Applied Thermal Engineering 27 (2007) 2455–2462

www.elsevier.com/locate/apthermeng

Isothermal sorption characteristics of the BaCl2–NH3 pair

in a vermiculite host matrix
a,*
Y. Zhong , R.E. Critoph a, R.N. Thorpe a, Z. Tamainot-Telto a, Yu.I. Aristov b

a
School of Engineering, University of Warwick, CV4 7AL, UK
b
Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia

Received 15 November 2006; accepted 24 February 2007

Available online 19 March 2007

Abstract

Chemisorption could be useful in adsorption systems due to the large concentration change compared with physisorption. Equilib-
rium concentration characteristics of ammonia with a composite adsorbent material (BaCl2 impregnated into a vermiculite matrix) are
investigated: the maximum concentration is about 0.4 kg ammonia/kg adsorbent. Hysteresis was observed between the synthesis and the
decomposition reactions. The analysis of the data suggests that the hysteresis could be due to the dimensional changes of the solid during
the reactions. The bi-variant behaviour observed was contrary to the mono-variant behaviour anticipated and the reasons are discussed.
The COP of a basic adsorption cycle for typical ice-making and air-conditioning applications utilizing ammonia and the composite mate-
rial were calculated. The results show that the material could be used for air-conditioning or other refrigeration applications. The COP
could reach up to 0.6 at typical conditions (Tev = 15 °C, Tcon = 35 °C).
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; Equilibrium; Hybrid material; Ammonia; Hystersis, Bi-variant

1. Introduction impregnated into various matrices, such as activated car-

Ammonia is widely used as a refrigerant in adsorption
refrigeration or heat pump systems. The advantages
include high enthalpy of vaporisation, stability, wide tem-
perature range and low freezing temperature. One of the
most commonly used adsorbents for ammonia sorption is
activated carbon [1,2]. Recently, a family of new composite
sorbents has been developed for adsorption heat pumps.
These so called hybrid materials, are two-component
adsorbents which consist of a porous host matrix with open
pores and a metallic salt impregnated into its pores. Due to
their physical structure the materials take an intermediate
position between solid adsorbents and pure metallic salts
and can be manufactured in such a way as to demonstrate
the best features of both systems. So far, composites for
ammonia sorption have been synthesized with CaCl2
*
Corresponding author. Tel.: +44 2476 523137; fax: +44 2476 418922.
E-mail address: zhongyong77@gmail.com (Y. Zhong).
bon [3,4], the synthetic carbon Busofit [5], CaSO4 [6,7].
These materials have greater sorption capacity compared
with non-impregnated matrices and better kinetics than
the bulk salt [8]. However, the salt swelling, due to its reac-
tion with ammonia, can damage the matrix structure [9], so
the choice of a proper host matrix is very important.
It was found that one promising inorganic host matrix is
an expanded vermiculite [10], in which the pore volume
reaches 3.2 cm3/g. It allows insertion of a large amount
of salt inside the pores, reaching an ammonia uptake of
68.5 wt% (for a composite ‘‘63.5 wt% CaCl2/vermiculite’’)
[10]. One more very important advantage of vermiculite,
which results from its large pore volume, is that it can effi-
ciently accommodate the salt swelling due to its reaction
with ammonia.
Barium chloride forms only one stable compound, and
the transition is treated in this study as a single step. The
equation for the synthesis and decomposition reactions
between BaCl2 and NH3 is,

