i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0

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Solar hydrogen production via thermochemical

iron oxideeiron sulfate water splitting cycle

Rahul R. Bhosale*, Anand Kumar, Leo J.P. van den Broeke, Shahd Gharbia,
Dareen Dardor, Mehak Jilani, Jamila Folady, Mashail Shaif Al-Fakih,
Mahsa Ali Tarsad
Department of Chemical Engineering, College of Engineering, Qatar University, Doha, Qatar

article info abstract

Article history: This paper reports the thermodynamic analysis of solar H2 production via two-step ther-
Received 18 September 2014 mochemical iron oxideeiron sulfate (IOeIS) water splitting cycle. The first step belongs to
Received in revised form the exothermic oxidation of FeO via SO2 and H2O producing FeSO4 and H2 and second step
19 November 2014 corresponds to the endothermic reduction of FeSO4 into FeO, SO2, and O2. The products,
Accepted 25 November 2014 FeO and SO2 can be recycled to step 1 and hence, reutilized for the production of H2 via
Available online 20 December 2014 water splitting reaction. Thermodynamic equilibrium compositions and variations in
enthalpy, entropy and Gibbs free energy of the thermal reduction and water splitting re-
Keywords: actions were computed as a function of reaction temperatures. Furthermore, the effect of
Solar fuel molar flow rate of inert Ar (n_ Ar ) on thermal reduction temperature (TR) and equilibrium
Iron oxideeiron sulfate water compositions during the thermal reduction of FeSO4 was also examined. Second law
splitting cycle thermodynamic analysis was performed to determine the cycle efficiency ( hcycle ) and solar
Thermodynamics to fuel energy conversion efficiency ( hsolar
to
fuel ) attainable with and without heat recu-
Hydrogen production peration for varying n_ Ar (0e30 mol/s) and TR (1280e1510 K). Results obtained indicate
hcycle ¼ 39.56% and hsolar
to
fuel ¼ 47.74% (without heat recuperation) and hcycle ¼ 51.77% and
hsolar
to
fuel ¼ 62.43% (by applying 50% heat recuperation) at TR ¼ 1510 K.
Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

favored thermodynamically as it requires process heat at

Introduction
H2 is considered as one of the potential energy carriers due to
its capacity of producing 143 MJ/kg of energy (higher in
comparison with the oil, gas, and coal individually) and its
environmentally friendly nature (burning of H2 produces
water with no other polluting gases). Water splitting reaction
is considered as one of the most promising ways for the pro-
duction of H2. However, direct water thermolysis is not
temperatures above 2723 K for obtaining a significant degree
of dissociation of water [1]. Furthermore, to avoid the forma-
tion of an explosive mixture comprised of H2 and O2, a gas
separator unit (for the separation of H2 and O2 at high
temperatures) needs to be equipped near to the water disso-
ciation reactor which further enhances the overall cost of the
H2 production process.
As the direct dissociation of water is not practical due to
the high operating temperature and gas separation problem,

