripts
M molar mass (g/mol)
I first law (–)
m _ mass flow rate (kg/s) II second law (–)
P pressure (bar) cond condenser (–)
PP pinch point temperature difference (°C) evap evaporator (–)
Q_ heat transfer rate (kW)
ext external (–)
s specific entropy (kJ/kg K) hc heat carrier (–)
T temperature (°C) in input stream (–)
DT hs temperature glide cooling fluid (°C) int internal (–)
T pp pinch point temperature heat carrier (°C)
N number of discretizations (–)
W_ work (kW) o dead state (–)
wf working fluid (–)
Abbreviations
HTC heat transfer coefficient (–)
ORC Organic Rankine Cycle (–)

Systematic studies which investigate the thermodynamic influ-
ence of varying mixture composition on the Organic Rankine Cycle
components are valuable but scarce. Second law analysis provides
the tools for this research. The use of second law analysis on Or-
ganic Rankine Cycles is well-known in open literature. Mago
et al. [15] examined the exergy destruction in Organic Rankine Cy-
cles. Visual representations using an exergy wheel clearly show the
exergy accounting for each thermodynamic process. The results
show that the evaporator has by far the highest exergy destruction
rate, followed by the turbine. Therefore, it seems that cycle modi-
fications, of which the aim is to reduce exergy destruction in the
evaporator, have a major potential to increase the power output
of the ORC. Roy et al. [16] studied the output power, the second
and first law efficiency and irreversibilities of an ORC using R12,
R123 and R134a as working fluids. The ORC was driven by flue
gas waste heat at 140 °C. Their results show that the point of max-
imum thermal efficiency and maximum power output do not coin-
cide. Furthermore the second law efficiency is strongly affected by
the pinch point temperature difference in the evaporator. The opti-
mal evaporation temperature for a subcritical ORC based on max-
imization of the second law efficiency was investigated by Liu et al.
[17].
Only a few studies investigate the ORC with zeotropic mixtures
from a second law perspective. Furthermore, only a limited selec-
tion of working fluids are considered. Heberle et al. [18] investi-
gated the second law efficiency of an ORC with zeotropic
mixtures of isobutane–isopentane and R227ea–R245fa as working
fluids. The results show that for temperatures below 120 °C the
second law efficiencies increased in the range of 4.3–15%. The opti-
mal second law efficiency was achieved when the temperature
glide of condensation and cooling water matched. Ho et al. [5]
compared the Organic Flash Cycle (OFC) to an optimized basic
ORC cycle, a zeotropic rankine cycle with a binary ammonia–water
mixture and a transcritical CO2 cycle. A distinction is made be-
tween utilization efficiency and second law internal efficiency.
The former definition assumes that the exergy which is left in
the waste heat stream is discarded or unused, while the latter dis-
cards exergy destruction due to heat transfer in the evaporator. The
definition of second law efficiency is therefore not unique; it is
based on a carefully selected set of chosen input and output
streams. Therefore, a clear understanding of the purpose of the sys-
tem is needed before defining the second law efficiency [19].
The objective of this study is to analyze the performance of zeo-
tropic working fluids based on a second law analysis. The work
focusses on non-superheated subcritical cycles. Comparisons are
made among a selection of zeotropic working fluids. Special care
is taken to quantify the distribution of irreversibilities within the
system. The ORC is optimized and the cause of the optimization
potential is analyzed.
2. Cycle
2.1. Description of the ORC
The schematic diagram of the ORC analyzed in this study is gi-
ven in Fig. 1. Fig. 1a shows the basic cycle while Fig. 1b represents
the cycle with recuperator. The basic ORC consists of a pump which
pressurizes the working fluid and transports it to the evaporator. In
the evaporator the working fluid is heated to the point of saturated
vapor. Next, the working fluid expands through the turbine and
produces work. This shaft power is then converted to electric
power by the generator. The superheated working fluid at the out-
let of the turbine is condensed to saturated liquid in the condenser.
The liquid working fluid is again pressurized by the pump, com-
pleting the cycle. A recuperator (Fig. 1b) cools down the super-
heated vapor at the exit of the expander and heats up the
working fluid after the pump. As a result, the load on the condenser
is decreased.
2.2. Working fluid selection
The selected pure working fluids are all hydrocarbons and can be
found in Table 1. The selection corresponds with that of a previous
study by the authors [14]. Guidelines for mixture component selec-
tion in cryogenic applications are adopted [20,21]. The first compo-
nent is volatile at 1–1.5 bar and therefore, low temperatures after
expansion can be obtained without the need to reach vacuum. The

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
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 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx 3

(a) (b)

Fig. 1. Schematic diagram of the basic ORC (a) and ORC with recuperator (b).