1359-4311/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.applthermaleng.2007.02.011
2456 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462
Nomenclature
COP coefficient of performance
p pressure (kPa)
Dh Enthalpy of reaction (kJ kg1)
R gas constant (kJ kg1 K1)
T temperature (K)
Ds Entropy of reaction (kJ kg1 K1)
x mass concentration (kg ammonia /kg adsorbent)
BaCl2 þ 8NH3 $ BaCl2  8NH3
Both the decomposition and synthesis temperatures of
the ammonia – barium chloride complex can be determined
from the van’t Hoff equation for the equilibrium of a solid
gas reaction [10–12].
Dh Ds
ln p ¼  þ ð2Þ
RT R
Experimental isosteres and isotherms of NH3 sorption
on a new composite ‘‘BaCl2/expanded vermiculite’’ are pre-
sented here. The material was prepared by immersion of
the matrix with an aqueous solution of BaCl2 followed
by its drying at 200°C for 5 h. This gave a salt content of
58.7%, which is close to the maximum salt content, expend-
ing of which can be yet accommodated by the vermiculite
matrix. The typical grain size was 2.0–3.0 mm [8].
2. Experimental apparatus for determining equilibrium
adsorption properties
The experimental apparatus consists of Rubotherm
ISOSORP 2000, glycol water bath system and oil bath sys-
tem. A simplified schematic diagram of the experimental
rig is shown in Fig. 1. A photograph of the set-up is shown
in Fig. 2. The adsorbent sample was contained in a small
basket (Fig. 3), which was suspended inside the sealed steel
Valve
Liquid NH3
Water Bath
Thermocouples
Glycol Water Bath System
Fig. 1. Schematic diagram of porosity test rig.
Subscripts
con condensation
ev evaporation
dec decomposition
g gas
s solid
syn synthesis
ð1Þ chamber. The chamber was within a jacket, through which
heated oil circulates in order to maintain temperature of
the vessel and sample. At a given temperature, four ther-
mocouples within the chamber were used to measure the
adsorbent temperature and the wall temperature to ensure
an equilibrium state when measuring concentration. When
a new temperature was selected, readings were only taken
when the temperatures measured by the four thermocou-
ples were within 0.5 °C for a period of at least 30 min.
The system pressure was the saturation pressure of the
ammonia at the temperature of reservoir. The reservoir
was emerged into the glycol water bath system with the
temperature controlled by Cole–Parmer controlled bath.
The system pressure was measured directly with a cali-
brated pressure transducer (Druck PDCR 920). The mass
of the sample in the basket was measured by Rubotherm
magnetic suspension balance. The adsorbate concentration
was calculated directly from the mass, taking account of
gas buoyancy forces. The resolution of the equipment is
0.01 mg and the uncertainty less than 0.002%. The stan-
dard deviation of successive measurement is less than
±0.03 mg.
Before the tests, adsorbent was dried at 180 °C for at
least 12 h in the air at atmospheric pressure and then in
vacuum to make sure that all water vapour was eliminated
from the sample. The sample was then exposed to ammo-
nia and cooled to a set temperature to start equilibrium
Magnetic Suspension
Balance
Rubotherm ISOSORP 2000
Reactor
Sample Oil Bath
System
 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462
Fig. 2. A photograph of the set-up.
Fig. 3. Container and the sample.
tests. In this experiment, the system pressure was the satu-
rated pressure of liquid ammonia in a vessel submerged in a
glycol water bath whose temperature was controlled via a
personal computer. During the experiments, the sample
temperature ranged from 20 to 100 °C and the pressure
within the steel chamber was from 2 to 20 bar.
A Druck PDCR 920 absolute pressure transducer with a
0 to 35 bar range, a resolution of 0.35 bar/mV and an accu-
racy of ±1.5% was used to monitor the pressure. A Straw-
2457
berry Tree DATAshuttle (DA-16-8-TC-AO) was used to
acquire the data from thermocouples and pressure trans-
ducers and to control both baths. The stated accuracy of
the DATAshuttles is ±0.3 K on temperature and ±25
lV ± 0.05% of reading on voltage. The control process
and data logging was performed utilising the dedicated
WorkBench software running on a personal computer
operating in conjunction with the DATAshuttle. All of
the experimental data were logged at one second intervals
(sampling frequency of 1 Hz per channel) and written to
local hard-disk for processing and analysis at a later stage.
3. Results and discussion
A typical cycle (isothermal adsorption and desorption)
is represented by the open circles in Fig. 4. The temperature
was maintained at 37 ± 0.5 °C whilst the pressure increased
from 1.9 to 10.7 bar (T/Tsat ratio of 1.23 to 1.01 in Fig. 4)
and then decreased back to the starting value. The synthe-
sis reaction began at a T/Tsat of about 1.11 and ended at
1.07. The decomposition began at 1.13 and ended at 1.16.
The arrows showed the direction in which the experimental
measurements were performed. It can be seen that a hysteresis
2458 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462