* Corresponding author. Tel.: þ974 4403 4168; fax: þ974 4403 4131.
E-mail addresses: rrbhosle@yahoo.com, rahul.bhosale@qu.edu.qa (R.R. Bhosale).
http://dx.doi.org/10.1016/j.ijhydene.2014.11.118
0360-3199/Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
1640 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0
attempts are currently underway to achieve H2 production via
water-splitting reaction at lower operating temperatures and
via bypassing the formation of H2 and O2 explosive mixture.
Several thermochemical cycles such as iron oxide cycle [2e6],
zinc/zinc oxide cycle [7e10], tin/tin oxide cycle [8,11e13],
mixed ferrite cycle [14e21], ceria cycle [22e24], sulfureiodine
cycle [25e27], and hybrid sulfur cycle [28,29] were investigated
towards H2 production via water-splitting reaction. Among
these, the sulfureiodine cycle (reaction set I) and its variation
the hybrid sulfur cycle (reaction set II) are more appealing as
the required operating temperatures are lower as compared to
other thermochemical cycles.
Reaction set I: sulfureiodine cycle
H2 SO4 /SO3 þ H2 O ð673 KÞ
SO3 4SO2 þ 1=2O2 ð1123
1273 KÞ
SO2 þ 2H2 O þ I2 /H2 SO4 þ 2HI ð393 KÞ
2HI/H2 þ I2 ð573
723 KÞ
Reaction set II: hybrid sulfur cycle
H2 SO4 /SO3 þ H2 O ð673 KÞ
SO3 4SO2 þ 1=2O2 ð1123
1273 KÞ
SO2 þ 2H2 O/H2 SO4 ð353
393 KÞ
For both sulfureiodine cycle and hybrid sulfur cycle, the
most energy consuming step is the dissociation of SO3 into
SO2 and O2. The reduction of SO3 into SO2 and O2 is possible
only under catalytic conditions and takes place at high tem-
perature due to its endothermic nature. Several metal based
catalytic systems have been investigated previously towards
the decomposition of the gaseous SO3 [30]. As sulfation
poisoning is a major concern related to such reactions, the
Fig. 1 e Typical two-step solar thermochemical IOeIS water splitting cycle.
investigated metal catalysts were loaded either on non-
sulfating substrates or substrates forming very stable sul-
fates. At high reaction temperatures, most of the transition
metal catalysts (such as nickel, manganese based) undergo
formation of stable sulfates and resulted as inefficient in
terms of their catalytic activity towards the reduction of SO3
into SO2 and O2 [31]. In contrast, the noble metal catalysts (e.g.,
platinum based) supported on BaSO4eTiO2, ZrO2, or SiO2 were
observed to be active towards the endothermic dissociation of
SO3. Although, the noble metal catalysts are attractive for
such reactions, they are less preferable due to the limited
availability and high cost.
Utilization of metal oxides as the catalytic materials
(instead of noble metal catalysts) and converting the sul-
(1)
fureiodine and hybrid sulfur cycle into a ‘metal oxideemetal
sulfate’ cycle operated using concentrated solar energy is one
(2) of the alternative to achieve H2 production at moderate tem-
peratures. Solar ‘metal oxideemetal sulfate’ thermochemical
(3) cycle utilizes solar energy, metal oxide (MO), SO2 and H2O for
the production of H2 and O2. It is a two-step process in which
(4) the first non-solar step belongs to the exothermic oxidation of
MO by SO2 and H2O producing metal sulfate (MSO4) and H2
(reaction 8). The endothermic step two corresponds to the
(5) solar thermal reduction of MSO4 into MO, SO2, and O2. The MO
and SO2 produced in step 2 are recycled back to step 1 and
(6) hence can be used in multiple cycles.
MO þ SO2 ðgÞ þ H2 OðgÞ/MSO4 þ H2 ðgÞ ðNon
solarÞ (8)
(7)
MSO4 /MO þ SO2 ðgÞ þ 1=2O2 ðgÞ ðSolarÞ (9)
According to the previous investigations [2e24], among the
several MO systems examined for the solar thermochemical
water splitting application, iron oxide based redox materials
are considered as one of the most favorable materials. In this
viewpoint, this paper proposes the utilization of the ‘iron
oxideeiron sulfate’ (IOeIS) cycle for the production of solar H2
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0
via thermochemical water splitting reaction. Typical two-step
solar thermochemical IOeIS water splitting cycle is presented
in Fig. 1. In this study, the thermodynamic feasibility of this
cycle was investigated and obtained results are presented in
detail. At first, the thermodynamic equilibrium compositions
during the solar thermal reduction of FeSO4 under inert at-
mosphere and oxidation of FeO via water splitting reaction
were determined. The variation of the reaction enthalpy, en-
tropy and Gibbs free energy for the thermal reduction and
water splitting steps with respect to the operating tempera-
tures were studied. Furthermore, the maximum theoretical
solar energy conversion efficiency of the IOeIS cycle is
determined by performing the second law thermodynamic
analysis over different solar reactor temperatures and with/
without considering the heat recuperation.
Chemical thermodynamic equilibrium
Simplified chemistry of the solar thermochemical IOeIS water
splitting cycle involving thermal reduction of FeSO4 and water
splitting via FeO oxidation is shown below:
FeO þ SO2 ðgÞ þ H2 OðgÞ/FeSO4 þ H2 ðgÞ
FeSO4 /FeO þ SO2 ðgÞ þ 1=2O2 ðgÞ
The equilibrium thermodynamic calculations related to
Fig. 2 e a) and b) Variations in equilibrium composition as
a function of TS during H2 production via oxidation of FeO
by SO2 and H2O (P ¼ 1 atm, n_ Ar ¼ 0 mol/s).
1641
the IOeIS cycle were performed with the help of commercial
thermodynamic HSC Chemistry software and databases [32]
by assuming a) solar reactor operated in continuous mode
with inlet concentration of FeSO4 equal to 1 mol/s and b) by
considering FeO, SO2(g), H2O(g), FeSO4, H2(g), and O2(g) as the
reactive species.
H2 production via water splitting reaction
Fig. 2a and b represent variations in the equilibrium compo-
sition for step 1 with respect to water splitting temperature
(TS) (in absence of Ar). According to the results presented, the
production of H2 via oxidation of FeO by SO2 and H2O is
possible below 483 K. It is further observed that at lower
temperatures, FeSO4 and H2 are the major species, whereas
the molar concentration of FeO, H2O and SO2 increases with
the increase in TS.
Variations in DHWS , DSWS , and DGWS as a function of TS for
the production of H2 via oxidation of FeO by SO2 and H2O is
presented in Fig. 3a and b. Following are the mathematical
correlations derived from the obtained HSC simulation results
for the estimation of DHWS , DSWS , and DGWS at different TS.



