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Kinetics of water adsorption on silica Fuji Davison RD

Article  in  Microporous and Mesoporous Materials · November 2006

DOI: 10.1016/j.micromeso.2006.06.008

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 Microporous and Mesoporous Materials 96 (2006) 65–71
www.elsevier.com/locate/micromeso

Kinetics of water adsorption on silica Fuji Davison RD

Yuri I. Aristov a,*, Mikhail M. Tokarev a, Angelo Freni b,
Ivan S. Glaznev a, Giovanni Restuccia b
a
Boreskov Institute of Catalysis, Russian Academy of Sciences, Pr. Lavrentieva, 5, Novosibirsk 630090, Russia
b
CNR – Istituto di Tecnologie Avanzate per l’Energia ‘‘Nicola Giordano’’, Via Salita S. Lucia s. Contesse 5, 98126 Messina, Italy

Received 16 March 2006; received in revised form 5 June 2006; accepted 8 June 2006
Available online 28 July 2006

Abstract

The kinetics of water adsorption on loose grains of Fuji Davison RD silica gel was studied by a TG differential step method in the
temperature range 29–64 C and in the pressure range 6.5–34 mbar. Three grain sizes were selected, 0.3–0.325, 0.355–0.425 mm and 0.8–
1.0 mm. Furthermore, adsorption isobars at P H2 O = 9, 18 and 48 mbar were measured over the temperature range of 30–150 C by a TG
technique to determine pertinent equilibrium parameters which are used to calculate the coefficients of diffusion. The equilibrium uptake
was described as a linear function of the Dubinin–Polanyi adsorption potential.
It was found that the influence of particle size, temperature and pressure on the adsorption kinetics can be well described in terms of
the Fickian diffusion model. The apparent water diffusivity Dap was found to be an Arrhenius function of temperature with the apparent
activation energy Ea = 41.5 kJ/mol and the pre-exponential factor Dap0 = 2.9 · 104 m2/s. The apparent diffusivity of water in silica
pores was measured to be De = (3.7–4.7) · 107 m2/s and possessed a slight increase with temperature. This value is close to the Knudsen
diffusivity, calculated for a cylindrical pore of radius rp = 1.0 nm.
For smaller grains at T > 39 C the contribution of thermal effects was revealed, which decreases the rate of water sorption. In this
case, application of non-isothermal kinetic model of Lee and Ruthven allowed good description of experimental uptake curves as well as
the estimation of parameters which determine simultaneous heat and mass transfer.
 2006 Elsevier Inc. All rights reserved.

Keywords: Adsorption equilibrium; Adsorption kinetics; Silica gel; Water vapor; Coupled heat and mass transfer

1. Introduction which the kinetics of water adsorption on Fuji Davidson

In Ref. [1] the microporous silica gel type RD manufac-
tured by the Fuji Davison Ltd. was indicated as the adsor-
bent of water used in commercialized adsorption chillers
which utilize low-temperature heat (50–80 C) [2–4]. Exper-
imental equilibrium data for water adsorption on this silica
were reported in [1,5,6] and mathematical equations for
approximation of these data in [1,7]. For dynamic simula-
tion of a commercial chiller, the kinetic parameters of
water adsorption are commonly taken from Ref. [8], in
*
Corresponding author. Tel.: +7 3833309573.
E-mail address: aristov@catalysis.nsk.su (Y.I. Aristov).
type A silica gel was measured at T = 35, 50 and 80 C.
Although this type of silica is different from type RD, the
porous structures of both materials are close as reported
in [9]. For instance, the pore volume Vp and average pore
diameter Dp are Vp = 0.36 cm3/g, Dp = 2.2 nm for type A
and Vp = 0.4 cm3/g, Dp = 2.2 nm for type RD.
About 1 g of spherical pellets 2–4 mm size (5–10 mesh)
was used for measurements [8]. Vapor pressure varied from
0 up to the point of saturation. During the experiments a
small amount of vapor was introduced into a vessel with
the sample inside. The weight and pressure change curves
were analyzed to obtain the water diffusivity Ds by fitting
of these experimental curves with the theoretical model of
the diffusion from a well stirred solution of limited volume