50 1.1)is about x = 0.413, 0.408 and 0.382, respectively. So the

100% synthesis 0% decomposition
average ammonia concentration is about 0.40 ± 0.013 (the
Concentration, (%)

40
standard relative error is ±3.5%). Thus, the number of
30 moles of NH3 adsorbed per mole of salt is (0.4/17)/
20 (0.587/208.2) = 8.35 ± 0.30 moles, which is close to the sto-
ichiometrical numbers of moles in BaCl2 Æ 8NH3 complex.
10
0% synthesis 100% decomposition In principle, the remaining 0.35 moles may be attributed
0 to adsorption by the vermiculite.
1 1.05 1.1 1.15 1.2 1.25
The two key features of Figs. 4 and 5 are the bi-variant
T/T sat nature of the phase transitions and the hysteresis. These
Fig. 4. Concentration (mass of adsorbed ammonia/[mass of vermicu- will be addressed separately.
lite + BaCl2]) against T/Tsat at 37 °C.
3.1. Bi-variance
loop was formed. The isothermal hysteresis loops measured
It is evident that for a specific adsorbent temperature,
at around 43.5 and 54.5 °C are also shown in Figs. 5 and 6.
the reaction of synthesis and decomposition occurs over a
By comparing Figs. 4–6, it is seen that as the adsorbent
range of saturated temperature. In other words, the non-
temperature increases, the saturation temperatures (pres-
vertical hysteresis loop requires both temperature and pres-
sure) for both decomposition and synthesis also increase,
sure to be specified in order to determine the state of the
consistent with the van’t Hoff Equation. The circles and
system.
squares in Fig. 5 represent the first and second times that
According to the Gibbs phase rule the number of
the hysteresis loop was repeated, illustrating that the hys-
degrees of freedom v for the system with k components, f
teresis loops can be reproduced. It is worth pointing out
phases and r independent reactions could be calculated as
that to ensure that the test sample was at equilibrium con-
v = k + 2  f  r [13]. Normally, the salt and its resultant
ditions, the system pressure was kept constant for 10 h for
of adsorption reaction are considered as two different sol-
each data point shown in Figs. 4–6.
ids [16]. This system consists of three components (BaCl2,
The mass fraction of ammonia adsorbed per mass of
NH3 and BaCl2 Æ 8NH3) in three phases ([BaCl2]sol,
vermiculite plus salt composite at temperatures of 37,
[NH3]gas and [BaCl2 Æ 8NH3]sol). Therefore, the system
43.5 and 54.5 °C, and close to saturation pressure (T/Tsat 
should be mono-variant (v = 3 + 2  3  1 = 1), although
we observe it to be bi-variant.
One possible reason could be the formation of com-
50
plexes BaCl2 Æ nNH3 with variable n, which would add
Concentration, %

40 more degrees of freedom for this system. Such complexes

30 are known for bulk crystalline hydrates of Barium Oxalate
20 [14], but, as to our knowledge, such complexes have not
10 been detected for Barium Chloride. A more reasonable
0 explanation is that micro crystallites of the confined salt
1 1.05 1.1 1.15 1.2 1.25 are not homogeneous due to various sizes of these crystal-
T/T sat lites inside the pores. Each particular micro crystallite crys-
tal undergoes a mono-variant synthesis or decomposition
First cycle Second cycle
at its own temperature and pressure determined by the
Fig. 5. Concentration (mass of adsorbed ammonia/[mass of vermicu- van’t Hoff equation. Thus, the system behaves as bi-variant
lite + BaCl2]) against T/Tsat at 43.5 °C. due to the mentioned non-uniform micro crystallite crystal.
Similar effect was reported in [15] for hydration of calcium
nitrate confined to silica gels with various average pore
50 size. It was found that the hydration temperature depends
on the pore size which dictates the size of salt micro crys-
40
Concentration, %