Table 1 [22] provides the thermophysical data of the studied mixtures and
Thermophysical properties of the selected pure working fluids. pure fluids.
Fluid M (g/mol) T crit (°C) P crit (bar) T boiling (°C)
 A discretized model is developed for the evaporator.
Cyclohexane 84.2 280.5 40.8 80.3
Hexane 86.2 234.7 30.3 68.3 ev ap ev ap ev ap ev ap
_ wf ¼ cp;hc  m
ðhwf ;x  hwf ;ðx1Þ Þ  m _ hc  ðT hc;x  T hc;ðx1Þ Þ ð1aÞ
Isobutane 58.1 134.7 36.3 12.1
ev ap ev ap ev ap ev ap
Isohexane 86.2 224.6 30.4 59.8 hwf ;1 ¼ hwf ;in ; T hc;1 ¼ T hc;out ð1bÞ
Isopentane 72.1 187.2 33.8 27.4 ev ap ev ap ev ap ev ap
Pentane 72.1 196.6 33.7 35.7 hwf ;N ¼ hwf ;out ; T hc;N ¼ T hc;in ð1cÞ
R245fa 134.0 154.0 36.5 14.8 ev ap ev ap
PP ev ap ¼ minðT hc;x  T wf ;x Þ ð1dÞ
R365mfc 148.1 186.9 32.7 39.8

Numerical simulations show that discretization with N = 15 is ade-

quate to have an accuracy of one Watt of power output.
second component exceeds both the desired average condensation  The model of the condenser is analogous to that of the
temperature and the boiling point of the first component. The final evaporator.
selection of mixtures is: isopentane–hexane, isopentane–cyclohexane,  The model of the pump and turbine are characterized by their
isopentane–isohexane, pentane–hexane, isobutane–isopentane, isentropic efficiency:
R245fa–pentane, R245fa–isopentane and R245fa–R365mfc. The isen
most volatile component is always the first component in the
hpump;out  hpump;in
_ pump ¼ m
W _ wf  ð2aÞ
mixtures name. gpump
W _ wf  gturbine ðhturbine;in  hisen
_ turbine ¼ m
turbine;out Þ ð2bÞ
3. Model and assumptions
With these equations the model is fully defined and the thermal
The ORC is evaluated assuming steady state conditions of all efficiency is calculated as:
components. Furthermore, heat loss to ambient or pressure drops
are neglected. An upper pressure limit of 90% of the critical pres- _
W
gI ¼ _ net ð3Þ
sure of the fluid is imposed in order to ensure a stable and safe Q ev ap
operation. As each of the working fluids discussed are dry fluids X
N
ev ap ev ap
and superheating is omitted. The ORC, heat source and heat sink Q_ ev ap ¼ _ wf
ðhwf ;x  hwf ;ðx1Þ Þ  m ð4Þ
parameters are summarized in Table 2. The REFPROP 9.0 database x¼1

3.1. Second law analysis

Table 2
ORC, heat source and heat sink parameters. In this work an exergy approach was chosen to investigate the
potential of zeotropix mixtures for ORCs. As such, a direct compar-
ORC
Isentropic pump efficiency gpump 60%
ison is provided to the maximum attainable power output for a
Isentropic turbine efficiency gturbine 75% reversible cycle. However, an analysis on an energy basis [23]
DT pinch evaporator PP ev ap 10 °C should give the same optimization results.
DT pinch condenser PP cond 10 °C Exergy defines the work potential of a system or component. In
Heat source order to calculate the exergy, a dead state (P 0 ; T 0 ) needs to be de-
Inlet temperature heat carrier T hc;in 150 °C fined. This is typically the ambient condition. When the system
Mass flow rate heat carrier m_ hc 20 kg/s reaches thermal and mechanical equilibrium with the given dead
Heat carrier medium hc Water
state, there is no potential of doing work. Kinetic and potential con-
Heat carrier pressure P hc 5 bar
tributions on the flow exergies were assumed to be negligible.
Heat sink
Therefore, the specific exergy e for a steady state stream is given by:
Inlet temperature cooling water T hs;in 20 °C
Outlet temperature cooling water T hs;out 30 °C
e ¼ h  h0  T 0 ðs  s0 Þ ð5Þ