1387-1811/$ - see front matter  2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2006.06.008
66 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71
Nomenclature
a, b constants defined in Eq. (1)
c gas phase concentration of sorbate, kg/m3
c0 value of c at t = 0, kg/m3
Cp heat capacity, J/(m3K)
Dap apparent water diffusivity, m2/s
De effective pore diffusivity, m2/s
Dkn Knudsen diffusivity, m2/s
ha heat transfer coefficient W/(m2 K)
rp pore diameter, m
K adsorption equilibrium constant, m3/m3
k Boltzmann constant, J/K
Kd apparent diffusion time constant, s1
M molar mass kg/mol
mt/m1 fractional approach to the sorption equilibrium
NA Avogadro constant
P water pressure over the sample, Pa
taken from [9]. Unfortunately, neither the original experi-
mental uptake curves nor the comparison with the theoret-
ical curves were presented in [8], which did not allow the
estimation of the accuracy of this approximation. The dif-
fusivities were therefore approximated in [10] by the func-
tion Ds = Ds0 exp(Eact/RT) with Ds0 = 2.54 · 104 m2/s
and Eact = 42.0 kJ/mol, and used for description of the
kinetics of vapor adsorption on this silica gel by the linear
driving force (LDF) model [11]
dw=dt ¼ Kðw  wÞ
with K ¼ 15Ds =R2p . Here w* and w are the equilibrium and
current uptakes.
The main objective of this paper is to obtain direct
experimental data for the kinetics of water adsorption on
Fuji Davison RD silica gel in a temperature range close
to that typical for operation of a commercial chiller (30–
80 C) and compare these results with previous data for
Fuji Davison A silica gel. The data obtained were treated
to extract the diffusion constant, the apparent diffusivity
and pore diffusivity of water.
Many experimental methods have been developed to
measure these diffusivities [12]. A differential step isother-
mal method can be considered as the most preferable one
[10,12] as it allows to greatly reduce the contribution of
thermal effects caused by the water adsorption as well as
to obtain the diffusivity in the case of non-linear adsorption
isotherm. The theoretical background of this method for
both isothermal and non-isothermal cases can be found
elsewhere [10,12] (see brief review in Appendices A and
B). Here we applied this method to measure the kinetic
curves for water adsorption on Fuji Davison RD silica
and to extract the apparent and pore diffusivities of water.
Since the adsorption equilibrium parameters are required
for the data analysis, adsorption isobars were also
measured.
P/P0 relative water pressure
R radial coordinate, m
Rp particle radius, m
T temperature, K
t time, s
w current water uptake, g/g
w* equilibrium water uptake, g/g
w0 water uptake at t = 0, g/g
w/ water uptake at t = /, g/g
w average uptake given by Eq. (8)
DF Dubinin–Polanyi potential, J/mol
DH sorption enthalpy, J/mol
a, b parameters defined in Eq. (9)
e porosity of adsorbent particle
v pore tortuosity
2. Experimental
Granules of Fuji RD silica gel of 0.3–0.325, 0.355–0.425
and 0.8–1.0 mm in sizes were selected for measurements.
Porous structure of the silica was measured by a BET
method (specific surface area SBET = 820 m2/g, pore vol-
ume Vp = 0.4 cm3/g and the average pores diameter
Dp = 2.2 nm, that is in agreement with Refs. [1,6]).
Uptake curves of water adsorption were measured by a
differential step method [12] using a CAHN 2000 thermo-
balance with a small amount of silica (m0 = 7–10 mg) in
order to reduce thermal effects. The sample consisted of
only a few grains (for instance, 10–15 grains of the 0.8–
1.0 mm size). For further reduction of these effects the
grains of 0.355–0.425 or 0.8–1.0 mm in size were separated
from each other on the surface of aluminum pan
(weight  90 mg) and mixed with small pieces of copper
wire (weight  85 mg). All these precautions increased the
heat capacity of the measuring cell and made the sample
more isothermal.
A typical experiment was run as follows. The sample
was heated up to 150 C for 5–6 h and then cooled down
to the measuring temperature (29, 39, 49 and 64 C) under
continuous pumping (P  103 mbar). Then the measuring
cell was disconnected from the pump and connected to an
evaporator maintained at fixed temperature between 3.0
and 26.0 C, so that the pressure in the measuring cell
rapidly increased up to the pressure in the evaporator
and then remained constant. The typical pressure jump
was 2–3 mbar. The increase of the sample mass, due to
the adsorption of water, was measured as a function of
time at fixed T and P H2 O to calculate the amount of water
adsorbed mt. After the kinetic curve at fixed P H2 O had been
recorded, the evaporator was disconnected from the mea-
suring cell and its temperature was increased to fix the
proper pressure for the next kinetic test and so on. The
 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71 67

