Energy & Buildings 196 (2019) 178–193

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Energy & Buildings

journal homepage: www.elsevier.com/locate/enbuild

Characterization of potassium carbonate salt hydrate for

thermochemical energy storage in buildings
M. Gaeini∗, S.A. Shaik, C.C.M. Rindt
Eindhoven University of Technology, Department of Mechanical Engineering, P.O.Box 513, Eindhoven 5600MB, The Netherlands

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

Article history: Thermochemical heat storage in salt hydrates is a promising method to improve the solar fraction in the
Received 29 June 2018 built environment. One of the most promising salt hydrates to be used as thermochemical material is
Revised 11 March 2019
potassium carbonate. In this study, the use of potassium carbonate in heat storage applications is inves-
Accepted 13 May 2019
tigated experimentally. The most important objective is to form a kinetic model for the de/re-hydration
Available online 15 May 2019
reaction of the material. In order to do so, it is crucial to understand the behavior of the salt when it
Keywords: reacts with water vapor. Reaction kinetics and mechanism are investigated for K2 CO3 , as one of the most
Thermochemical heat storage promising materials. Characterization of the materials is carried out with combined Thermo-Gravimetric
Potassium carbonate Analysis (TGA) and Differential Scanning Calorimetry (DSC) methods. By employing the experimental re-
TGA-DSC sults, kinetics models are developed for the hydration and dehydration reactions of the material. The
Kinetics kinetics model can be further used to predict the performance of a heat storage system working with
Energy storage density
K2 CO3 . In addition, cyclability and reaction enthalpy are investigated.
Reaction model
© 2019 Elsevier B.V. All rights reserved.

1. Introduction por to the dehydrated material. For low temperature sorption heat
storage, adsorption of water vapor on sorption materials [3] and
In Europe, energy consumption for domestic purposes accounts hydration of salt hydrates [4,5] are frequently studied. Based on
for almost 40% of the total energy demand [1]. Therefore, a signif- theoretical energy storage density, salt hydrates (such as potassium
icant potential to reduce green house gas emissions exists by the carbonate) are better candidates compared to sorption materials
reduction in fossil fuel consumption in this sector. Energy storage (such as zeolite) [6].
is a key step to shift to low carbon energy sources, which are in- In recent years, intense research has been performed on in-
herently intermittent. Solar energy, as one of the most exploitable novative system design for integrating the sorption heat storage
renewable energy sources, is available more than required to be concept into an overall system, and lab or pilot scale setups are
harvested in residential houses during summer, while the demand developed and tested [7]. Several Prototypes are built based on
cannot be met during winter. A solution is to store excess of so- zeolite [8,9] and some salt hydrates, such as magnesium chloride
lar energy in summer by a so-called thermal battery which can be [10] and strontium bromide [11]. More studies can be found in
discharged to provide heat for the residential demand in winter the extensive reviews on sorption heat storage, which are done
[2]. to summarize the state of the art on systems and reactors for
A promising method is heat storage using ThermoChemical Ma- building applications [12] and the advancements at material and
terials (TCMs), by which heat can be stored in a compact and prototype for long-term low-temperature applications [13].
quasi loss-free way over a long time. In the sorption heat storage An interesting material for thermochemical heat storage should
process, heat is stored into an endothermal dissociation reaction be non-toxic, non-corrosive and stable with high energy storage
(charging), and at a later time, the energy can be retrieved from density [4]. In addition, the price of the material is a crucial fac-
the reverse exothermal reaction (discharging). In the built environ- tor affecting the economic feasibility of a heat storage system [14].
ment, heat generated by a solar collector during summer can be More specifically, depending on the application, operating bound-
employed to desorb water from the material. The energy stored in ary conditions are important [5], such as hydration/dehydration
this way can be released during winter by introducing water va- temperature and vapor pressure, which are also effective on kinet-
ics (and is directly related to power output) and deliquescence. For
application in the built environment, heat storage at temperatures
∗
Corresponding author. around 100 ◦ C is needed, which is a obtainable temperature by us-
E-mail addresses: [email protected] (M. Gaeini), [email protected] (C.C.M. Rindt). age of solar thermal collectors. A great body of material research

https://doi.org/10.1016/j.enbuild.2019.05.029
0378-7788/© 2019 Elsevier B.V. All rights reserved.
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 179