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By multiplying the specific exergy with the mass flow rate the  Condenser
exergy flow is obtained:
I_cond ¼ ðm
_ cf econd _ cond _ cond _ cond
cf ;in þ mwf ewf ;in Þ  ðmcf ecf ;out þ mwf ewf ;out Þ ð9Þ
E_ ¼ me
_ ð6Þ
 Recuperator
A qualitative exergy flow diagram for the ORC with recuperator
ev ap
is given in Fig. 2. The external exergy flow E_ ehc;in v ap
that enters the _ wf ½ðepump
I_recup ¼ m turbine cond
wf ;out þ ewf ;out Þ  ðewf ;in þ ewf ;in Þ ð10Þ
system amounts to the maximum attainable power production.
 Pump
Furthermore, there is an internal exergy flow E_ ewfv ap ;in
to the evapora-
tor. The irreversibilities in the heat exchangers related to finite I_pump ¼ W _ wf ðepump
_ pump  m pump
wf ;out  ewf ;in Þ ð11Þ
temperature heat transfer are given as I_ev ap ; I_cond and I_recup . There
are no internal irreversibilities associated to pressure losses in  Turbine
the heat exchangers. The exergy flow E_ ewfv ap enters the turbine,
;out
_ turbine is produced and an exergy flow E_ turbine leaves. Part I_turbine ¼ m
_ wf ðeturbine turbine _
wf ;in  ewf ;out Þ  W turbine ð12Þ
work W wf ;out
of this exergy goes to the recuperator, while the remaining part
E_ cond
wf ;in goes to the condenser. The cooling water that enters the con- In order to make a fair comparison between cycle designs, a
denser has an exergy flow E_ cond _ cond
cf ;in and an exergy flow Ecf ;out is rejected consistent thermodynamic performance criterion is necessary. This
to the ambient. Irreversibilities in the pump and turbine are criterion should in essence be an indicator of the availability of the
respectively indicated as I_pump and I_turbine . studied thermodynamic cycle to convert waste heat to work. This
The irreversibility rates of the components for a steady state is accomplished by defining efficiencies based on exergy. DiPippo
flow are calculated as follows: [19] states that the efficiency based on the second law of thermo-
X 
T0 _ X X dynamics is the best comparison criteria. The framework of exergy
0¼ 1 _ þ
Qj  W _ in ein 
m _ out eout  I_
m ð7Þ
Tj analysis is extensively discussed in the work of among others Bejan
j in out
et al. [24], Moran and Shapiro [25] and Winterbone [26]. The
This gives for the components: second law efficiency gII is given as:
_
W
 Evaporator gII ¼ _ evnet ð13Þ
E ap hc;in
ev ap ev ap
I_ev ap ¼ ðm
_ hc ehc;in _ wf ewf
þm _ ev ap _ ev ap
;in Þ  ðmhc ehc;out þ mwf ewf ;out Þ ð8Þ
ev ap ev ap ev ap
E_ hc;in _ hc  ðhhc;in
¼m  h0  T 0 ðshc;in  s0 ÞÞ ð14Þ
v ap
With E_ ehc;in
the exergy flow to the system. The second law effi-
ciency is further decomposed in a second law external efficiency
(gII;ext ) and a second law internal efficiency (gII;int ). The former is
related to the heat input to the cycle and the latter is related to
the irreversibilities in the ORC.

gII ¼ gII;ext  gII;int ð15Þ

ev ap ev ap
E_ hc;in  E_ hc;out
gII;ext ¼ ð16Þ
E_ ev ap
hc;in
_
W
gII;int ¼ _ ev ap net_ ev ap ð17Þ
E E
hc;in hc;out

The exergy destruction ratio yD is introduced to compare rela-

tive component irreversibilities in case of different exergy inputs:

I_component
yD;component ¼ ð18Þ
_Eev ap  E_ ev ap
hc;in hc;out

This factor gives the percentage of exergy input to the cycle that
is destroyed in a component due to irreversibilities.
A comparative analysis is made by evaluating the exergy
destruction ratio to reference values of a pure working fluid. The
most volatile component in the mixture is chosen as working fluid
for the reference case.

DyD;component ¼ yD;component  yref

D;component ð19Þ

The sum of DyD;component over the different components is a mea-

sure of the change in irreversibilities between a thermodynamic
cycle with a zeotropic mixture as working fluid and a pure working
fluid.

3.2. Optimization

Throughout this work the second law efficiency gII is

Fig. 2. Exergy flow diagram of the ORC cycle with recuperator. maximized, unless otherwise stated. The optimization variables