temperature in the measuring cell was controlled with an 0.3

accuracy of ±0.3 C.
Sorption equilibrium of water vapor on Fuji RD silica
gel was measured at T = 30–150 C and P H2 O = 10–
50 mbar using the same CAHN 2000 thermobalance. 0.2

Before measurements, the sample was heated up to

150 C under vacuum until reaching constant weight m0.
The amount of water adsorbed Dm was measured as a
0.1
function of T at constant P H2 O = 9, 18 and 48 mbar. To
maintain constant vapor pressure, the internal volume of
the balance was connected with an evaporator. The water
uptake w was calculated as w = Dm/m0. 0.0
0 5000 10000 15000 20000
3. Results ΔF, J/mol

Fig. 2. Temperature-invariant curves of water sorption on Fuji RD silica

3.1. Adsorption equilibrium
gel. Symbols – experimental data, line – approximation by Eq. (1).

Experimental isobars of water adsorption on Fuji RD

silica gel demonstrate the gradual decrease of the water
uptake with increasing of temperature and reduction of
vapor pressure (Fig. 1). The equilibrium data for the Fuji
silica, obtained in this study, are in good agreement with
those reported in [1,6]. If they are presented as the equilib-
rium loading w vs. the Dubinin–Polanyi potential DF ¼
RT lnðP H2 O =P s Þ [13,14], the data obtained at different T
lie on the same curve, so-called ‘‘the temperature-invariant
curve of adsorption’’ (Fig. 2). Thus, the equilibrium
depends on just one parameter (DF) instead of two com-
mon parameters (T and P H2 O ), and the loading w can be
quite precisely described by simple polynomial expression
lnðwÞ ¼ a þ b  DF ;
where a and b are constants determined from experimental
equilibrium data. This approximation with only two fitting
parameters was shown to give better accuracy than the
more complicated Freundlich [7] and Toth [1] models with
8 and 4 parameters, respectively. The best fit was obtained
with a = 0.8841 and b = 3.0757 · 104, that gives a
standard deviation SD = 0.0013, while the SD = 0.023
and 0.028 for the Freundlich and Toth models. Thus, the
simple Eq. (1) provides a good analytical description of
the whole set of experimental data (see fitting lines in Figs.
1 and 2) and can be used to perform mathematical model-
ing of the commercial water chiller based on Fuji silica as
adsorbent. We applied this equation to calculate the equi-
librium uptakes as well as the derivatives (dw/dc)T and
(dw/dT)P (see AAppendices A and B), which are necessary
for treating kinetic data.
3.2. Adsorption kinetics
ð1Þ Typical temporal variation of the vapor pressure over
the sample as well as its weight is shown in Fig. 3. The
dependence of the water uptake on the square root of time pffi
(Fig. 4) turned out to be linear at short times mt =m/ ¼ A t
that is in line with the isothermal Fickian diffusion (FD)
model (see details in AAppendices A and B). The process
is faster for smaller grains and higher temperatures
(Fig. 4). The slope [12]