is available on high potential salts for temperature storage be-

low 100 ◦ C, such as MgSO4 [15–19], MgCl2 [19,20], SrBr2 [21] and
CaCl2 [20,22,23]. In most of the available literature, some impor-
tant criteria, with respect to application in the built environment,
are missing while studying the salts, which will be denoted below.
Donkers et al. [5] published a review on 563 thermochemical
materials in search for the most promising material for application
in the built environment. A list of 25 candidates is composed first
based on four criteria, i.e. energy storage density on material level
above 1.3 GJ/m3 , hydration temperature above 50 ◦ C, dehydration
temperature below 120 ◦ C and a melting point above the dehy-
dration temperature. The list is analysed further considering ad-
ditional critical parameters: Safety, chemical stability, kinetics and
price. It turns out that one of the largest problems is the price.
Finally, potassium carbonate (K2 CO3 ) is concluded to be the best
candidate among the studied material in the review. Potassium car-
bonate is investigated further in depth by Sögütoglu et al. [24] with
respect to energy density, power output and stability, presenting
a critical assessment of potential chemical side reactions in open
Fig. 1. Phase diagram of K2 CO3 constructed based on Clausius–Clapeyron relation
and closed reactor concepts. It is concluded that, given the chemi- using data from literature [33].
cal robustness and the power output, 1 m3 of material can be used
with a frequency of 12–52 cycles a year (i.e. monthly to weekly),
yielding a yearly basis energy of 15 − 66 GJ, which can be main- Potassium carbonate appears as a white odorless powder. It ex-
tained over at least 20 years. This makes the material suitable for ists in two states, namely an anhydrate state and a sequihydrate
application in the built environment. state (1.5 H2 O). The sesquihydrate occurs as small, white, translu-
For thermochemical heat storage systems with application in cent crystals. At room temperature, it has an equilibrium relative
the built environment, output temperature and power are two im- humidity of approximately 43% [29]. It reaches to a deliquescent
portant parameters. For systems being used for domestic hot wa- state when left open to room atmosphere, so proper storing of the
ter production, a relatively high output temperature of at least 60 material is critical. The following equation describes the reversible
◦ C is required, in order to prevent bacteria growth. Although, ther-
hydration-dehydration reaction for potassium carbonate.
mal output power might drop at high temperatures [25]. Therefore,
Heat added
possible thermal output power from a thermochemical heat stor- K2 CO3 · 1.5 H2 O(s )  K2 CO3 (s ) + 1.5 H2 O(g). (1)
age systems working by the material potassium carbonate needs to Heat Extracted
be investigated. Reactions occurring locally in the reactor are criti- On heating a sesquihydrate form of potassium carbonate
cal for the global performance of the system [26], such as thermal (K2 CO3 · 1.5 H2 O), it dissociates to anhydrous form (K2 CO3 ) and
output power. Therefore, the reaction kinetics should be included water vapor, leading to an endothermic reaction. When the anhy-
mathematically in heat and mass transfer models, which are re- drous form reacts with water vapor, it forms a sesquihydrate lead-
quired to study such systems. Such a correlation which describes ing to an exothermic reaction. It is a single step reaction leading
the rate equation can be estimated from kinetic analysis of the re- to a simple kinetic mechanism. The only stable states of hydration
action. Important recommendations for performing kinetic analysis reported in literature [5,24,30,31] and experimentally observed in
are given in the literature [27]. These recommendations are taken the present work are the anhydrate and sesquihydrates forms.
as a starting point to understand the concepts about chemical ki- In order to perform hydration-dehydration reactions, it is im-
netics and the knowledge is used in the present work. portant to understand the thermodynamic properties of the salt
In this work, the reaction kinetics and mechanism of K2 CO3 hydrate. Using the concept of reversible reactions, heat can be ex-
de/re-hydration are investigated. Characterization of the material is tracted. In real life, a thermal storage system can be designed us-
carried out with combined Thermo–Gravimetric Analysis (TGA) and ing the concept. However, in order to actually utilize the concept,
Differential Scanning Calorimetry (DSC) methods. By employing the it is necessary to control the operating conditions such as water
experimental results, kinetics models are developed for the hydra- vapor pressure and temperature. For K2 CO3 , these conditions can
tion and dehydration reactions of the material. The kinetics model be retrieved from the constructed phase diagram based on thermo-
can be further used to predict the performance of a heat storage dynamics properties as shown in figure Fig. 1. The phase diagram
system working with K2 CO3 . Finally, the performance of the ma- can be constructed using the Clausius–Clapeyron equation [32]:
terial is discussed based on the developed kinetics and measured
enthalpy of reaction, in view of application in the built environ- d ln(Peq ) h
= (2)
ment. d(1/T ) R
where Peq [Pa] is the equilibrium water vapor pressure between
2. Materials and methods
the two hydrate phases, T[K] is the corresponding temperature, R
[J/kg/K] is the gas constant and h [J/mol] is the reaction enthalpy
2.1. Potassium carbonate
per mole of H2 O.
In Fig. 1, the blue line represents the equilibrium line be-
The interest in potassium carbonate has been sparked by its
tween the two states of hydration of potassium carbonate (K2 CO3 ·
easy availability and subsequently low price (around 0.50 € /kg
1.5 H2 O − K2 CO3 ). The equilibrium vapor pressure Peq [Pa] is fitted
[28]), high capacity for water uptake and energy storage density,
by:
better chemical stability than other salt hydrates, low corrosive-
ness and non-toxicity. Furthermore, the material dehydrates at low  7337 
temperature (below 100 ◦ C), which makes it suitable for applica- Peq = 4.228 × 1012 exp − (3)
T
tion in the built environment.
180 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

where T [K] is temperature. The ratio between water vapor pres-

sure (Pw ) and equilibrium water vapor pressure (Peq ), called the
pressure ratio (= Pw /Peq ), is an important parameter in reaction ki-
netics. To find out the pressure ratio, the equilibrium water vapor
pressure can be calculated from Eq. (3) and the actual water vapor
pressure is known from experimental conditions.
During the hydration process, after a certain state of hydration
liquefaction (deliquescence) occurs, which is caused by the depres-
sion of the melting point upon water uptake. This is caused by the
highly hygroscopic nature of the material. In Fig. 1, the red line
represents the deliquescence transition. In practice, this means the
formation of an aqueous solution instead of a solid state material.
Dehydration of such an overhydrated solution yields an agglomer-
ated bulk of solid material, instead of the initial powdery porous
form. Agglomeration is an undesirable behavior of the material,
because it prevents or decelerates the subsequent water uptake
process [23]. Therefore, the operation condition should be chosen
such to avoid overhydration. By controlling the conditions in an Fig. 2. Schematic view of TGA-DSC setup.

experiment, as well as in a storage system, it becomes possible to

stay below the deliquescence line.
The material used in this study is the pure salt (Sigma–Aldrich)
in powder form (500 − 1000 μm particles) and the state of hy-
dration for the material in the container is 1.5 moles of water
per mole of potassium carbonate (sesquihydrate K2 CO3 · 1.5 H2 O ).
However, due to the hygroscopic nature of the material, the water
uptake after being taken out of the container and exposed to room
conditions is fast. Since the initial state of hydration is generally
unknown for a sample, the experiments are always started with
an initial dehydration cycle (at a temperature of 100 ◦ C).