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 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx
are the evaporating pressure and the mixture concentration. If the
mixture concentration is fixed, only the evaporation pressure is
optimized. Optimization is done with a Generalized Reduced Gra-
ev ap
dient (GRG) nonlinear multistart algorithm [27]. Since E_ hc;in is con-
stant for a given heat source, optimization of the second law
efficiency is equal to optimization of the net power output.
4. Results
4.1. Effect of zeotropic mixtures
In this section R245fa–isopentane is used as a reference case to
illustrate the different effects of zeotropic mixtures. Deviations and par-
ticularities for other mixtures (R245fa–pentane, R245fa–R365mfc,
isopentane–isohexane, isopentane–cyclohexane, isopentane–
isohexane, isobutane–isopentane, pentane–hexane) are discussed
in Section 4.2.
In Fig. 3c, gII is plotted in function of the mixture concentration.
An optimal mixture concentration of 0.28/0.72 gives an increase of
8.45% in second law efficiency compared to the pure working fluid
R245fa. Both are evaluated at their optimal evaporation pressure.
The source of this increase and the underlying optimization strat-
egy are analyzed further.
4.1.1. Internal and external second law efficiency
In a first step the absorbed heat and heat conversion to power
are decoupled by plotting gII;ext and gII;int (see Fig. 4c) for R245fa–
isopentane. By using a mixture as working fluid more heat is
transferred to the ORC (higher gII;ext ) and heat is converted more
effectively to power (higher gII;int ). Furthermore, for R245fa–
isopentane, the optimal concentration which maximizes gII;ext and
gII;int is equal and coincides with that of maximum second law
efficiency gII .
An increase in gII;int is the result of a lower overall exergy
destruction in the cycle. The source of the reduced exergy destruc-
tion is investigated by calculating DyD for all components. For
R245fa–isopentane DyD;cond and DyD;ev ap are given in Fig. 5c while
DyD;turbine and DyD;pump are given in Fig. 6c. Note that the values of
DyD;cond are generally larger than that of DyD;ev ap ; DyD;turbine or
DyD;pump . Especially the pump has a low effect on the cycle internal
performance when varying mixture concentration. Furthermore it
is important to notice that the minimum value of DyD;cond is found
at the same concentration that maximizes gII;int .
Fig. 7 gives the QT diagram for the optimized ORC with pure
working fluid (R245fa, full line) and with mixture (R245fa–isopen-
tane, dashed line). The heat carrier is cooled down to a lower tem-
perature when using a mixture. Firstly, this is due to the matching
(a) (b)
Fig. 3. Second law efficiency of zeotropic mixtures in function of mixture concentration (optimal evaporation pressure), (a) isopentane-isohexane, isopentane-cyclohexane,
isopentane-hexane, (b) isobutane-isopentane, pentane-hexane, (c) R245fa-pentane, R245fa-isopentane, R245fa-R365mfc.
Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028
5
temperature glide in the condenser which lead to a decrease in
working fluid outlet temperature at the condenser. Also, the pinch
point temperature is reduced, lowering the heat input limitation
induced by the pinch point temperature difference. This is the fur-
ther is discussed in Section 4.1.2. Furthermore, an increase in heat
input follows when the latent heat capacity rate of the mixture is
reduced [28]. This shifts the pinch point to the right in a QT dia-
gram allowing a larger cooling of the heat carrier.
4.1.2. Analysis of the optimal pinch point temperature
In this section, the difference between the optimal pinch point
temperature for pure fluids and zeotropic mixtures is discussed.
The pinch point temperature T pp in this work, is defined as the tem-
perature of the heat carrier at the point of minimum temperature
difference between working fluid and heat carrier. The evaporation
pressure unambiguously determines the pinch point temperature
and vice versa. A cycle with R245–isopentane is constructed with
as reference T pp the optimal T pp of an ORC with pure R245fa
(103.8 °C). Only the second optimization variable, the concentra-
tion, is optimized in this cycle.
Fig. 8 gives the QT diagram for this suboptimal reference cycle.
The cycle with pure R245fa is shown as a full line. Again, the heat
input to the cycle is increased due to matching temperature pro-
files in the condenser and the location of the pinch point. However,
the heat input is lower than with an optimal pinch point temper-
ature (see Fig. 7). The discussion below explains what happens if
the pinch point temperature is optimized.
From Fig. 9 it is clear that, between mixture concentrations 0 to
0.7 the optimal pinch point temperature is larger than that of the
reference case. The results for external and internal second law
efficiency for the reference case and the optimal case is given in
Fig. 10. Between mixture concentrations 0–0.7 the internal second
law efficiency gII;int is larger for the reference cycle while the exter-
nal second law efficiency gII;ext is lower. For the cycle with optimal
pinch point temperature, internal second law efficiency is thus sac-
rificed for increased heat input. Mixture concentrations from 0.7 to
1 are optimized by increasing the pinch point temperature. Inter-
nal second law efficiency is increased in detriment of a decreased
heat input. By optimizing the evaporating pressure and thus the
pinch point temperature an optimal balance is found between
gII;int and gII;ext maximizing the internal efficiency gII .
4.1.3. Glide slopes
For the mixture R245fa–isopentane the optimal concentration
(0.28/0.72) corresponds to the maximum glide slope possible in
the condenser and evaporator (see Fig. 11). As discussed earlier,
matching the glide slope of the working fluid in the condenser to
the glide slope of cooling fluid increases the heat input (gII;ext )
(c)
6 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx

(a) (b) (c)

Fig. 4. Internal gII;int and external gII;ext second law efficiency of zeotropic mixtures in function of mixture concentration (optimal evaporation pressure), (a) isopentane-
isohexane, isopentane-cyclohexane, isopentane-hexane, (b) isobutane-isopentane, pentane-hexane, (c) R245fa-pentane, R245fa-isopentane, R245fa-R365mfc.

(a) (b) (c)

Fig. 5. DyD;cond and DyD;ev ap for zeotropic mixtures in function of mixture concentration (optimal evaporation pressure), (a) isopentane-isohexane, isopentane-cyclohexane,
isopentane-hexane, (b) isobutane-isopentane, pentane-hexane, (c) R245fa-pentane, R245fa-isopentane, R245fa-R365mfc.

(a) (b) (c)

Fig. 6. DyD;turbine and DyD;pump for zeotropic mixtures in function of mixture concentration (optimal evaporation pressure), (a) isopentane-isohexane, isopentane-cyclohexane,
isopentane-hexane, (b) isobutane-isopentane, pentane-hexane, (c) R245fa-pentane, R245fa-isopentane, R245fa-R365mfc.

but also contributes considerably to the increase of conversion effi- C without recuperator ¼ 0:28=0:72). However, compared to the ORC with-
ciency gII;int . As a result matching the glide slopes in the condenser out recuperator, the internal second law efficiency (gII;int ) is higher
is crucial when optimizing the power output. while the external second law efficiency (gII;ext ) and second law
efficiency (gII ) are lower. This is illustrated in Fig. 12 where the rel-
4.1.4. Effect of the recuperator ative change of gII;int ; gII;ext , and gII is shown in function of the mix-
In this section, the influence of adding a recuperator to the basic ture concentration. An increase in gII;int implies that the conversion
ORC is analyzed. The optimal pressure and concentration to maxi- from exergy to electric power occurs more efficiently. In contrast, a
mize the net power output are approximately equal for an ORC decrease in gII;ext implies that the heat input to the ORC is reduced.
with and without recuperator (P recuperator
ev ap ¼ 8:47 bar, The second law efficiency gII is reduced, since the decrease in heat
recuperator without recuperator
C ¼ 0:29=0:71 versus P ev ap ¼ 8:43 bar, input is slightly larger than the increase in conversion efficiency.