tals. This effect was attributed in [15] to contribution of

30 the surface energy of confined salt and its hydrate.
20
3.2. Hysteresis
10

0 A possible explanation for hysteresis is that the mea-

1.02 1.04 1.06 1.08 1.1 1.12 1.14
sured gas phase temperature could be somewhat different
T/T sat
to the temperature within the interior of the salt particle.
Fig. 6. Concentration (mass of adsorbed ammonia/[mass of vermicu- The exothermicity of the synthesis reaction and endo-
lite + BaCl2]) against T/Tsat at 54.5 °C. thermicity of the decomposition reaction could cause such
 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462
8.23
8.22
8.21
Mass, g
8.2
8.19
8.18
8.17
0 2 4 6 8 10 12
Time, hours
Fig. 7. Change in mass against time (min) when the saturation temper-
ature was changed from 17 to 20 °C at an adsorbent temperature of
22 °C.
a temperature difference. In this situation, the solid temper-
ature, TS, would lag the gas temperature, TG. In other
words, TS < TG during decomposition, and TS > TG during
synthesis. If the temperature lag, DT = jTS–TGj, increased,
then the width of the hysteresis loop would increase.
The time required to approach equilibrium after the sat-
urated temperature had been decreased from 17 to
20 °C, and held constant at 20 °C for around 10 h, is
shown in Fig. 7. Initially, the rate of mass loss was rapid
but then decreased to a much slower value. After a long
time (8 h) the change of the mass still occurred at a steady
rate (1.17 mg/h). The slow rate of reaction is probably
caused by the small chemical driving force, Dp = jpG–pSj,
where pG is the ammonia pressure in the gas phase and
pS is the equilibrium ammonia vapour pressure over the
solid at the existing conditions (temperature, extent of solid
conversion), given by the van’t Hoff equation. By defini-
tion, the chemical driving force for the reaction at constant
temperature becomes small when the gas phase pressure
approaches the solid ammonia vapour pressure. As equilib-
rium is approached, Dp becomes smaller and the reaction
rate becomes slower. If the time to obtain equilibrium state
at constant temperature had been extended beyond 10 h to
much longer (100 or 1000 h), perhaps real equilibrium may
have eventually been attained.
Although, this explanation that hysteresis may be
caused by a temperature lag between the solid and the
gas may be valid for short equilibrium time, it is unlikely
to be valid when the temperature is held constant for sev-
eral hours. The data in Fig. 7 indicate that after 4 h the
reaction rate has become slow, which means that the heat
generation rate would also be slow. It also means that little
departure from thermal equilibrium would be expected.
Therefore, in this case, it is unlikely that temperature lag
could be the cause of hysteresis [16].
There is another explanation for the hysteresis loop, that
it is related to the expansion and contraction of the crystal
lattice as the ammonia content in the BaCl2–NH3 complex
changes. The hysteresis loops are somewhat reminiscent of
the pore filling–pore emptying phenomena that occur dur-
ing physical adsorption [17], and these have been ascribed
to dimensional changes of the solid [18]. The hysteresis
2459
phenomena shown in Figs. 4–6 may be associated with
the expansion of the BaCl2 salt when the synthesis reaction
occurs and the contraction of the BaCl2 Æ 8NH3 salt when
decomposition occurs. The unit cell dimensions increase
as the crystal density changes. Hysteresis may be caused
by solid phase changes, in which different solid phases have
different crystal structures. An activation barrier is neces-
sary to expand the solid, while the work of expansion is
not recovered on contraction [16,18]. The hysteresis area
is a measure of the irreversible energy loss during a com-
plete adsorption–desorption cycle [19].
3.3. Data fitting
For each hysteresis loop, obtained at a given adsorbent
temperature, four data points were selected, the onset of
synthesis (0% synthesis), the termination of synthesis
(100% synthesis), the onset of decomposition (0% decom-
position), and the termination of decomposition (100%
decomposition)as shown in Fig. 4. These four data are
determined by the following procedure: One straight line
was drawn through the decomposition data points. And
another line was drawn through the synthesis data points.
These lines intersected the horizontal lines corresponding
to 0 and 100% synthesis. The four intersection points were
the onset and termination of synthesis and decomposition.
The data for 0% synthesis (open circles) and 0% decompo-
sition (solid squares) are shown in Fig. 8. The 0% synthesis
point represents the first molecule of ammonia that reacts
with the salt during the synthesis reaction. Similarly, the
0% decomposition point represents the first molecule of
ammonia that is produced during the decomposition reac-
tion. The position of the starting points for synthesis and
decomposition is very important to the equilibrium and
dynamics of adsorption pair. These points were not influ-
enced by either heat transfer or mass transfer [16]. Also,
since both 0% synthesis and 0% decomposition are on the
same line, one can assume that the same micro-crystallites
of the salt are involved in sorbing the first molecule of
ammonia during the synthesis reaction and releasing the
first molecule of ammonia during the decomposition
reaction.
10000
Pressure, kPa
1000
100
-3.3 -3.25 -3.2 -3.15 -3.1 -3.05 -3
-1
-1000/ T sat , K
0% synthesis 0% decomposition
Fig. 8. Logarithm of ammonia pressure (kPa) vs. negative inverse
temperature (1000/K) for 0% synthesis and 0% decomposition.
2460 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462

