AN EXPERIMENTAL SET-UP TO EVALUATE THERMODYNAMIC

PARAMETERS IN THE SODIUM MANGANESE FERRITE

THERMOCHEMICAL CYCLES

F. Varsano, A. La Barbera, C. Alvani, F. Padella

ENEA-, Via Anguillarese 301, 00123 Roma, Italy

Ph. +390630483259 – francesca.varsano@enea.it

1. Introduction
Thermochemical cycles (TC) that split water into hydrogen and oxygen by using a renewable resource such
as concentrated solar heat are among the processes candidate to promote the transition to a sustainable energy
future. Among the numerous proposed TC, the two-step metal oxide-based processes are considered the most
suitable for a coupling with concentrated solar energy. In particular, ferrite-based cycles have been widely
studied by different groups and implemented inside solar chemical reactors [1].
Mixed metal ferrites MxFe2-xO4 (M= Mn, Co, Ni) are metal oxides whose ability to produce hydrogen from
water (WO step) and whose aptitude at loosing oxygen (TR step) are strictly correlated to the nature of the
metal M and to its quantity in the solid crystalline structure of the ferrite. Many questions remain unanswered
regarding the basic processes taking place during both the TR and WO steps. Nevertheless the
thermochemistry of mixed ferrites and the effect of metal substitution on both the production step and the
regeneration of intial reactants have been addressed by properly developed thermodynamic models [2, 3].
Differently from the mentioned cycles, where WO and TR steps are simply run by heating the material at
different temperatures, the mixed sodium manganese ferrite cycle consists of a multi – step system [4] where
hydrogen production and reactant regeneration reactions occur mediated by interaction with carbon dioxide,
emitted or reabsorbed by the solid reactant.
2MnFe2O4(s) + 3Na2CO3(s) + H2O(g) = 6Na(Mn1/3Fe2/3)O2(s) + 3CO2(g) + H2 (g) (1)
6Na(Mn1/3Fe2/3)O2(s) + 3CO2(g) = 2MnFe2O4(s) + 3Na2CO3(s) + ½O2(g) (2)
The main advantage of this cycle is the possibility of operating both WO and TR steps at temperatures as low
as 750°C. Taking advantage of this aspect, a laboratory setup has been realized with the scope of determining
experimentally the thermal quantity involved in the single reactions. Knowledge of reaction enthalpies in fact
are required for the assessment of the cycle efficiency.
In this paper the experimental setup and procedures aiming at the reaction enthalpies achievement will be
described.

2. Methodology
The method followed to determine reaction enthalpies relies on the van’t Hoff equation [5]
d ln K ∆H O
=−
1 R
d
T
i.e if one is able to measure the equilibrium constant of the reaction at different temperatures, a plot of the
natural logarithm of the equilibrium constant versus the reciprocal temperature gives a straight line. The
slope of the line is equal to minus the standard enthalpy change divided by the gas constant.
Reaction (1) is a solid/gas reaction and it was demonstrated [4] that it takes place as a sequence of two steps:
the first one is a reaction of the solid reactants promoted by temperature to form a solid intermediate phase
and releasing two moles of carbon dioxide (4). The second one is the hydrogen generation reaction from
water (5).
2MnFe2O4(s) + 3Na2CO3(s) = 2(MnO*2NaFeO2)(s) + Na2CO3+ 2CO2(g) (4)
2(MnO*2NaFeO2)(s) + Na2CO3 + H2O = 6Na(Mn1/3Fe2/3)O2(s) + CO2(g) + H2 (g) (5)
Considering the activities of the solid phases as unitary, the equilibrium constant of reaction (4) and (5) can
be written as
2
K p ≅ pCO (6)
2

pCO2 pH 2 (7)
Kp ≅
p H 2O

(due to the low pressure conditions, fugacity of the gaseous species f is approximated with the pressure term
p). The equilibrium constant and the enthalpy of reaction (4) can be determined by measuring the equilibrium
carbon dioxide pressure as a function of temperature. The equilibrium constant (7) can be expressed as a
function of the species molar fraction x and the total pressure P (8) experimentally measured.
xCO2 xH 2 (8)
Kp ≅ P
xH 2O

3. Experimental setup and procedure.

The experimental set-up consists of a modular reactor as depicted in figure 1. The apparatus was realized in
glass, except for the reaction chamber which is in quartz. Reactants are placed inside a 1cm long boat placed
in the center of the tubular oven. The reactor can be evacuated or filled with inert gas. A known amount of
water is injected through a septum located on the left of the oven when the reactants reach the desired
temperature. The glass reactor is kept at a temperature exceeding 100°C to avoid water condensation on the
walls by means of a 1Kwatt infrared lamp (not in the picture). Un-reacted water and gases produced by
interaction with the solid mixture are collected in the sampling bottle. Known volumes of gases are sampled
from the bottle (isolated from the reacting mixture by means of a stopcock) and injected into a TPR
(temperature programmed reaction) apparatus to be quantitatively analyzed. The experimental setup was
validated by measuring the decomposition equilibrium constant (KCaCO3) of a reference solid carbonate
(CaCO3 = CaO+CO2) in the temperature range of interest (684-728°C). The obtained decomposition enthalpy
value is 164±4KJ/mol very close to tabulated 167-168KJ/mol.

pressure sensor
-2,4
septum

-2,6

-2,8
3
lnKCaCO

-3,0

-3,2
∆H = 164 +/- 4 kJ/mol
-3,4

-3,6
0,00099 0,00100 0,00101 0,00102 0,00103 0,00104 0,00105
to vacuum sampling bottle
-1
1/T (K )

Fig.1. (a) Picture of the experimental setup utilized for the determination or reaction constants. (b) Diagram
of lnK vs 1/T for the experimental, non calorimetric, determination of CaCO3 decomposition enthalpy.

4. References
[1] T. Kodama, N. Gokon, Chem. Rev. 107 (2007) 4048-4077
[2] M. Allendorf, R. Diver, N. Siegel, J. Miller, Energy & Fuels 22 (2008) 4115-4124
[3] M. Roeb, N. Gathmann, M. Neises, C. Sattler, R. Pitz-Paal, Int. J. Energy Res. 33 (2209) 893-902
[4] C. Alvani, A. La Barbera, G. Ennas, F. Padella, F. Varsano, Int. J. Hydrogen Energy 31 (2006) 2217 –
2222
[5] P. W. Atkins, (1999). Physical Chemistry, Oxford University Press