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
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 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx 7

Fig. 7. QT diagram R245fa–isopentane (optimal concentration and evaporation pressure) and pure working fluid R245fa (optimal pressure).

Fig. 8. QT diagram R245fa–isopentane (optimal concentration, fixed pinch point temperature 103.8 °C) and pure working fluid R245fa (optimal pressure).

Fig. 10. gII;ext and gII;int in function of mixture concentration for optimal and
Fig. 9. Pinch point temperature and pressure in function of mixture concentration
reference pinch point temperature (=103.8 °C) (R245fa–isopentane).
with optimal and reference pinch point temperature (=103.8 °C) (R245fa–
isopentane).

and outlet of the condenser increases. As a result, the logarithmic

In Fig. 12, the higher temperature glide of the working fluid (the mean temperature difference increases, leading to a higher heat
glide slope peaks at a concentration of 0.2/0.8) result in a larger de- recuperation and a decreased heat input at the evaporator.
crease of gII . This is due to the imposed pinch point temperature The cause of the improved gII;int is further explained by plotting
difference at the recuperator. When the temperature glide gets ywithout recuperator
D;component  ywith recuperator
D;component in function of mixture concentration,
higher, the temperature difference between the exit of the turbine as is done in Fig. 13. This shows that the irreversibilities in the

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028
8 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx
Fig. 11. Glide slope of R245fa–isopentane in evaporator and condenser in function
of concentration.
Fig. 12. Relative difference in % between ORC with and without recuperator in
function of mixture concentration for: gII ; gII;int ; gII;ext (optimal evaporation pressure,
R245fa–isopentane).
Fig. 13. ywithoutrecuperator
D;component  ywithrecuperator
D;component in function of mixture concentration for:
evaporator, condenser, recuperator (optimal evaporation pressure, R245fa–
isopentane).
evaporator and condenser are lower for an ORC with a recuperator.
This agrees with the general interpretation that the average heat
rejection temperature is lowered and the average heat addition
temperature is increased by the incorporation of a recuperator.
As a result, the working fluid better matches the temperature pro-
files of the cooling and heating medium, reducing the irreversibil-
ities at the condenser and evaporator.
For other mixtures as working fluid, the effect is similar. The
second law efficiency of an ORC with recuperator closely approxi-
mates the second law efficiency of the ORC without recuperator.
Only when the cooling of the heat carrier is constrained or the heat
after the ORC is used, a recuperator can be beneficial. This is the
Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028
case in geothermal, combined heat and power, or in waste heat
applications when condensation of the flue gas should be avoided.
Furthermore, the recuperator adds an extra pressure drop, which is
not taken into account in this study, but will further decrease the
second law efficiency. In addition, the investment cost of the ORC
is increased by adding a recuperator. Therefore, no recuperator is
added to the ORC in the following discussions.
4.2. Comparison of mixture compositions
Besides R245fa–isopentane other mixtures are investigated:
R245fa–pentane, R245fa–R365mfc, isopentane–isohexane, isopen-
tane–cyclohexane, isopentane–isohexane, isobutane–isopentane,
pentane–hexane. With the above discussion in mind the specifics
of these mixtures are examined.
For the mixtures isopentane–cyclohexane, isopentane–hexane
and isobutane–isopentane two local maxima are observed for gII
in function of the mixture concentration (Fig. 3). These maxima oc-
cur when the temperature glide of the mixture condensation ex-
ceeds the temperature glide of the cooling water. This leads to a
decrease in gII;int between these two maxima (Fig. 4) due to an in-
crease in irreversibilities in the condenser (DyD;cond , Fig. 5). The
external second law efficiency is constant or increases and thus
does not contribute to the creation of the local maxima. There is
however only one global maximum. This is primarily accounted
to the variation in pump irreversibilities, as can be noticed in
Fig. 6. High pump irreversibilities are found for large pumping
powers. The large pumping power is a result of a high mass flow
rate or a high pressure difference over the pump.
Especially for isobutane–isopentane the irreversibilities in the
pump have a noticeable effect when changing mixture concentra-
tion (Fig. 6b). The cause is the large decrease of pressure difference
over the pump: from 14.6 bar for pure isobutane to 4.62 bar for
pure isopentane. For the other mixtures, the pressure difference
over the pump is only around 5 bar or lower. Furthermore, for
the mixture isobutane–isopentane, there is a large increase in
DyD;ev ap when going to higher concentrations of isopentane
(Fig. 5b). This is explained by the optimization strategy. In order
to maximize the second law efficiency, the pinch point tempera-
ture is strongly reduced (12 °C in comparison to pure isobutane).
This in turn increases the irreversibilities in the evaporator.
4.3. Optimal mixture composition
In Table 3 the results of the optimization of pressure and mix-
ture concentrations are summarized. It is clear that the use of zeo-
tropic mixtures increases gII . For working fluids with optimal
mixture concentration and optimal pressure the variation in sec-
ond law efficiency is low (between 30.94% and 32.05%). The best
result (gII = 32.05%) is found for a mixture of isobutane–isopentane
with a concentration of 0.81/0.19. Both the internal and external
second law efficiencies are higher for the ORC with mixtures as
working fluid. The optimal condensing glide slope is slightly smal-
ler than the glide slope of the cooling fluid. This is a result of the
change in DyD for the evaporator, pump and turbine when chang-
ing mixture composition (Figs. 5 and 6). The optimal evaporation
pressures for the mixtures are lower than those of the most volatile
component in the mixture. This is favorable in view of construction
and operation.
The relative improvement in second law efficiency is within
7.1% to 14.2% and is presented in Fig. 14. The increase of perfor-
mance between pure working fluid and mixture is the largest for
isopentane when mixing with isobutane (an increase of 14.2%).
R245fa is best mixed with pentane to maximize the power output.
The working fluid which is the least volatile in the mixture benefits
most from adding a more volatile component.
 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx 9