0.3
8
30

25
6
0.2
P=9 mbar 20
P=18 mbar
P=48 mbar
4
15
0.1
10
2
5

0.0
20 40 60 80 100 120 140 0 0
0 50 100 150
T, °C Time, min

Fig. 1. Isobars of water adsorption on Fuji RD silica gel. Symbols – Fig. 3. Typical temporal evolution of the pressure over the sample (s)
experiment, lines – calculated using Eq. (1). and its weight (h) (T = 59 C, grain size 0.8–1.0 mm).
68 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71

Table 1
1.0 Conditions (P H2 O init, P H2 O fin) and results of kinetic measurements (A,
Dap, De) for water sorption on silica Fuji RT 2060 (grain size 0.8–1.0 mm)
T, C P H2 O init, P H2 O fin, A, s1/2 Dap, m2/s Dp, m2/s
0.8
mbar mbar
28.8 10.0 11.4 0.0373 2.1 · 1011 3.3 · 107
0.6 11.6 12.4 0.0381 2.2 · 1011 4.1 · 107
38.8 10.0 12.4 0.0342 2.1 · 1011 2.3 · 107
0.4 12.4 14.6 0.0342 2.1 · 1011 2.3 · 107
13.4 15.0 0.0480 4.0 · 1011 4.8 · 107
15.6 17.8 0.046 3.7 · 1011 3.9 · 107
0.2
17.6 19.8 0.045 3.6 · 1011 3.6 · 107
19.6 22.2 0.046 3.7 · 1011 3.7 · 107
0.0 49.0 12.4 14.2 0.073 8.7 · 1011 6.3 · 107
0 1 2 3 4 5 14.4 16.8 0.068 8.2 · 1011 5.7 · 107
t 0.5, min0.5 17.0 19.6 0.061 6.5 · 1011 4.5 · 107
pffi 19.6 22.2 0.067 7.8 · 1011 5.2 · 107
Fig. 4. Plot of the water sorption curves in the form mt/m/ vs. t. s – 22.0 24.2 0.0644 7.3 · 1011 4.8 · 107
T = 64 C, grain size 0.8–1.0 mm, h – T = 39 C, grain size 0.8–1.0 mm, j 24.4 26.8 0.055 5.3 · 1011 3.4 · 107
– T = 39 C, grain size 0.355–0.415 mm. Solid lines were calculated 26.2 30.4 0.058 5.9 · 1011 3.7 · 107
according to Eq. (6) with the values of Dap derived from the initial slope of 30.0 27.8 0.054 5.1 · 1011 3.3 · 107
experimental curves. 27.2 16.6 0.057 5.7 · 1011 3.8 · 107
64.0 7.8 12.4 0.087 1.4 · 1010 5.4 · 107
sffiffiffiffiffiffiffi 14.0 15.4 0.0794 1.1 · 1010 4.4 · 107
6 Dap 15.4 17.8 0.082 1.2 · 1010 4.6 · 107
A ¼ pffiffiffi  1=Rp ð2Þ 1.1 · 1010 4.4 · 107
p R2p 17.8 15.6 0.0794
10.0 12.6 0.93 1.5 · 1010 6.1 · 107
allows the calculation of the diffusion constant k D ¼
Dap
as 12.6 14.4 0.078 1.1 · 1010 4.3 · 107
R2p 14.4 16.8 0.0794 1.1 · 1010 4.4 · 107
2 2
well as the apparent water diffusivity Dap ¼ A pRp =36, 16.8 20.0 0.082 1.2 · 1010 4.5 · 107
where Rp is the radius of silica grains. The values of A 20.0 23.4 0.0816 1.2 · 1010 4.45 · 107
and Dap for every pressure jump are presented in Table 1 23.2 28.2 0.087 1.3 · 1010 4.9 · 107
28.0 31.0 0.076 1.0 · 1010 3.9 · 107
(for large silica grains), while the values averaged for a