(10) DHWS ¼ 9  10
6 T2s þ ð0:0129ÞTs
ð123:08Þ 300
900 K
(12)
(11)



DSWS ¼
9  10
6 T2s þ ð0:0499ÞTs
257:35 300
900 K
(13)


5


DGWS ¼
2  10 T2s þ ð0:2532ÞTs
119:36 300
900 K
(14)
Fig. 3 e Variations in a) enthalpy and entropy, and b) Gibbs
free energy as a function of TS during H2 production via
oxidation of FeO by SO2 and H2O (P ¼ 1 atm, n_ Ar ¼ 0 mol/s).
1642 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0
According to the results presented in Fig. 3a, DHws is varied
by 11.35% with the increase in the TS from 300 to 900 K. Pre-
sented results further indicate that more amount of
exothermic heat will be released if the water splitting reaction
is carried out at 300 K (
117.94 kJ/mol) instead of 900 K
(
104.56 kJ/mol). Likewise, DSws is also observed to be altered
by 10.79% (from
242.39 J/K mol to
216.23 J/K mol) due to the
increase in the TS from 300 K to 900 K. As the water splitting
reaction has a negative enthalpy and entropy change, this
reaction seems to be more feasible at lower temperatures. The
data related to change in the DGws with respect to TS presented
in Fig. 3b indicate a decrease of 149.40% in DGws with the
decrease in the TS from 900 to 300 K. Furthermore, the results
reported confirm that the production of H2 via oxidation of
FeO by SO2 and H2O is feasible below 483 K.
Step 2: thermal reduction of FeSO4
Similar to the H2 production step, equilibrium thermody-
namic analysis of the thermal reduction of FeSO4 (in absence
of Ar) was also simulated with the help of HSC Chemistry
software and databases. Variations in DHTR , DSTR , DGTR , and
equilibrium compositions as a function of TR are presented in
Figs. 4(a and b) and 5, respectively. The mathematical ex-
pressions (15)e(17) represents the change in the DHTR , DSTR ,
DGTR with respect to TR.



DHTR ¼
7  10
6 T2R
ð0:0079ÞTR þ ð363:93Þ 300
900 K
(15)
Fig. 4 e Variations in a) enthalpy and entropy, and b) Gibbs
free energy as a function of TR during reduction of FeSO4
into FeO, SO2 and O2 (P ¼ 1 atm, n_ Ar ¼ 0 mol/s).



DSTR ¼ 3  10
6 T2R
ð0:029ÞTR þ 297:6 300
900 K (16)



DGTR ¼ 1  10
5 T2R
ð0:296ÞTR þ 361:29 300
900 K (17)
According to Fig. 4a, energy required for performing the
endothermic thermal reduction of FeSO4 i.e. DHTR is decreased
by 6.50% as the TR increased from 300 to 1500 K. Similarly, DSTR
is also reduced by 9.047% with the increase in TR (from 300 to
1500 K). It is further realized that the thermal reduction of
FeSO4 is more viable at high temperature as the reaction
enthalpy and entropy has positive variation. This realization
is further confirmed from the data reported in Figs. 4b and 5.
According to Fig. 4b, DGTR for the thermal reduction of FeSO4
becomes negative above 1290 K (in absence of Ar) which
confirms that this reaction is possible at higher temperatures
as compared to water splitting reaction. Furthermore, the
variations in equilibrium composition related to the thermal
reduction of FeSO4 also confirm the above mentioned
observation.
According to the results reported in previous investigations
[2e24], the thermal reduction of MO can be achieved at lower
temperatures if inert carrier gas is used during the thermal
reduction step. Based on this observation, we examined the
effect of Ar as an inert carrier gas during the thermal reduc-
tion of FeSO4 in a solar reactor. The results reported in Fig. 6a
and b shows the influence of molar flow rate of Ar (n_ Ar ) on
equilibrium composition of gaseous and solid species during
thermal reduction of FeSO4. It is observed that the slope of the
decrease in the molar concentration of FeSO4 and increase in
the molar concentration of FeO, SO2 and O2 is shifted towards
lower TR as the n_ Ar increases. As per the Le-Chatelier's prin-
ciple, due to the inclusion of the inert gas during the solar
thermal reduction of FeSO4, the thermodynamic equilibrium
shifts towards the lower TR as the entropy of the product
gaseous species decreases.
Effect of n_ Ar on TR required for complete conversion of
FeSO4 into FeO, SO2 and O2 is shown in Fig. 7. The results re-
ported indicate that in absence of Ar, the complete conversion
is possible at TR ¼ 1510 K. As the n_ Ar increases upto 5 mol/s, the
required TR for complete conversion decreases to 1410 K. A
further decrease in the TR down to 1280 K is observed with the
Fig. 5 e Variations in equilibrium composition as a
function of TR during reduction of FeSO4 into FeO, SO2 and
O2 (P ¼ 1 atm, n_ Ar ¼ 0 mol/s).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0
Fig. 6 e Effect of n_ Ar on equilibrium composition of a)
gaseous and b) solid species as a function of TR during
reduction of FeSO4 into FeO, SO2 and O2.
increase in n_ Ar upto 30 mol/s. However, additional increase in
n_ Ar upto 100 mol/s is of not much use as required TR reduces
only by 30 K.
Second law thermodynamic analysis
Process configuration and assumptions
To assess the maximum possible energy conversion efficiency
of the solar thermochemical IOeIS water splitting cycle, a
second law thermodynamic analysis (exergy analysis) was
carried out and obtained results are reported in this section. A
process flow configuration for the continuously operated solar
thermochemical IOeIS water splitting cycle is shown in Fig. 8.
This process is comprised of a solar reactor, FeO oxidizer (H2
generator), theoretical H2/O2 ideal fuel cell, gas separator, and
few heaters and coolers. Production of H2 is carried out at
1 atm and steady state conditions with negligible viscous
losses and changes in kinetic and potential energies. It is
worthy to note that, the energy penalty associated with the
separation of SO2 from O2 and Ar are not accounted during the
efficiency calculation. Also, the heat exchangers required for
recovering the sensible latent heat are omitted from thermo-
dynamic considerations. In addition, several other assump-
tions are made as follows:
 The solar reactor is assumed to be a perfectly insulated
blackbody absorber
 No convective/conductive heat losses
1643
 Effective emissivity and absorptivity equal to unity
 All the products separates naturally without expending
any work
 All reactions reach 100% completion
The exergy analysis was carried out by following the
methodology and governing equations derived and used pre-
viously for other MO based solar thermochemical cycles [7,33].
Thermodynamic properties were extracted from HSC soft-
ware and databases and the analysis is normalized to the
FeSO4 molar flow rate (1 mol/s) entering the solar reactor.
Exergy analysis
Solar energy absorption efficiency
The solar energy absorption efficiency is defined as the net
rate at which energy is being absorbed by the solar reactor
divided by the solar energy input through the aperture of the
solar reactor. The solar energy absorption efficiency can be
calculated as:
 4
sTR
habsorption ¼ 1
(18)
IC
where,
I ¼ direct-normal solar irradiance (normal bean
insolation) ¼ 1000 (W/m2)
C ¼ solar flux concentration ratio (ratio of the solar flux
intensity achieved after concentration to the normal beam
insolation, dimensionless number) (suns)
TR ¼ solar reactor temperature required for the thermal
reduction of FeSO4 (K)
s ¼ StefaneBoltzmann constant ¼ 5:6705  10
8 (W/m2 K4)
Fig. 7 represents variation in habsorption as a function of n_ Ar
and TR at constant I ¼ 1000 (W/m2) and C ¼ 5000 suns. Simu-
lation results indicate that the habsorption increases with the
increase in n_ Ar and decrease in the TR. For instance, at
TR ¼ 1510 K (n_ Ar ¼ 0 mol/s), habsorption is equal to 94.10%. How-
ever, as n_ Ar increases from 0 to 30 mol/s and corresponding TR
decreases from 1510 to 1280 K, habsorption is increased upto
96.96%.
Fig. 7 e habsorption and required n_ Ar at chemical equilibrium
as a function of TR.
1644 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0