Table 3
Characteristic cycle parameters for heat carrier at 150 °C (optimal evaporation pressure and concentration).

Working fluid C [mole frac.] gI (%) gII gII;ext gII;int P ev ap P cond Slope evap Slope cond m_ wf W_ turbine W_ pump
(%) (%) (%) (bar) (bar) (°C) (°C) (kg/s) (kW) (kW)
Isopentane 1 9.05 28.07 75.92 36.98 6.08 1.46 0.0 0.0 46.5 1810 59.6
Hexane 1 8.94 27.65 74.57 37.08 1.95 0.36 0.0 0.0 42.5 1741 17.6
Cyclohexane 1 9.14 26.71 71.39 37.42 1.35 0.24 0.0 0.0 39.1 1675 9.5
Pentane 1 9.05 27.84 75.11 37.07 4.91 1.12 0.0 0.0 43.5 1781 45.4
Isohexane 1 8.91 27.87 75.36 36.98 2.48 0.48 0.0 0.0 44.9 1761 23.6
R245fa 1 9.39 28.67 76.31 37.58 11.29 2.43 0.0 0.0 90.8 1888 99.7
R365mfc 1 8.95 28.39 76.67 37.03 4.85 0.96 0.0 0.0 82.8 1814 43.7
Isobutane 1 10.04 29.14 77.20 37.74 19.78 5.19 0.0 0.0 46.5 1810 239.4
Isopentane–hexane 0.19–0.81 9.09 30.94 79.70 38.82 2.41 0.42 7.0 8.8 44.8 1952 23.2
Isopentane–cyclohexane 0.08–0.92 9.27 30.06 76.88 39.11 1.56 0.26 7.4 9.3 41.7 1886 11.9
Isopentane–isohexane 0.44–0.56 9.22 31.63 80.52 39.29 3.75 0.72 7.1 8.7 47.5 2011 38.3
Pentane–hexane 0.54–0.46 9.32 31.39 79.30 39.59 3.19 0.57 7.0 8.3 44.3 1988 30.6
Isobutane–isopentane 0.81–0.19 9.61 32.05 81.91 39.13 13.48 3.36 6.9 9.3 52.0 2154 156.0
R245fa–pentane 0.33–0.67 9.46 31.76 80.27 39.57 7.35 1.50 8.0 7.5 60.9 2053 72.8
R245fa–isopentane 0.28–0.72 9.38 31.11 80.01 38.88 8.43 1.85 6.4 5.7 61.9 2027 87.6
R245fa–R365mfc 0.41–0.59 9.29 31.39 80.46 39.01 7.20 1.37 5.7 6.4 88.3 2025 68.0

The irreversibility distributions are given for zeotropic mixtures
as working fluid with optimal mixture concentration and pressure
(Fig. 15) and for pure working fluids with optimal pressure
(Fig. 16). The evaporator contributes the most to the losses in the
ORC (around 50%) followed by the condenser (around 30%), turbine
(around 19%) and pump (around 1%). For pure isobutane, but also
for the mixture isobutane–isopentane, the pump takes a relatively
large share of the total irreversibilities compared to other working
fluids. The reason and effect of this was discussed in Section 4.2.
Important to notice is the shift in irreversibility distribution be-
tween the pure working fluid and a mixture as working fluid. As
discussed earlier, the improved performance is the result of a
reduction in irreversibilities in the condenser. The result of the
optimization therefore reduces the share of condenser losses rela-
tive to the total losses in the cycle. For the current working fluids
the reduction lies between 3 and 6 percentage points.
4.4. Sensitivity studies
dominant, this results in an increased pinch point temperature dif-
ference for a fixed heat exchanger area and vice versa. Therefore, in
a cost benefit analysis a thermo-economic approach is crucial. To
have a first assessment, the sensitivity of the pinch point temper-
ature difference on the second law efficiency is studied. The pinch
point temperature difference in both the evaporator and condenser
are incrementally increased from 10 °C tot 13 °C.
In Fig. 18 the results of this analysis is given for the different
mixtures under consideration. The decrease in gII in the given
range is approximately linear. For a decrease of 1 °C in both the
condenser and evaporator, an absolute reduction of around 1 per-
centage point in second law efficiency is observed. It is interesting
to note, that in general a pinch point temperature increase of 3 °C
in the condenser and evaporator, already outweighs the observed
performance benefit associated to zeotropic mixtures. Further-
more, the ranking in terms of gII stays the same for each calculated
pinch point temperature difference.