2.2. TGA-DSC setup

The characterization of TCM is based on measurement data, ob-

tained through the methods of Thermo–Gravimetric Analysis (TGA)
and Differential Scanning Calorimetry (DSC). A Simultaneous Ther-
mal Analysis (STA) apparatus (Netzsch STA 449 F3 Jupiter) con-
nected to a Modular Humidity Generator (MHG ProUmid) is used, Fig. 3. Temperature program used in the experiments.
which allows for simultaneous measurement of both the mass
change (TGA) and the heat release/uptake (DSC) of a sample. The
STA apparatus consists of a thermally controlled environment (fur-
nace), which is subjected to a pre-defined temperature program. 2.3. Experimental conditions
The sample is situated in an aluminium crucible located in the
furnace, with a typical sample mass of around 10 mg. An empty The typical experiments are conducted in an air atmosphere
crucible is located just beside the sample crucible as reference for with a flow rate of 500 ml/min. A sample of K2 CO3 · 1.5 H2 O is
the DSC measurement. The crucibles are assumed to be subjected first dehydrated in a dry air atmosphere with a heating rate of
to identical conditions. Both crucibles are positioned on a sample 10 K/min from the ambient temperature to 100 ◦ C. Afterwards,
holder, which is mounted on top of a balance. The humidity gener- the furnace is cooled down to the ambient temperature and kept
ator provides an air flow with a controlled flow rate, temperature at this temperature. Then humid air is introduced to the furnace
and humidity. The air flow is from top to the bottom of the fur- in order to hydrate the sample. In this work, the reference water
nace. A schematic view of the setup is shown in Fig. 2. vapor pressure of 13 mbar is chosen, being the saturation water
The TG signal shows the weight change of a sample during vapor pressure at 10 ◦ C, which is a typical borehole (humidity
an experiment with respect to the initial mass, as measured generator) temperature in the Dutch climate [10].
with the balance. The temperature of each crucible is measured The temperature program used in the experiments is shown
with a thermocouple attached at the bottom of each platform in Fig. 3. The initial heating is implemented for the sample to
on which the respective crucible is situated. The temperature completely dehydrate and reach anhydrous state at a maximum
difference between the sample crucible and the neighbouring temperature of 100 ◦ C. Also, through the course of the experi-
reference crucible is recorded. The temperature difference serves mentation, a cycling effect was observed; as hydration reaction
as a measure for the heat flux towards or from the sample. The becomes faster after each cycle till a certain number of cycles. The
DSC signal is a measure for the heat flow to or from the sample: experimental data used in the analysis are from the cycles where
negative values indicate exothermic reactions, positive values there is no further cycling effect.
indicate endothermic reactions; the direction of exothermic values Table 1 shows the experimental conditions used for de/re-
is indicated on the respective axis. Generally, hydration and thus hydration experiments. While performing these experiments, all
mass gain, implies an exothermic reaction, whereas dehydration the other half-cycles in between are of similar conditions (typi-
implies an endothermic reaction. cal experiment), in order to avoid any after effects due to different
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 181

Table 1 The DSC signal shows the power with which the heat is ad-
Experimental conditions for de/re-hydration experiments.
sorbed (in endothermic reaction of dehydration) or released (in
Operating parameter Dehydration Rehydration exothermic reaction of hydration) by the sample. In theory, the
Initial temperature (◦ C) 27–30 27–30 baseline (BL) should have a value of approximately zero. The devi-
Dehydration temperature (◦ C) 26–57 85–150 ation of the DSC signal from the baseline indicates the occurrence
Water vapor pressure (mbar) 8.4–17.5 0.3-2.5 of a chemical process, involving thermal effects.
Heating/cooling rate (K/min) 10 0.5–20 The reaction rate (presented in Eq. (4)) is used in the fitting
De/re-hydration time (min) 15–300 40–120
procedure through the experimentally calculated reaction rates. In
the implemented fitting, unknown parameters are determined such
that residual sum of squares. The reaction rate equation is rewrit-
experimental conditions of preconditioning as observed by Stanish
ten based on the fitting parameters as:
and Perlmutter [31].
dα Pw
 
2.4. Evaluation of reaction kinetics = [Y (1 )].(1 − α )[Y (2)] . [Y (3 )]
(9)
dt Peq

The rate of conversion of a reaction can be generally described where [Y(1)], [Y(2)] and [Y(3)] are the fitting parameters for the
by the following equation [27,34,35]: rate constant k(T), reaction order n and order of the pressure ratio
term, respectively.
dα
= k (T ) · f (α ) · h ( p )
dt
dα
 E  P  3. Results
· f (α ) ·
a w
= A f · exp − (4)
dt RT Peq Different samples are investigated through the water adsorption
where k(T) is the temperature function which is an Arrhenius type and energy exchange of the materials during de/re-hydration reac-
function. This function contains the activation energy Ea [J/mol], tions, which are measured by the TGA and DSC methods. In this
pre-exponential factor A f [1/min] and the gas constant R [J/kg/K]. section, results of typical experiments are presented, firstly. Sec-
f(α ) is the conversion function or the reaction model, where α ondly, dependencies on the sample mass and cycling are investi-
is the extent of conversion. Finally, h(p) is the pressure function, gated. Then, kinetics models for hydration and dehydration are de-
which is usually the ratio between the water vapor pressure and veloped. Finally, the reaction enthalpy is studied.
the equilibrium pressure. The sample mass, used in the figures and tables, represents the
In order to evaluate the performance of the materials, TG and mass of the active material in a sample (dry potassium carbonate
DSC signals can be converted to performance indication factors, content), which would be the sample mass after the first dehy-
such as loading (or state of hydration), conversion, conversion rate, dration. In addition, the salt content of each sample can be de-
and reaction enthalpy. termined using the experimental results, by comparing the calcu-
The loading L, or state of hydration, is the number of water lated equilibrium loading based on measurements and the theoret-
molecules NH2 O per number of potassium carbonate crystal units ical equilibrium loading from Fig. 1. This method gives results that
NK2CO3 , and can be calculated by: are accurate with in one percent.