Fig. 8 e Process configuration for H2 production via two-step solar thermochemical IOeIS water splitting cycle.

Effect of C on habsorption is also examined at different n_ Ar and Heat energy required to produce steam by heating the
TR and findings are reported in Fig. 9. According to Fig. 9, liquid water can be determined as:
habsorption increases with the increase in C. At n_ Ar ¼ 5 mol/s and
_
Qheater
2 ¼ nDHj (21)
TR ¼ 1410 K, an increase in the habsorption from 77.58 to 97.76% is H2 OðlÞ@298 K/H2 OðgÞ@398 K

observed as C increases from 1000 to 10,000 suns. Similarly, at Energy penalty associated with the heating of steam from
different TR such as 1510 K (n_ Ar ¼ 0 mol/s), 1375 K (n_ Ar ¼ 10 mol/ 398 K upto TS can be estimated as:
s), 1340 K (n_ Ar ¼ 20 mol/s), and 1280 K (n_ Ar ¼ 30 mol/s), the
habsorption increases by 26.53%, 18.24%, 16.45%, and 13.70% with _
Qheater
3 ¼ nDHj (22)
H2 OðgÞ@398 K/H2 OðgÞ@473 K
the increase in C from 1000 to 10,000 suns.
Equation (23) gives the amount of energy needed to heat
the inert Ar from ambient conditions upto TR:
Net solar energy absorbed for the operation of IOeIS cycle
To operate the solar thermochemical IOeIS water splitting _
QAr
heating ¼ nDHj ArðgÞ@298 K/ArðgÞ@TR (23)
cycle, several energy requirements associated with following
steps needs to be fulfilled by solar energy input. The Energy required for the complete reduction of FeSO4
into FeO, SO2, and O2 is given by following equation:
 Energy required for the complete reduction of FeSO4 into
_
QFeSO4
reduction ¼ nDHj (24)
FeO, SO2, and O2 FeSO4 @473 K/FeOþSO2 ðgÞþ 1=2O2 ðgÞ@TR

 Energy required for heating of Ar from ambient conditions

upto TR
 Energy required for heating of SO2 from ambient condi-
tions upto TS
 Energy required for the conversion of liquid water (298 K)
into steam (398 K)
 Energy required for the heating of steam from 398 K upto TS