set of experiments performed at constant temperature – 69.0 12.6 14.2 0.081 1.2 · 1010 3.9 · 107
14.4 17.8 0.076 1.0 · 1010 3.2 · 107
in Table 2. For the sake of comparison, we calculated the
apparent diffusivity from the data displayed in Fig. 3 of
Ref. [8] and found that it is close to that obtained in our Table 2
experiments (see Table 2). Experimental kinetic parameters of water adsorption on Fuji silica RD
Substituting the so derived apparent diffusivities to the T, C A, s1/2 Dap, m2/s De, m2/s
appropriate isothermal equation (Eq. (6) in Appendix A), Grains 0.355–0.415 mm
the conformity is observed between the experimental and 28.8 0.0845 1.8 · 1011 3.5 · 107
theoretical uptake curves (Fig. 3). Thus, the kinetic curves 38.9 0.105 3.6 · 1011 3.7 · 107
of water sorption on Fuji RD silica gel show a non-expo- 49.0 0.114 4.1 · 1011 2.8 · 107
nential shape consistent with the FD model rather than 64.0 0.119 6.3 · 1011 2.4 · 107
with the LDF model which predicts the dependence mt/ Grains 0.8–1.0 mm
m/ = 1  B exp(Ct) (Fig. 5). The LDF model strongly 28.9 0.0361 2.1 · 1011 3.9 · 107
underestimates uptake at short times and overestimates it 35.0 – 2.1 · 1011 –
at long times. If the dynamic behavior of an adsorption 38.8 0.046 3.8 · 1011 4.0 · 107
chiller with a granulated layer of the silica is controlled 49.1 0.062 6.7 · 1011 4.5 · 107
50.0 – 6.4 · 1011 –
by the intraparticle diffusion of water vapor, taking these 63.9 0.082 1.2 · 1010 4.7 · 107
deviations into account could be of high importance and
The apparent water diffusivity calculated from Fig. 3 of Ref. [8] are
will lead to an appropriate improvement of simulation marked in bold.
results [7].
According to the FD theory [12], the ratio of the initial
slopes for smaller and larger silica grains should be equal to thermal effects caused by the heat released during water
the inverse ratio of the average grain sizes, namely, 2.35. sorption. Indeed, for small particles at high T, the adsorp-
This is indeed observed at low temperatures (Fig. 6). At tion rate is sharply increased and the heat sink to the
T > 39 C, the slopes and hence the diffusion constants surrounding medium is not sufficient to dissipate it. This
are smaller than the values predicted by the isothermal causes an increase in the sample temperature, which
FD theory. This is probably due to the contribution of restricts the rise of the adsorption rate. To avoid, or at least
 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71 69