NH2 O mH2 O /MH2 O

L= = (5) 3.1. Typical experimental results
NK2CO3 mK2CO3 /MK2CO3
where mH2 O is the mass increase of the sample starting from the A typical experimental result is shown in Fig. 4. A sample of
anhydrous state due to the absorption of water, and mK2CO3 is the K2 CO3 · 1.5 H2 O is first dehydrated in a dry air atmosphere in
mass of the anhydrous salt, and MH2 O and MK2CO3 are the molar the apparatus. The temperature increases firstly from 26 ◦ C to 100
mass of water and potassium carbonate, respectively. The anhy- ◦ C with a heating rate of 10 K/min (red dotted line). Afterwards

drous state is recognized when the TG signal is more or less con- the furnace is cooled down to 26 ◦ C and kept at this tempera-
stant in time at high temperatures. ture (blue dotted line). Then humid air with a water vapor pres-
The conversion of dehydration (deH) and rehydration (reH) re- sure of 13 mbar is introduced to the furnace in order to rehydrate
actions are calculated based on the TG signal α , which can also be the sample. The TG and DSC signals are shown vs. time in Fig. 4(a)
presented based on loading as: and (b), respectively.
 As can be observed in Fig. 4(a), during dehydration, the sam-
L − Li ( 1.5 − L )/1.5 ,deH
α= = (6) ple loses mass (red solid line), indicating the desorption of water
L f − Li L/1.5 ,reH
molecules from the salt crystal structure and eventually reaches to
where L is the loading at a certain moment in time, and Li and Lf the complete anhydrous state, as the TG signal is constant. When
are the initial and final loading values, respectively. the humidity is introduced to the furnace during hydration, the
The enthalpy of reaction is determined through the energy sample gains mass again (blue solid line).
change during a reaction. The stoichiometry of the reaction itself In the measured DSC data (Fig. 4(b)), negative values indicate
is identified through the mass change, and is used to calculate the an endothermic process (dehydration) and positive values indicate
change of state of hydration. The reaction enthalpy is the energy an exothermic process (hydration). The direction of exothermic sig-
released or absorbed per mole of water and can be obtained by: nal is indicated on the respective axis. The TG signal can be related
H to the DSC signal as rate of mass change corresponds to the rate
h = (7) of heat flux to or from the sample. The step changes in TG signal
NH2 O
corresponds to energy peaks in the DSC signal. As water molecules
where H is the released heat, as measured in the STA appara- are desorbed from the sample during dehydration, a mass loss is
tus, which can be calculated by integrating the heat flow over the seen in TG signal leading to energy storage in the sample observed
course of a reaction, according to: as a negative peak in DSC signal. Conversely, as water molecules
 tf  tf are absorbed by the sample during hydration, a mass gain is seen
H = [DSC (t ) − BL(t )]dt = Q˙ dt (8) in TG signal, consequently, leading to release of energy observed
ti ti
as a positive peak in DSC signal.
182 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

Fig. 4. Typical result of a 8mg K2 CO3 · 1.5 H2 O sample subjected first to dehydration in dry air atmosphere with a heating rate of 10 K/min from 26 ◦ C to 100 ◦ C, and then
subjected to rehydration in a humid air atmosphere with a water vapor pressure of 13 mbar and a temperature of 26 ◦ C.

In Fig. 4(b), blue and red shaded regions indicate the integrated 3.2. Sample mass in-dependency
area, which represent the released and stored energies during the
hydration and dehydration reactions, respectively. Also, the peaks The mass of sample is an important parameter regarding
show the maximum power required for dehydration and released kinetics [23]: During hydration, the diffusion of vapor through
during hydration. Since the released power during hydration reac- the sample is limited for large samples; and during dehydration,
tion directly translates to a power output, it is an important pa- temperature distribution over the sample is not uniform for large
rameter while varying different experimental parameters [35], and samples, which leads to limited reaction rate in the core of the
will be discussed further in Section 4. sample. Therefore, a set of experiments is performed to identify a
The extent of conversion can be calculated based on TG signal suitable range of sample mass at which the effects are minimum.
by Eq. (6), and then reaction rate can be calculated by derivative In addition, the temperature of the reference program used in
of the conversion over time. Fig. 5 shows the conversion and re- the experiment should be similar to temperature of the sample un-
action rate vs. time for the experiment presented above. For both der investigation. There is difference between the former and latter
hydration and dehydration, conversion is changing from 0 at the on two occasions: the first being the usage of high heating rates
beginning to 1 at the end of the reactions. For dehydration, reac- and the second when large sample masses are used. Both cause
tion rates start from a minimum and then reach a maximum value, undesirable thermal effects which give an error in kinetic param-
because the sample loses mass when the temperature is ramped eter estimation [27]. In order to avoid the undesirable thermal ef-
up, as seen in the temperature profile. Whereas for hydration, the fects, sample mass in-dependency experiments are performed.
reaction rate (rate of conversion) is maximum at the start of the Fig. 6 shows the results for hydration reaction rate of samples
reaction (at around t = 100 min as indicated in the figure), as soon with various masses vs. time. Samples with large masses exhibit
as humid air is introduced to the system. slower reaction rates. The curves of samples with mass of 9 and
For all the experiments so forth, the same procedure is followed 10 mg show similar reaction rates. Hence, a sample mass of around
to calculate the conversion and reaction rates for both hydration 10 mg can be used in experiments, so the experimental results are
and dehydration. independent of the sample mass.

Fig. 5. Extent of conversion and reaction rate calculated for the experiment shown in Fig. 4.
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 183

Fig. 6. Hydration reaction rates as a function of time for various initial sample
masses.
Fig. 8. Hydration Conversion plotted as a function of time at a hydration isotherm
of 30 ◦ C for various water vapor pressure Pw using an initial sample mass of 10 mg.

ple is increased. Higher porosity ease the vapor transport through

the sample, and hence, speed up the kinetics. This phenomenon
happens till the sample reaches a certain openness, and then stays
the same. The experiments presented in the following sections are
with the samples which are stabilized through cyclic precondition-
ing.

3.4. Hydration kinetics

The following section presents the results of hydration experi-

ments with operating conditions presented in Section 2.3. Differ-
ent parameters are varied to investigate effects on reaction rate.
Finally, a kinetic parameter estimation is done and a numerical
model is constructed based on the experimental results.