The net solar energy absorbed for the operation of solar

thermochemical IOeIS water splitting cycle can be calculated
as:

Qreactor
net ¼ QFeSO4
reduction þ QAr
heating þ Qheater
1 þ Qheater
2 þ Qheater
3

(19)

The energy required for the heating of SO2 from ambient

conditions upto TS is given by:

_
Qheater
1 ¼ nDHj (20)
so2 ðgÞ@298 K/so2 ðgÞ@473 K Fig. 9 e Effect of C on habsorption .
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0 1645

Fig. 10 e Effect of n_ Ar and TR on Qreactor
net : a) n_ Ar ¼ 0 mol/s, TR ¼ 1510 K, b) n_ Ar ¼ 5 mol/s, TR ¼ 1410 K, c) n_ Ar ¼ 10 mol/s,

TR ¼ 1375 K, d) n_ Ar ¼ 20 mol/s, TR ¼ 1340 K, and e) n_ Ar ¼ 30 mol/s, TR ¼ 1280 K (1 ¼ Qheater
1 , 2 ¼ Qheater
2 , 3 ¼ Qheater
3 ,
4 ¼ QAr
heating , 5 ¼ QFeSO4
reduction ).

Variations of Qreactor
net , QFeSO4
reduction ; QAr
heating ; Qheater
1 ; enhances from 0 to 613.35 kW as n_ Ar increases from 0 to
Qheater
2 ; and Qheater
3 as a function of n_ Ar and TR are shown 30 mol/s. Overall Qreactor
net increases by 50.665% (from
in Fig. 10. The results presented indicate that the 563.522 kW to 1142.243 kW) with the increase in n_ Ar (from 0 to
Qheater
1 ; Qheater
2 ; and Qheater
3 does not vary with respect to 30 mol/s) and decrease in the TR (from 1510 to 1280 K).
n_ Ar and TR and observed to be fixed at equal to 8.072 kW,
47.366 kW, and 2.625 kW, respectively. As per the results ob- Solar energy input
tained, with the increase in n_ Ar , required TR decreases and The amount of solar energy input required for the operation of
correspondingly QFeSO4
reduction also decreases. For example, as solar thermochemical IOeIS water splitting cycle can be
n_ Ar increases from 0 to 30 mol/s and TR decreases from 1510 K calculated as:
to 1280 K, correspondingly QFeSO4
reduction reduces from Qreactor
net
Qsolar ¼ (25)
505.46 kW to 470.83 kW. In contrast to this, the QAr
heating habsorption
1646 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0

From the results reported in Fig. 11, Qsolar is observed to be

maximum (1178.12 kW) at TR ¼ 1280 K as the large amount of
energy is required for Ar heating. Furthermore, Qsolar decreases
with the increase in the TR as less energy is required to in-
crease the temperature of the decreasing Ar molar flow. As the
TR increased from 1280 K (n_ Ar ¼ 30 mol/s) upto 1510 K
(n_ Ar ¼ 0 mol/s), Qsolar decreases by 49.17%. To avoid the
excessive energy penalty associated with the heating of the
Ar, lower n_ Ar or a larger reactor aperture and concentration
system should be used in practice.

Radiation heat losses

The amount of loss of heat energy due to re-radiation from the Fig. 12 e Effect of TR on Qre
radiation and
solar reactor associated with the solar thermochemical IOeIS % re
radiation losses.
water splitting cycle can be calculated as:

Qre
radiation ¼ Qsolar
Qreactor
net (26)

Opposite to this, Qcooler
2 increases with the increase in the TR
Also, % re-radiation losses can be determined as:
as the heat energy that can be recovered from the solid FeO
Qre
radiation will be higher if the thermal reduction is carried out at higher
% re
radiation losses ¼  100 (27)
Qsolar temperatures.

According to the simulation results presented in Fig. 12,

Rate of heat rejected to the surrounding by FeO oxidizer and
Qre
radiation remain constant in the range of 30e37 kW with
cooler 3
respect to the increase in the TR. However, as the habsorption and
FeO generated via thermal reduction of FeSO4 is transferred to
Qsolar decreases with the increase in TR, % re
radiation losses
the FeO oxidizer and reacted with the combined stream of SO2
increases from 3.045 upto 5.90%, respectively.
and H2O at 473 K for the production of H2. By assuming 100%
oxidation of FeO producing FeSO4 and H2 via water splitting
Rate of heat rejected to the surrounding by cooler 1 and cooler 2
reaction, the rate of heat rejected to the surrounding by FeO
Gaseous (SO2, O2, and Ar) and solid (FeO) products generated
oxidizer is estimated as 118.43 kW according to equation (30).
during thermal reduction of FeSO4 exits the solar reactor and
further cooled down via passing through cooler 1 and cooler 2. _
QFeO
oxidizer ¼
nDHj (30)
FeOþH2 OðgÞþSO2 ðgÞ@473 K/FeSO4 þH2 ðgÞ@473 K
The rate of heat rejected by cooler 1 and cooler 2 is given by:
H2 generated at 473 K via water splitting reaction is allowed
_
Qcooler
1 ¼
nDHj (28) to pass through cooler 3 before entering the ideal fuel cell
SO2 ðgÞþ0:5O2 ðgÞþArðgÞ@TR /SO2 ðgÞþ0:5O2 ðgÞþArðgÞ@298 K