4.4.1. Sensitivity on inlet heat carrier temperature

In a next step, the inlet temperature of the heat carrier is varied
between 120 °C and 160 °C, while optimizing the pressure and
concentration in order to maximize the net output power. In
Fig. 17 the resulting second law efficiency is shown for the various
mixtures investigated. The second law efficiency in function of the
inlet temperature shows an almost linear behavior for all the
investigated mixtures. The difference between the best and worst
performing working fluid is between 1 to 3 percentage points.
Therefore in order to further differentiate the best working fluid
thermo-economic considerations [29] should be taken into ac-
count. A mixture of isopentane–isobutane has the highest second
law efficiency in the range 130 °C to 160 °C. At 120 °C a mixture
of isopentane–isohexane has the highest second law efficiency.
For increasing heat carrier inlet temperatures the difference be-
tween second law efficiency of isopentane–isohexane and isopen-
tane–isohexane increases. In contrast to the optimal evaporation
pressure, the optimal concentration only changes slightly from
the values given in Table 3. Again, this indicates that primarily
the condenser operating conditions affect the use of zeotropic
mixtures.
4.4.2. Sensitivity on pinch point temperature difference
The convective heat transfer coefficient (HTC) of zeotropic mix-
tures is usually lower compared to pure fluids. An extensive over-
view of the degradation effects on the HTC is found in the work of
Rajapaksha [8]. If the convective HTC on the working fluid side is
4.4.3. Sensitivity on cooling fluid glide slope
The sensitivity with respect to the temperature glide of the
cooling fluid DT hs is evaluated by performing calculations for a
variety of temperature glides, i.e. 5, 10 and 15 °C. These correspond
with a cooling fluid outlet temperature of 25, 30, 35 °C. In Table 4
the results of the sensitivity analysis on the cooling fluid tempera-
ture glide are given. The working fluid with the highest second law
efficiency is R245fa–R365mfc for DT hs ¼ 5 °C, isobutane–isopen-
tane for DT hs ¼ 10 °C and isopentane–hexane for DT hs ¼ 15 °C.
Mixtures with R245fa have the lowest glide slope for the work-
ing fluid. They provide the highest second law efficiency for a
DT hs ¼ 5 °C. For larger DT hs these mixtures are not able to achieve
a good match with the cooling fluid. Mixtures with R245fa are
therefore preferred for low DT hs . Isopentane–cyclohexane has as
only working fluid a good match for DT hs ¼ 15 °C. Still, isopen-
tane–hexane has a larger second law efficiency due to a better tem-
perature glide match in the evaporator associated to a lower latent
heat of the mixture.
In contrast to a change in pinch point temperature difference or
heat carrier inlet temperature, the glide slope of the cooling fluid
has a decisive effect on the selection of the optimal working fluid.
This supports the importance of matching the cooling fluid glide
slope in the condenser. For DT hs ¼ 5 °C, all the mixtures provide
a good temperature glide match. However, for larger DT hs not all
the mixtures achieve a sufficient large glide slope in the condenser,
which is reflected in a lower second law efficiency.

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
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10 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx

4.5. Comparison to other work

Some noteworthy remarks from literature related to the pre-

Fig. 14. Relative improvement when using mixtures compared to the pure working
fluids (optimal evaporation pressure and concentration).
sented results are listed in this section.
First of all, Heberle et al. [18] investigated mixtures of R245fa–
R227ea and isobutane–isopentane as working fluids for geother-
mal ORCs. Their results showed that for temperatures below
120 °C the second law efficiency increased in the range of 4.3–
15% by using zeotropic mixtures. In this work, more fluids were
investigated and a comparable improvement of second law effi-
ciency is found for a heat carrier of 150 °C. In addition, the impor-
tance of matching the temperature glide at condensation with the
temperature difference of the cooling water is supported.
Garg et al. [12] investigated mixtures of isopentane and R245fa. A
mixture concentration of 30% R245fa and 70% isopentane was specifi-
cally chosen to suppress flammability of isopentane. In this study,
approximately the same mixture concentration leads to a maximiza-
tion of the second law efficiency under the conditions given in Table 2.

Fig. 15. Irreversibility distribution for an ORC with zeotropic mixtures as working fluid (optimal evaporation pressure and concentration).

Fig. 16. Irreversibility distribution for an ORC with pure working fluids (optimal evaporation pressure).

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028
 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx 11

Fig. 17. Second law efficiency gII in function of variable heat carrier temperature between 120 °C and 160 °C (optimal evaporation pressure and concentration).