3.4.1. Effect of water vapor pressure

Fig. 7. Extend of conversion after 1 h for 10 hydration-dehydration cycles of a
A set of experiments is designed to see the influence of the va-
10 mg sample. Typical conditions (as presented in Section 2.3) are applied for hy- por pressure on the kinetics. In these experiments, the hydration
dration and dehydration. isotherm is kept at 30 ◦ C and hydration is only started when water
vapor is introduced to the system while the isotherm temperature
is maintained. The water vapor pressure (Pw ) is varied for each hy-
3.3. Cyclability dration cycle using the humidity generator.
Fig. 8 shows the effect of water vapor pressure on the hydra-
Cyclability of thermochemical materials is one of the most im- tion conversion. It can be observed that hydration of K2 CO3 has an
portant features to be considered, since a system should be able to expected dependency with regard to vapor pressure; conversion is
work through multiple cycles in order to be feasible. Performance faster for experiments with higher water vapor pressure. This im-
of the materials usually degrades over cycles. Especially, in case the plies that with higher vapor pressure, there is more driving force
deliquescence phenomenon occurs during hydration of the mate- to complete the hydration process.
rial, porous structure of the material will be lost, which leads to a To identify a relationship between reaction rate and water
degradation in performance. The cyclability of potassium carbonate vapor pressure, Fig. 9 is plotted. It shows the relation between
is studied in this section. average (Fig. 9(a)) and maximum (Fig. 9(b)) reaction rate with re-
Fig. 7 shows extend of conversion of hydration after 1 h for spect to the pressure ratio (Pw /Peq ). The equilibrium pressure (Peq )
10 hydration-dehydration cycles of a potassium carbonate sam- is known from the phase diagram of K2 CO3 (Fig. 1 and Eq. (3)). The
ple. As can be seen, the extend of conversion is increased in important finding is that the overall reaction rate is directly pro-
each cycle compared to the previous one. Therefore, performance portional to the vapor pressure, hence a linear relationship is es-
of potassium carbonate improves over cycles, and its kinetic be- tablished. Applying higher pressure ratios means having high water
comes faster after each cycle. Based on observation, the volume vapor pressure values away from the equilibrium line, as seen in
of the sample increases after each cycle, which can be the expla- the phase diagram of K2 CO3 , which leads to faster reaction rates.
nation for the improvement in performance. After each hydration, In order to have a uniform spread of values, the average rate
the crystal expands as expected, because of placement of water is taken over an uniform time interval for all the cases. From the
molecules in its structure. During subsequent dehydration, water obtained results, Eq. (10) shows that reaction rate for hydration of
molecules are removed from the structure, but the powder is not K2 CO3 follows a linear dependence with water vapor pressure ra-
contracted to the original form. Therefore, the porosity of the sam- tio. This is further confirmed with the kinetics parameter estima-
184 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

Fig. 9. Hydration reaction rate versus pressure ratio at a hydration isotherm of 30 ◦ C using an initial sample mass of 10 mg.

Here, the higher temperatures are closer to the equilibrium tem-

perature (in this case Teq =60 ◦ C for a vapor pressure of 13 mbar),
which leads to slower reactions. Having point of operation in the
region close to the equilibrium line leads to a low reactivity.
Fig. 12 shows the range of maximum reaction rates obtained by
varying vapor pressures and isotherms for K2 CO3 from the differ-
ent experiments performed for hydration.
Fig. 11(a) shows the reaction rate plotted against extent of con-
version. Clear peaks exist once the hydration is started (α = 0). In
order to find the Arrhenius dependence of the reaction rate, aver-
age and maximum reaction rates are plotted in Fig. 11(b). It can be
seen that at higher temperatures, the reaction rate proceeds very
slowly. However, the trend is not as clear for the average reaction
rates as the maximum reaction rates.
From the Arrhenius law, it is known that as temperature is in-
creased, the rate constant (k(T) as presented in Eq. (4)) increases,
which ultimately increases the reaction rate. However, the results
here show that with the increase in temperature, the reaction rate
decreases. The Arrhenius dependence needs to established after
finding out the values of individual rate constants for these exper-
Fig. 10. Conversion vs. time for hydration at various hydration isotherms with va-
por pressure of 13 mbar using an initial sample mass of 8mg. iments. This is done in Section 3.4.4.

3.4.3. Shape of reaction model

tion presented in Section 3.4.4. As mentioned earlier, the hydration of potassium carbonate fol-
lows a single step reaction. The procedure to obtain an appropriate
dα Pw
∝ h ( p) = (10) reaction model for a single step reaction is stated in the work of
dt Peq Vyazovkin et al. [27]. The single-step model can be selected by a
variety of numerical and graphical methods.
3.4.2. Effect of temperature It is stated in the work of Vyazovkin et al. [27], that when
A set of experiments is designed to identify the effect of tem- the reaction rate is at its maximum value as soon as the sample
perature on the reaction rate. This way, it can be found out if reaches the isothermal temperature, then the reaction is deceler-
the hydration reaction of potassium carbonate follows an Arrhe- atory. Models of the decelerating type represent processes whose
nius type of temperature dependency as presented in Eq. (4). The rate has maximum rate at the beginning of the process and de-
experiments were carried out at a fixed water vapor pressure Pw creases continuously as the extent of conversion increases. A sim-
of 13 mbar. ilar behavior for the hydration of K2 CO3 is observed in Fig. 11(a),
Fig. 10 shows conversion of hydration reaction vs. time for where the hydration process has maximum rate at the beginning
different isothermal temperatures. As can be seen, higher tem- of the conversion. The most common example of a deceleratory re-
perature leads to slower reaction. The reason is that the higher action model is,where n is the reaction order:
temperatures Teq are closer to the equilibrium temperature. The
f ( α ) = ( 1 − α )n (11)
equilibrium temperature is the temperature at which, for a specific
vapor pressure, the two phases (anhydrous and sesquihydrate) are Fig. 13 shows the plot ln(1 - α ) vs. time for the conversion val-
in equilibrium, and hardly any conversion from one phase to an- ues obtained from the results presented in Fig. 10. After analyzing
other one happens. The equilibrium temperature for the 13 mbar the shape of the plot from Fig. 13, the first order reaction (n = 1)
vapor pressure can be seen in the phase diagram Fig. 1 as the blue and contracting sphere (n = 2/3) models are possible for hydration
curve. From the phase diagram, it can be seen that the equilibrium of K2 CO3 , which are the first-order reaction model and the con-
temperature for a vapor pressure of 13 mbar is equal to 60 ◦ C. tracting volume reaction model, respectively. However, a more ex-
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 185

Fig. 11. Hydration reaction rate vs. conversion and temperature at a water vapor pressure of 13 mbar.