(operated at 298 K). According to equation (31), 5.035 kW of

_
Qcooler
2 ¼
nDHj (29) heat is released by cooler 3 due to the cooling of H2 from 473 K
FeO@TR /FeO@473 K
to 298 K.
As per the results reported in Fig. 13, with the increase in
the TR from 1280 upto 1510 K, Qcooler
1 reduces from 1135.52 kW _
Qcooler
3 ¼
nDHj (31)
H2 ðgÞ@473 K/H2 ðgÞ@298 K
to 92.72 kW. This radical drop in the Qcooler
1 is because of the
decrease in the required n_ Ar as the thermal reduction of FeSO4 Rate of entropy produced across the solar reactor, cooler 1, and
is carried out at higher temperatures. As the utilization of n_ Ar cooler 2
during the thermal reduction decreases, the heat energy that The rate of entropy produced across the solar reactor (during
can be recovered from the gaseous products also decline. thermal reduction of FeSO4), cooler 1 (during cooling of

Fig. 11 e Effect of TR and n_ Ar on Qsolar . Fig. 13 e Effect of TR on Qcooler
1 and Qcooler
2 .

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0 1647

Rate of entropy produced across the FeO oxidizer and cooler 3

Similar to the previous section, this section is related to the
estimation of the rate of entropy produced across the FeO
oxidizer (during H2 generation via water splitting reaction)
and cooler 3 (during cooling of H2 from 473 to 298 K). The en-
tropies produced across the FeO oxidizer and cooler 3 are
calculated with the help of equations (35) and (36) and
observed to be equal to 0.010598 kW/K and 0.0035 kW/K.
 
QFeO
oxidizer
s_ FeO
oxidizer ¼
473
_
þ nDSj (35)
FeOþH2 OðgÞþSO2 ðgÞ@473 K/FeSO4 þH2 ðgÞ@473 K

Fig. 14 e Effect of TR on s_ reactor , s_ cooler
1 , and s_ cooler
2 .  

Qcooler
3 _
s_ cooler
3 ¼ þ nDSj H2 ðgÞ@473 K/H2 ðgÞ@298 K (36)
298

Rate of theoretical work performed and heat rejected by the

gaseous products), and cooler 2 (during cooling of solid prod- ideal fuel cell
ucts) are given by following equations: Solar thermochemical IOeIS water splitting cycle is completed
    with the addition of an ideal H2/O2 fuel cell with 100% work

Qsolar Qre
radiation efficiency (assumption). This ideal fuel cell is added to the
s_ reactor ¼ þ
TR 473
cycle to extract the maximum work from the net H2 produced
_
þ nDSj (32)
FeSO4 þArðgÞ@473 K/FeOðsÞþSO2 ðgÞþ0:5O2 ðgÞþArðgÞ@TR by this process. The rate of theoretical work performed by the
ideal fuel cell is calculate by equation (37) and observed to be
 
Qcooler
1 equal to 237.05 kW. Likewise, the rate of heat energy released
s_ cooler
1 ¼
298 by the ideal fuel cell is determined as equal to 48.56 kW [ac-
_
þ nDSj (33) cording to equation (38)].
SO2 ðgÞþ0:5O2 ðgÞþArðgÞ@TR /SO2 ðgÞþ0:5O2 ðgÞþArðgÞ@298 K

̇
  WFC
Ideal ¼
n DGjH2 ðgÞþ0:5O2 ðgÞ@298 K/H2 OðlÞ@298 K (37)
Qcooler
2 _
s_ cooler
2 ¼ þ nDSj FeO@TR /FeO@473 K (34)
473
̇
Fig. 14 represents the change in the rate of entropy pro- QFC
Ideal ¼
ð298Þ  n DSjH2 ðgÞþ0:5O2 ðgÞ@298 K/H2 OðlÞ@298 K (38)
duced across the solar reactor, cooler 1, and cooler 2 as a
function of TR. According to the obtained simulation results, Process efficiency
s_ reactor decreases by 32.96% due to the increase in the TR from Cycle efficiency of the solar thermochemical IOeIS water
1280 upto 1510 K. Similarly, 93.79% reduction in s_ cooler
1 is seen splitting process is defined as the ratio of theoretical work
with the similar increase in the TR. n_ Ar plays an integral role as performed by the ideal fuel cell to the solar energy input:
both s_ reactor and s_ cooler
1 decreases until Ar dilution is no longer
WFC
Ideal
required. As Ar dilution is not in the picture, s_ cooler
2 increases hcycle ¼ (39)
Qsolar
by a factor of 1.489 as TR increases from 1280 to 1510 K.

Fig. 15 e Effect of TR on hcycle and hsolar
to
fuel .