Fig. 18. Second law efficiency gII in function of variable pinch point temperature difference between 10 °C and 13 °C) (optimal evaporation pressure and concentration).

Table 4
Results of the sensitivity analysis on the cooling fluid temperature glide DT hs : second law efficiency and working fluid temperature glide (optimal evaporation pressure and
concentration).

Working fluid Temperature glide cooling fluid condenser DT hs

5 °C 10 °C 15 °C
gII Slope WF gII Slope WF gII Slope WF
cond (° C) cond (° C) cond (° C)
Isopentane–hexane 32.08 4.4 30.94 8.8 30.43 12.8
Isopentane–cyclohexane 32.30 5.6 30.06 9.3 29.73 18.4
Isopentane–isohexane 32.65 5.4 31.63 8.7 28.70 8.7
Pentane–hexane 32.45 5.4 31.39 8.3 28.44 8.3
Isobutane–isopentane 33.71 4.8 32.05 9.3 30.37 11.8
R245fa–pentane 33.41 5.3 31.76 7.5 28.80 7.6
R245fa–isopentane 33.56 4.7 31.11 5.7 28.18 5.8
R245fa–R365mfc 33.59 4.7 31.39 6.4 28.39 6.4

Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
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12 S. Lecompte et al. / Energy Conversion and Management xxx (2014) xxx–xxx
4.5.1. Irreversibility distribution
Several authors report a similar irreversibility distribution as in
this work. Heberle et al. [18] indicates values around 25% for the
share in condenser exergy losses, dependable on the mixture con-
centration of isobutane–isopentane. Zhu et al. [30] compares
water, ethanol, R113, R123 and R245fa as working fluids in an
ORC for engine exhaust heat recovery. Their values for the share
in condenser exergy losses range between 20% and 30%. El-Emama
and Dincer [31] provide an exergoeconomic analyses of a geother-
mal ORC. For an optimized ORC configuration with a heat carrier
inlet temperature of 160 °C, the condenser accounts for 30.68% in
the total exergy losses. Shengjun et al. [32] compared subcritical
and transcritical ORCs for geothermal applications. Their results
indicate that the share in condenser exergy losses lies between
18.6% and 23.2% for subcritical ORCs. In the works cited above, dif-
ferent boundary conditions are used, yet all of the values fall in a
range between 18.6% and 30%.
However, some studies report a lower share of condenser exer-
gy destruction (between 2% and 5%). This is attributed to two rea-
sons. Firstly, the exergy destruction in the condenser is low if an
isothermal heat sink is used whose temperature is close to the con-
densation temperature of the working fluid [33]. However, this im-
plies an infinite cooling fluid mass flow rate. Secondly, some papers
impose unrealistic temperature profiles in the condenser. In the
work of Tchanche et al. [34] the cooling fluid (water) exits the
condenser at a higher temperature than the working fluid inlet
temperature. Also in the work of Mago et al. [35] the temperature
profiles cross in the condenser. As a result, exergy is locally gener-
ated in the condenser, in violation of the second law. As a conse-
quence, the overall exergy destruction in the condenser is
unrealistically low.
5. Conclusions
Using mixtures in subcritical ORCs as working fluids has been
studied in this paper by using second law analysis. This result in
three interesting conclusions.
Using mixtures results in an improvement of second law effi-
ciency between 7.1% and 14.2% compared to pure working fluids.
The source of this improvement lies in a combination of a higher heat
input (gII;ext ) and a higher heat conversion efficiency (gII;int ) and is
mainly ascribed to decreased irreversibilities in the condenser.
The distribution of irreversibilities has changed and the share of
condenser losses is reduced with 3 to 6 percentage points relative
to the pure working fluid. Exergy losses in the condenser are re-
duced by matching the glide slope of the working fluid with the
glide slope of the cooling fluid. Consequently, an optimal mixture
concentration exists which maximizes the second law efficiency.
The optimal condensing glide slope is slightly smaller than the
glide slope of the cooling fluid due to the exergy losses in the
pump, turbine and evaporator.
The second law efficiency of an ORC using zeotropic mixtures as
working fluid with or without recuperator are approximately
equal.
The second law efficiency in function of the heat carrier temper-
ature between 120 °C and 160 °C shows an almost linear behavior
for all the investigated mixtures. Between 120 °C and 130 °C iso-
pentane–isohexane has the highest second law efficiency. While
between 130 °C and 160 °C isobutane–isopentane has the highest
second law efficiency. However, the difference in second law effi-
ciency between optimized ORCs with zeotropic mixtures as work-
ing fluid is small (around 3 percentage points). As such, thermo-
economic criteria should be taken into account in order to further
differentiate the optimal mixture.
Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028
Acknowledgements
The results presented in this paper have been obtained within
the frame of the IWT SBO-110006 project The Next Generation Or-
ganic Rankine Cycles (www.orcnext.be), funded by the Institute for
the Promotion and Innovation by Science and Technology in Flan-
ders. This financial support is gratefully acknowledged.
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Please cite this article in press as: Lecompte S et al. Exergy analysis of zeotropic mixtures as working fluids in Organic Rankine Cycles. Energy Convers
Manage (2014), http://dx.doi.org/10.1016/j.enconman.2014.02.028