Table 2
Fitting parameters in the rate equation.

Tiso [o C] [Y(1)] [Y(2)] [Y(3)]

26 0.67 x 10−2 0.66 1.0024

30 1.67 x 10−2 0.6552 0.9824
40 2.21 x 10−2 0.6529 0.9929
48 2.94 x 10−2 0.6706 0.9848

Fig. 12. Reaction rate variation with respect to changes in hydration isotherms and
vapor pressure.

Fig. 14. Arrhenius Plot values for Hydration of K2 CO3 .

act value of n is attempted to be found out from the model fitting

method in the following section.

3.4.4. Estimation of parameters

As presented in Section 2.4, the reaction rate is fitted with
Eq. (9) and results are presented in Table 2. The fitting parameters
[Y(1)], [Y(2)] and [Y(3)] are the rate constant k(T), reaction order n
and order on the pressure ratio term respectively.
The parameter Y(1) gives the rate constant k(T) for the different
hydration isotherms. Once the rate constants k(T) is known, the
Arrhenius parameters, activation energy Ea and exponential pre-
factor Af are obtained from Fig. 14 and presented in Table 3, by
constructing a reordered Arrhenius equation:
E  1
a
Fig. 13. ln(1 - α ) vs. time plot to identify reaction models f(α ).
ln(k(T )) = − . + ln(A f ) (12)
R T
186 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

Fig. 15. Comparison between experimental data and numerical kinetic model data for hydration at isotherm temperature of 26 ◦ C.

Table 3 degree of accuracy, however at the point of completion of reaction,

Kinetic parameters for hydration of K2 CO3 .
the model underestimates the conversion.
Ea,hyd Af,hyd The numerically obtained reaction rates and conversions using
[kJ/mol] [1/min] Eq. (13) are shown in Fig. 16, for all the isotherm temperatures.
Hydration 46.220 1.0838 × 106
3.5. Deydration kinetics

Table 4
The following section presents the results of dehydration exper-
Arrhenius law validation for hydration ex-
periments performed with different hydration iments with operating conditions presented in Section 2.3. Differ-
isotherms. ent parameters are varied to investigate effects on reaction rate.
Tiso [◦ C] k [1/min] Pw /Peq (-) R2
Finally, a kinetic parameter estimation is done and a numerical
model is built based on the experimental results.
26 0.0067 16.25 0.97
30 0.0167 10 0.98
3.5.1. Effect of water vapor pressure
40 0.0221 5.41 0.97
48 0.0294 2.7 0.96 Similar to the hydration experiments, the dehydration driving
force is investigated. Using the relative humidity generator device,
the water vapor pressure is changed. For a favorable dehydration
cycle, the Pw should be close to 0 mbar. In reality, it is not possible
It can be seen from Table 2 that the order of reaction model
to attain a 0% R.H. in the experimental environment. The minimum
n (parameter Y(2)) takes up a power of approximately 0.66, which
attainable R.H. value in the apparatus is 1.1%, which corresponds to
represents a contracting sphere model ( f (α ) = (1 − α )2/3 ). In ad-
0.3 mbar water vapor pressure. The aim of these experiments is to
dition, the dependency on the pressure ratio is found to be linear
vary the vapor pressure, in order to understand the dependency of
(Y(3) ≈ 1).
reaction rate to pressure ratio. Fig. 17 shows the results for dehy-
Table 4 shows the values of rate constants and the pressure ra-
dration of K2 CO3 . The sample is heated up to 100 ◦ C with a heating
tios, which are used in the hydration experiments for various hy-
rate of 10 [K/min], as seen in the temperature profile in Fig. 17(a).
dration isotherms. It is observed that as the temperature increases,
It can be observed that as the vapor pressure is increased,
the rate constant also increases which validates the Arrhenius law.
the conversion slows down. In order to validate this, the reaction
However, as seen in Fig. 11(b), reaction rates are slower for higher
rates are plotted against the pressure ratios. Fig. 17(b) shows that
temperatures. This is explained by the pressure ratio values as seen
as pressure ratio increases, the reaction rate decreases. According
in Table 4, which decrease by increasing temperature.
to the literature [30], similar experimental results have been ob-
served, that is, when the pressure ratio (Pw /Peq) approaches to 1,
3.4.5. Final hydration reaction model reaction rates becomes closer to zero. Analogous to the case of hy-
To conclude, the kinetics of hydration reaction of K2 CO3 can be dration, it can be concluded that the pressure function is also a
modelled using Eq. (13) with the kinetic parameters in Table 3. driving force for dehydration. For dehydration of K2 CO3 , reaction
The experimental data for each isotherm temperature is compara- rate is inversely proportional to water vapor pressure.
ble with mathematically constructed reaction rate. Table 4 shows
their corresponding R2 values determining the accuracy of the fit. 3.5.2. Effect of temperature
The values are close to 1 indicating the model to be a good fit for A set of experiments is designed to identify the effect of tem-
the experimental results. perature on the reaction rate. The dehydration is carried out while
dα
 Ea
 P  heating up from ambient temperature to different temperatures
· ( 1 − α ) 2/3 ·
w
= A f · exp − (13) using a constant heating rate of 10 [K/min]. The expected result is
dt RT Peq
that a trend could be achieved when temperature is varied similar
As an example, Fig. 15 shows the comparison between the ex- to the hydration process.
perimental and numerical kinetics model data for the isotherm at Fig. 18(a) shows the conversion for dehydration reaction when
26o C. The model predicts the extent of conversion to an acceptable heating up a sample to different temperatures. No expected trend
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 187

Fig. 16. Numerically modelled reaction rates and conversions for various hydration isotherms.