1648 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0

capable of achieving higher hcycle  34.09% as compared to the

Table 1 e hcycle and hsolar
to
fuel of solar thermochemical
other thermochemical cycles if operated at and above 1410 K.
IOeIS water splitting cycle.
Furthermore, if the energy required for the heating of inert Ar is
TR (K) hcycle (%) hsolar
to
fuel (%)
neglected, this cycle can attain maximum hcycle ¼ 44.83% at
Recuperation ¼ 0% lower temperatures of 1280 K.
1510 39.56 47.73
1410 34.09 41.11
Heat recuperation
1375 31.12 37.52
1340 23.54 28.40
The hcycle and hsolar
to
fuel for the solar thermochemical IOeIS
1280 20.12 24.26 water splitting cycle can be enhanced further if the heat
Recuperation ¼ 10% rejected by the cooler 1, cooler 2, cooler 3, and FeO oxidizer is
1510 41.54 50.09 recuperated and utilized to operate this cycle. The total
1410 36.07 43.50 amount of heat that can be recuperated is given as:
1375 33.23 40.08
1340 25.22 30.42 Qrecuperable ¼ Qcooler
1 þ Qcooler
2 þ Qcooler
3 þ QFeO
oxidizer (42)
1280 23.59 28.45
Recuperation ¼ 25% Furthermore, the solar energy input required for the
1510 44.86 54.10 operation of this cycle after heat recuperation can be esti-
1410 39.52 47.66 mated as:
1375 37.02 44.65
1340 28.35 34.18 Qsolar; with recuperation ¼ Qsolar
ð% recuperationÞ  Qrecuperable (43)
1280 27.86 33.60
Recuperation ¼ 40% The hcycle and hsolar
to
fuel after heat recuperation can be
1510 48.77 58.81 determined as:
1410 43.71 52.70
1375 41.79 50.39 WFC
Ideal
hcycle ¼ (44)
1340 32.36 39.01 Qsolar;with recuperation
1280 36.21 43.67
Recuperation ¼ 50% HHVH2
1510 51.77 62.43 hsolar
to
fuel ¼ (45)
Qsolar;with recuperation
1410 47.02 56.63
1375 45.71 55.12 Influence of heat recuperation on hcycle and hsolar
to
fuel is
1340 35.72 43.07 listed in Table 1. Reported data indicate that as the heat
1280 45.26 54.58 recuperation increases, both hcycle and hsolar
to
fuel increases
significantly. For instance, at TR ¼ 1280 K, the hcycle and
Furthermore, the solar-to-fuel energy conversion effi- hsolar
to
fuel increases by 25.14% and 30.32% if 50% heat recu-
ciency of the solar thermochemical IOeIS water splitting peration is applied to the solar thermochemical IOeIS water
process is defined as the ratio of higher heating value (HHV) of splitting cycle.
the H2 produced to the solar energy input:
Verification
HHVH2
hsolar
to
fuel ¼ (40) The exergy analysis performed for the solar thermochemical
Qsolar
IOeIS water splitting cycle was further verified by performing an
Where, energy balance and by evaluating the maximum available pro-
̇
cess efficiency from the total available work and from the total
HHVH2 ¼
n DHjH2 ðgÞþ0:5O2 ðgÞ@298 K/H2 OðlÞ@298 K (41) solar energy input [7]. The energy balance conducted for the
solar thermochemical IOeIS water splitting cycle confirms that
As per the HSC simulations, both hcycle and hsolar
to
fuel in-
creases with the increase in TR. For instance, at 1280 K, hcycle is WFC
Ideal ¼ Qsolar
ðQre
radiation þ Qcooler
1 þ Qcooler
2 þ Qcooler
3
equal to 20.12% and hsolar
to
fuel is equal to 24.26%, and as the TR
þ QFeO
oxidizer þ QFC
Ideal Þ (46)
increases upto 1510 K, hcycle and hsolar
to
fuel also enhanced upto
39.56% and 47.74% (Fig. 15). The energy balance at TR ¼ 1510 K, TS ¼ 473 K, and n_ Ar ¼ 0 mol/
According to previous studies, the maximum cycle efficiency s confirms the accuracy of the analysis as WFC
Ideal ¼ 237.05 kW
reported for different thermochemical cycles are as follows: 29% calculated from Eq. (37) equals WFC
Ideal determined from Eq. (46).
in case of ZnO/Zn cycle [7], 29.8% in case of SnO2/SnO cycle [11], The available work can be calculated as the sum of the
20.2% in case of ceria cycle [22], and 30% in case of Fe3O4/FeO work done by the ideal fuel cell, and the lost work due to
cycle [34]. It is worthy to note that the cycle efficiencies of all the irreversibility's in solar reactor, cooling units, and the FeO-
above mentioned thermochemical cycles were calculated by oxidizer. For the solar thermochemical IOeIS water splitting
neglecting the amount of energy required for heating the inert cycle, the maximum cycle efficiency was calculated by Eq. (47)
gas. The results obtained during the presented investigation and it was observed to be equal to the Carnot heat engine
indicate that solar thermochemical IOeIS water splitting cycle is operating between hot and cold temperature reservoirs.