10000 50

40
Pressure, kPa

Concentration (%)
1000 30

20

10
100
-3.3 -3.25 -3.2 -3.15 -3.1 -3.05 -3 0
-1000/ T (K -1 ) 1 1.05 1.1 1.15 1.2 1.25
T/T sat
100% synthesis 100% decomposition
Experimental results Data fits of synthesis
Fig. 9. Logarithm of ammonia pressure (kPa) vs. negative inverse Data fits of decomposition
temperature (1000/K) for 100% synthesis and 100% decomposition.
Fig. 10. Comparison between experimental results and data fits of
synthesis and decomposition processes at the adsorbent temperature of
The position of the onset points for synthesis and 37 °C.
decomposition, which are referred to as a transition line,
is important to the determination of the equilibrium and
The slope of 100% synthesis and decomposition are both
dynamic characteristics of an adsorption pair. At a given
larger that those obtained for 0% synthesis and 0% decom-
adsorbent temperature, adsorption happens when the sys-
position, that indicates higher activation barrier and stron-
tem pressure is greater than onset pressure of synthesis
ger reformation of salt structure for micro crystals
and desorption happens when the system pressure is less
responsible for sorbing the last NH3 molecule during the
than onset pressure of decomposition. The transition line
synthesis reaction and releasing the last molecule of ammo-
shown in Fig. 8 is given by:
nia during the decomposition step.
1000 Assuming during the transition between 0 and 100% of
ln pNH3 ¼ 4:98 þ 22:26 ð3Þ
T synthesis and decomposition, respectively, the concentra-
tion is linear with,T/Tsat, the equation to describe the pro-
where, T is the temperature of reaction bed.
cesses of synthesis and decomposition can be obtained by
The data for 100% synthesis (open circle) and 100%
combining Eqs. (3)–(5),
decomposition (solid square) are shown in Fig. 9. These
For synthesis,
data points represent the conditions at which the last mol-
ecule reacted during our experiments. The line for 100% 1000
ln pNH3 ¼ ð4:98 þ 0:3xÞ  þ 22:26 þ 2x ð6Þ
synthesis has a slightly smaller slope, which according to T
Eq. (2), means that Dhdec > Dhsyn, where, Dhdec, is the endo-
For decomposition,
thermic energy required to break the bonds between the
ammonia and the salt. While Dhsyn is the exothermic energy 1000
ln pNH3 ¼ ð5:9  2:3xÞ  þ 24:85  6:5x ð7Þ
released when the ammonia – salt bonds are formed, minus T
the endothermic energy required to expand the lattice of where, x is the concentration of the adsorbent (from 0 to
the salt. The smaller slope for 100% synthesis suggests that 0.4 kg ammonia/kg adsorbent). These equations provide
during decomposition, only the endothermic energy to a relationship between temperature, pressure and concen-
break the ammonia – salt bond must be supplied instanta- tration (T, p, and x).
neously and the salt can relax to its former dimensions The state of the hystersis loop can be determined by
slowly. Therefore, this exothermic relaxation energy may specifying two of these variables. Fig. 10 shows the fairly
not be available, and it may not contribute to the Dhdec good agreement between the experimental data and Eqs.
value. A synthesis line having a smaller slope than (6) and (7).
the decomposition line was also observed by Marty [18] In a real chemical heat pump, the temperature will be
for the MnCl2–NH3 system and Ternana [16] for the changed at a substantial rate to provide a reasonably large
CoCl2–NH3 system. chemical driving force, which implies that non-equilibrium
The van’t Hoff equation can also be used to describe the effects will be important. However Eq. (3) is still of practi-
termination of synthesis and decomposition, cal significance in the design of a chemical heat pump using
For 100% synthesis, the NH3–BaCl2 system since it can be used to predict the
1000 onset of the phase change.
ln pNH3 ¼ 5:10  þ 23:05 ð4Þ
T
4. Modelling of thermodynamic cycles
For 100% decomposition,
1000 It is possible to calculate a cooling COP (Coefficient of
ln pNH3 ¼ 5:90  þ 24:85 ð5Þ
T performance = Cooling/Heat input) for this material used
 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462 2461