Fig. 17. Effect of water vapor pressure on conversion and reaction rates for dehydration of a sample with an initial mass of 8 mg. The heating rate used is 10 [K/min] and
the temperature profile can be seen in (a).

is observed, moreover, all the conversion curves have almost the action, which is related to the amount of heat provided per unit of
same completion time. Fig. 18(b), that shows the reaction rates, time, and is exactly the function of heating rate.
also does not show a particular trend. This is because the dehydra- Fig. 19 shows the dehydration conversion and reaction rate for
tion process is completed in the heating up ramp, from the initial various heating rates. It can be clearly observed that conversion
start temperature to the final set temperature as seen in Fig. 18(a), is faster for higher heating rates. For higher heating rates, more
where the dotted lines show the temperature profiles. Irrespective amount of heat is provided per minute, leading to a faster con-
of the final temperature, dehydration starts as soon as an appro- version and higher reaction rate. This data will be used for kinetic
priate driving force is available with increase in temperature. So, model prediction for dehydration of K2 CO3 .
even before the final isotherm is reached, most of the dehydration
reaction is completed. 3.5.4. Estimation of parameters
Since dehydration occurs at a non-isothermal temperature con- In order to utilize the isoconversional methods, peak temper-
dition, as opposed to hydration, the procedure to obtain kinetics atures Tmax (the temperature at which the rate is maximum) are
for dehydration will differ from the procedure used for hydration. needed to be retrieved from the DSC/DTG signals of the experi-
The use of single heating rate methods for the purpose of kinetic ments. Fig. 20 shows the peak temperatures for each heating rate,
predictions of dehydration experiments is not capable of produc- for both the differential scanning calorimetry (DSC) signals as well
ing meaningful results [27], so multiple temperature programs are as derivative thermo–gravimetric (DTG) signals. The DSC signals
used. Iso-conversional methods will be used, which employs the only for this set of experiments were recorded with the values be-
use of different heating rates to investigate the dehydration pro- ing positive for dehydration.
cess. For the DSC signals, Tmax is retrieved from the curves at the
point where the difference is maximum relative to the baseline of
3.5.3. Effect of heating rate the curve. In this manner, peak temperatures extracted from DSC
A set of experiments is designed to investigate dehydration pro- and DTG are listed in Fig. 20(a) and (b), respectively. Peak tempera-
cess with varying heating rates with a final temperature of 100 ◦ C tures from both the signals are almost equal with not much drastic
and a vapor pressure 13 mbar. Dehydration is an endothermic re- differences, as expected.
188 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

Fig. 18. Effect of temperature on dehydration conversion and reaction rate for a water vapor pressure of around 1 mbar using a heating rate of 10 [K/min].

Fig. 19. dehydration conversion and reaction rate for various heating rates with a final temperature of 100 ◦ C and an initial sample mass of 10mg.

Fig. 20. Peak temperature estimation for dehydration using various heating rates.

Based on so-called Kissinger method, a plot between ln(β /Tmax

2 ) Table 5
Kinetic parameters obtained using Kissinger
vs. (1/Tmax ) is made, as seen in Fig. 21. The method is based on
Method.
the Eq. (14), where β [K/min] is the heating rate and Tmax [K] is
the maximum peak temperature. The drawback of this method Ea,dehyd Af,dehyd
[kJ/mol] [1/min]
is that it gives only one set of kinetic parameters, which means
one value for Activation energy and exponential pre-factor for Dehydration 78.30563 8.8980 × 1010
whole range of conversion. This could possibly lead to over pre-
dicting Ea values. Table 5 shows the values of activation energy
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 189

Table 7
Specific reaction enthalpy, energy storage density per unit of mass and
unit of volume, based on the experiment presented in Fig. 25.

β h h E/V
3
[K/min] [kJ/mol] [MJ/kg] [GJ/m ]
10 64.01 0.71 1.27

dehydration and hydration. The values of energy storage density,

energy stored/released and peak power is determined based on the
hydration isotherm and heating rate for the hydration and dehy-
dration processes, respectively. The setup can log the TG and DSC
signals simultaneously, which allows to estimate the thermal en-
ergy change per mole of H2 O. The principle of determining the
released heat during hydration or dehydration of a sample is ex-
plained in Section 2.4.
Fig. 25 shows the DSC signal and loading vs. time for a 8 mg
sample, which was dehydrated with a heating rate of 10 [K/min].
It can be seen that the state of hydration is anhydrous after the
Fig. 21. Kissinger method plot indicating the slope equation and R2 value.
dehydration process is finished. Correspondingly, a DSC peak can
be seen, which is integrated to obtain the stored heat during the
Table 6
R2 , Goodness of fit coefficient for the numerically ob- endothermic reaction of dehydration. The interval for integration
tained α values compared to experimental α values for is the time in which the loss of water molecules starts until the
all heating rates. sample is anhydrous. The area under the peak is obtained through
β [K/min] R2 integration. Fig. 25(a) indicates the energy stored in [mJ] and the
peak power in [mW]. Using the obtained values, the specific reac-
0.5 0.98
1 0.97
tion enthalpy (per mole of water), energy storage density per unit
2 0.96 of mass (of dry salt) and volume (of the crystal of the salt) are
7.5 0.94 calculated and presented in Table 7.
10 0.90 A similar analysis is done for hydration of K2 CO3 using the
15 0.93
same principle as used for dehydration. The released heat during
hydration of K2 CO3 between an- and sesquihydrate state for vari-
ous hydration isotherm temperatures is shown in Fig. 26.
and exponential pre-factor calculated based on the Kissinger Fig. 26(a) shows the DSC data for hydration of a 8 mg K2 CO3
method. sample for varying temperatures using a water vapor pressure of
 β  A R  E  13 mbar. The energy released in [mJ] and the maximum released
f a
ln = ln − (14) power in [mW] are also indicated. The energy released obtained
Tmax 2 Ea RTmax
through integration is the area under the peak above the zero
3.5.5. Final dehydration reaction model baseline, which is the horizontal axis for all signals. The maximum
Using Eq. (15) with the kinetics parameters in Table 5, the ex- released power is the power released once the hydration is initi-
perimental results can be estimated for dehydration of K2 CO3 . ated, which keeps decreasing as the reaction progresses. Fig. 26(b)
dα