WFC
Ideal þ TS ðs_ reactor þ s_ cooler
1 þ s_ cooler
2 þ s_ cooler
3 þ s_ FeO
oxidizer Þ TS

hcycle;maximum ¼ ¼1
¼ hcarnot (47)
Qsolar TR
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 1 6 3 9 e1 6 5 0 1649

For instance, at TR ¼ 1510 K, TS ¼ 473 K, and n_ Ar ¼ 0 mol/s, Qcooler
1 heat rejected to the surrounding from cooler 1, kW
hcycle;maximum ¼ hcarnot ¼ 68.67%. Qcooler
2 heat rejected to the surrounding from cooler 2, kW
Qcooler
3 Heat rejected to the surrounding from cooler 3, kW
QFC
Ideal heat rejected to the surrounding from ideal fuel cell,
Summary and conclusions kW
QFeO
oxidizer heat rejected to the surrounding from FeO
Two-step solar thermochemical iron oxideeiron sulfate oxidizer, kW
(IOeIS) water splitting cycle for the production of H2 have been QFeSO4
reduction energy required for the thermal reduction of
thermodynamically investigated. Thermodynamic equilib- FeSO4, kW
rium calculations performed at 1 atm pressure and in absence Qheater
1 energy required for heating of SO2, kW
of inert Ar indicate that the H2 production via water splitting Qheater
2 energy required for production of steam, kW
reaction is feasible below 483 K and thermal reduction of Qheater
3 energy required for heating of steam, kW
FeSO4 is possible above 1290 K. The change in the enthalpy Qreactor
net net energy input required for the operation of IOeIS
and entropy for the water splitting reaction is observed to be cycle, kW
negative (indicating that this reaction is more feasible at lower Qre
radiation radiation heat loss from the solar reactor, Kw
temperatures), whereas the variation in enthalpy and entropy Qrecuperable total amount of heat that can be recuperated, kW
associated with the thermal reduction of FeSO4 is observed as Qsolar solar energy input, kW
positive (confirming that this reaction is more feasible at Qsolar;with recuperation solar power input after heat recuperation,
higher temperatures). The TR required for the complete con- kW
version of FeSO4 into FeO, SO2, and O2 is observed to be TR thermal reduction temperature, K
decreased from 1510 to 1280 K with the increase in the n_ Ar TS water splitting temperature, K
from 0 to 30 mol/s. WFC
Ideal work output of an ideal fuel cell, kW
The second law thermodynamic analysis indicate that the habsorption solar absorption efficiency
habsorption decreases by 2.86% with the increase in TR from 1280 hcarnot carnot efficiency
to 1510 K (at C ¼ 5000 suns) and increases by 26.53% with the hcycle cycle efficiency
increase in C from 1000 to 10,000 suns (at TR ¼ 1510 K). Simi- hcycle;maximum maximum cycle efficiency
larly, Qreactor
net and Qsolar are observed as increased by 50.665% hsolar
to
fuel solar to fuel energy conversion efficiency
and 49.17% with the decrease in the TR from 1510 to 1280 K. DG Gibbs free energy change, kJ/mol
The reason for this increase is the high energy requirement for DGWS Gibbs free energy change for water splitting reaction,
the heating of inert Ar. A decrease in the s_ reactor and s_ cooler
1 is kJ/mol
realized until Ar dilution is no longer required. The achieve- DGTR Gibbs free energy change for thermal reduction
ment of maximum hcycle ¼ 39.56% and hsolar
to
fuel ¼ 47.74% is reaction, kJ/mol
observed at higher TR ¼ 1510 K. At similar TR, increase in the DH enthalpy change, kJ/mol
hcycle and hsolar
to
fuel upto 51.77% and 62.43% is possible by DHWS enthalpy change for water splitting reaction, kJ/mol
applying 50% heat recuperation. Furthermore, the hcycle and DHTR enthalpy change for thermal reduction reaction, kJ/
hsolar
to
fuel of this cycle are higher as compared to other solar mol
thermochemical water splitting cycles. The results obtained DS entropy change, J/mol$K
provide a foundation for pursuing an experimental study for DSWS entropy change for water splitting reaction, J/mol$K
producing solar H2 via thermochemical IOeIS water splitting DSTR entropy change for thermal reduction reaction, J/
cycle. mol$K
s StefaneBoltzmann constant, 5.670  10
8 (W/m2$K4)
s_ cooler
1 rate of entropy produced across cooler 1, kW/K
s_ cooler
2 rate of entropy produced across cooler 2, kW/K
Acknowledgments s_ cooler
3 rate of entropy produced across cooler 3, kW/K
s_ FeO
oxidizer rate of entropy produced across FeO oxidizer, kW/
The authors gratefully acknowledge the financial support K
provided by the Qatar University internal grant QUUG-CENG- s_ reactor rate of entropy produced across the solar reactor,
CHE-13/14-4. kW/K

Nomenclature

C solar flux concentration ratio, suns references

CSP concentrated solar power
HHV higher heating value
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