20

18

16

pcon 14 T2 T3

12
Pressure, bar

10

8
pev T1 T4
6

4 Pure NH3
0% Tansition (Adsorption and Desorption)
2 100% Synthesis (Adsorption)
100% Decomposition (Desorption)
0
-20 0 20 40 60 80 100 120
Temperature, oC

Fig. 11. A basic adsorption cycle on the Clapeyron diagram.

Table 1
Performance of adsorption system for the idealised basic cycle
Tev 10 0 10 15
Tcon T1 T3 COP T1 T3 COP T1 T3 COP T1 T3 COP
25 20 56 0.658 27 56 0.674 33 56 0.688 37 56 0.696
30 20 58 0.617 27 58 0.632 33 58 0.645 37 58 0.653
35 20 61 0.566 27 61 0.58 33 61 0.592 37 61 0.598
45 20 67 0.536 27 67 0.548 33 67 0.56 37 67 0.566

in a basic adsorption cycle, which is shown in Fig. 11.
Heats of desorption (decomposition) and adsorption (syn-
thesis) may be calculated from the slopes of the lines of
Figs. 8 and 9, as is shown in Eqs. (6) and (7). Then, using
an estimated specific heat of 1000 J/(kg K) for vermiculite,
it is possible to estimate COP to a particular evaporating
temperature (Tev), condensing temperature (Tcon). The
onset temperatures of the decomposition and synthesis
reaction (T2 and T4) are obtained from Eq. (3). The final
adsorption temperature (T1) and the driving temperature
needed for desorption (T3) are calculated from Eqs. (4)
and (5). For a typical ice-making application (Tev =
10 °C, Tcon = 25 °C), the calculated T1, T2, T3 and T4
are 20, 51, 56 and 27 °C, respectively. The minimum and
maximum heats of desorption are 1600 and 1942 kJ/kg.
The minimum and maximum heats of adsorption are
1748 and 1837 kJ/kg. Table 1 shows the COP for some typ-
ical air-conditioning and ice-making applications. It is
worth pointing out that these calculated results are idea-
lised, since there is no allowance for the thermal mass of
a containing vessel and higher driving temperatures will
be needed to achieve a reasonable rate of reaction, but
gives an upper limit to the performance. Also the calcu-
lated final adsorption temperature (T1) for some cases, in
particular for the ice-making application, is less than the
condensation temperature (Tcon), which is not practical
for a real adsorption system. So, to use this material in
an ice-making adsorption system, the condensation tem-
perature will have to set to be a low value or T1 is set to
above the calculated final adsorption temperature, which
means incomplete adsorption and therefore smaller COP.
5. Conclusions
A new composite ammonia sorbent was synthesized and
studied. The isotherms of ammonia sorption were
measured at T = 20 to 100 °C and P = 2 to 20 bar. The
maximum concentration is about 0.4 kg ammonia/kg
adsorbent. It was found that the modification of host
matrices by the salt dramatically increases the ammonia
uptake due to the formation of BaCl2 Æ 8NH3 complex.
The large concentration change makes this sorbent attrac-
tive for adsorption heat pumps. The interesting advantage
of vermiculite is that it can accommodate the salt swelling
2462 Y. Zhong et al. / Applied Thermal Engineering 27 (2007) 2455–2462
during reaction between ammonia and the salt. Hysteresis
between the synthesis and decomposition reaction was
investigated and the phase transition was found to be bi-
variant. Simple thermodynamic model of basic adsorption
cycles shows that the material could have applications in
air-conditioning: the COP could reach up to 0.6 at typical
conditions (Tev = 15 °C, Tcon = 35 °C).
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