Ea
 P  shows the corresponding loading calculated based on the TG sig-
· ( 1 − α ) 2/3 ·
eq
= A f · exp − (15) nal.
dt RT (t ) Pw It can be observed that even though the maximum released
Fig. 22 shows the results of the kinetic model compared to the power values decrease with increase in temperature, the area
experimental data for the dehydration of K2 CO3 using a heating under the peaks is more or less the same, between 4700 −
rate of 15 [K/min] from 30 to 100 ◦ C. It is an acceptable fit, how- 4800 [mJ]. Fig. 11 shows the results of reaction rates for the same
ever, the conversion is different towards the end. This is due to set of experiments. It can be seen that, the reaction rates di-
the thermal lag in the temperature program. Fig. 23 shows the lag rectly translates to maximum power released. Higher the reaction
in an experimentally measured temperature compared to the pro- rate, higher is the maximum power released for varying isotherm
grammed temperature. It is not possible to follow the temperature temperature.
program during the final increase of temperature between 90–100 As the dependence of maximum power released on various
◦ C. temperature is observed, a similar dependence can be observed
To conclude, Fig. 24(a) and (b) show the numerically modelled between maximum power released and different values of the ap-
reaction rates and extent of conversion for different heating rates plied water vapor pressure. However, dependence of water vapor
from 30 to 100 ◦ C using Eq. (15). Table 6 shows the corresponding pressure on power released for K2 CO3 is not considered in this
R2 values for the model fits with experimental data for determin- study. Such dependencies between peak power and water vapor
ing the accuracies of the fits. The values are close to 1 indicating pressure have been observed with the use of salt hydrates like cal-
the model to be a good fit compared with the experimental results, cium chloride and magnesium chloride [20].
except for higher heating rates, which can be explained due to the The experimental values of specific reaction enthalpy and en-
thermal lag in the temperature profiles. ergy densities for hydration of K2 CO3 are presented in Table 8.
Based on NBS tables [36], the literature value for specific enthalpy
3.6. Enthalpy of reaction is 65.4 [kJ/mol]. The experimental values for enthalpy are lower
than the theoretical value by 6 − 7%.
This section presents the results of experiments performed to So far, the energy storage density values that have been calcu-
find the enthalpy of reaction calculated using DSC signals, for both lated are based on the crystal density. However, bulk energy stor-
190 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

Fig. 22. Comparison between experimental data and numerical kinetic model data for dehydration using a heating rate of 15 [K/min] from 30 to 100 ◦ C.

Table 8
Specific reaction enthalpy, energy storage density per unit of
mass and unit of volume for various hydration isotherms using
a water vapor pressure of 13 mbar.

Tiso h h E/V
3
[K/min] [kJ/mol] [MJ/kg] [GJ/m ]

26 61.54 0.67 1.22

30 60.90 0.66 1.20
40 60.22 0.65 1.19
48 60.87 0.66 1.20

4. Performance in view of application

Based on the developed kinetics and measured enthalpy of re-

action, the thermal power of the reaction can be calculated for
different conditions. Fig. 27 shows hydration reaction rate vs. ex-
tend of conversion at 20 ◦ C hydration isotherm temperature using
a water vapor pressure of 13 mbar. As can be seen the maximum
Fig. 23. Modelled temperature profile versus experimental temperature profile of reaction rate occurs at the beginning of the process when α = 0.
15 [K/min]. Therefore, the maximum power is also achieved at the beginning
of the process.
As discussed, the hydration reaction rate varies with tempera-
age density can be calculated based on the porosity of the salt hy- ture in two ways: first, the kinetics constant follows an Arrhenius
drate. For a porosity of around 40%, the bulk energy storage density type of temperature dependency, and second, the equilibrium
3
can be calculated to be around 0.75 [GJ/m ]. vapor pressure is dependent on temperature. In Eq. (4), the former

Fig. 24. Numerically modeled reaction rates and extent of conversions for dehydration using various heating rates from 30 to 100 ◦ C.
 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193 191

Fig. 25. Dehydration of a 8 mg K2 CO3 sample using a heating rate of 10 [K/min].

Fig. 26. Hydration of a 8mg K2 CO3 sample using various hydration isotherm temperatures using a water vapor pressure of 13 mbar.

Fig. 27. Reaction rate vs. extend of conversion at 20 ◦ C hydration isotherm temper-
Fig. 28. Temperature and pressure functions for various hydration isotherm tem-
ature using a water vapor pressure of 13 mbar.
peratures using a water vapor pressure of 13 mbar.

dependency is considered in the kinetics constant k(T) and the

latter one in pressure ratio h(p). Fig. 28 shows temperature and the temperature leads overall to a decrease in the rate, and hence,
pressure functions of reaction rate at its maximum for different in the power. On the other hand, it can be concluded that even
temperatures. As can be seen, k(T) increases with temperature, though the thermal output is lower at higher temperature, it is still
while h(p) decreases. high enough for domestic purposes. For instance at 60 ◦ C, thermal
Fig. 29 shows the maximum rate and thermal power of the hy- power is around 0.77 W/g at its maximum and more than 0.5 W/g
dration reaction. As can be seen, the twofold effect of increasing on average.
192 M. Gaeini, S.A. Shaik and C.C.M. Rindt / Energy & Buildings 196 (2019) 178–193

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