1.0 1.0

0.8 0.8
mt / m

m t /m
0.6 0.6

0.4 0.4

0.2
0.2

0.0 1 2 3 4 5
0 1 2 3 4 5
t0.5, min0.5
t 0.5 , min 0.5
Fig. 7. Comparison of water uptake curves in the case of weak () and
Fig. 5. Approximation of the experimental data by the FD (bold) and strong (n) thermal effects. Dot line is the uptake curve calculated using the
LDF (dashed) models. T = 49.0 C, initial pressure P = 22.0 mbar, final isothermal model (Eq. (6)). Solid and dashed lines were calculated with the
D
pressure 24.2 mbar. Grain size 0.8–1.0 mm. non-isothermal model (Eq. (9)) with the value Rap2 taken from isothermal
p
experiments and the fitting parameters a = 3.6, b = 0.5 (a/b = 7.8) and
a = 6.0, b = 3.4 (a/b = 1.8), respectively. Grain size 0.355–0.425 mm.
2.4 T = 64 C; P0 = 23 mbar.

sionless parameters a and b (Fig. 7). Within the frames of

2.2
this model the ration a/b provides a useful criterion for
assessing the deviation from isothermal behavior. For a/
2.0
b > 60 the error in the value of Dap =R2p obtained by match-
ing the uptake curve to the isothermal solution does not
1.8 exceed 15% over the range 0–85% fractional approach to
equilibrium [12,15]. In our case of weak and strong thermal
1.6 effects the ratio a/b was 7.8 and 1.8, respectively (Fig. 7).
It was found that the apparent water diffusivity in Fuji
silica RD strongly increases with the temperature rise. Pre-
25 30 35 40 45 50 55 60 65 sentation of this dependence in the Arrhenius coordinates
T, °C (Fig. 8) gives
Fig. 6. The ratio of slopes for the large and small silica grains (j – ln Dap ðm2 =sÞ ¼ 4:955=T  8:12;
experiment, s – theoretical prediction).
which yields the apparent activation energy of water diffu-
sion inside the large silica grains Ea = 41.5 kJ/mol as well
reduce, these effects it is necessary either to intensify the
as the pre-exponential factor Dap0 = 2.9 · 104 m2/s. These
dissipation of adsorption heat or to increase the heat
capacity of the measuring cell, for instance, by mixing the
sample with small pieces of copper wire as we did.
If these special warnings are not applied and the sample -23.0

of 20–25 mg weight is directly put inside the standard mea-

suring pan which weights about 30 mg, thermal effects can
-23.5
strongly influence the adsorption rate (Fig. 7). The kinetic
curves atpffi short times can still follow the relation
mt =m/  t, although the process is slower and the slopes -24.0
cannot be described by Eq. (2). In this case the adsorption
rate is influenced by both mass and heat transfer, and
should be analyzed within non-isothermal models [12]. This -24.5
was done using the kinetic model of Lee and Ruthven [15–
17], briefly described in AAppendices A and B. It neglects
the heat transfer resistance inside grains and considers the 0.0028 0.0030 0.0032 0.0034
-1
heat release from the external grain surface as limiting fac- 1/T, K
tor. The non-isothermal kinetics of water adsorption can be Fig. 8. The dependence of the apparent diffusivity of water in Fuji RD
D
well described by this model with the value Rap2 taken from 2060 silica gel grains on temperature. j – grains size 0.8–1 mm, s – 0.355–
p
isothermal experiments and reasonable values of the dimen- 0.425 mm. n – data taken from [8].
70 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71

Dap0 = 2.9 · 104 m2/s. The apparent diffusivity in silica

pores was measured to be De = (3.7–4.7) · 107 m2/s which
is close to the Knudsen diffusivity for such pores.
For smaller grains at T > 39 C the contribution of ther-
mal effects was revealed, which decreases the rate of water
sorption. Application of non-isothermal kinetic model
allowed good description of experimental uptake curves
as well as the estimation of parameters which determine
simultaneous heat and mass transfer.

Acknowledgments

This work was supported in part by INTAS (grant no.

03-51-6260) and RFBR (grants 04-02-81028, 05-02-16953
Fig. 9. The temperature dependence of the apparent diffusivity of water in and 05-08-50223).
pores (grain size 0.8–1.0 mm).
Appendix A. Isothermal differential step method
values are close to those obtained in [8] for Fuji Davison
silica type A, as may be expected, because of the similar The uptake rate is given by the appropriate solution of
pore structure of these materials. For small grains the ther- the differential mass balance equation. For uniform spher-
mal effects cannot be neglected, and partially moderates the ical adsorbent particles it may be written in the form:
temperature dependence Dap(T), especially at high temper-  2 
ow oc o c 2 oc
atures (Fig. 8). ð1  eÞ þ e ¼ eDe þ ð3Þ
ot ot oR2 R oR
Another information that can be obtained from kinetic
data is the effective pore diffusivity De that can be calcu- in which the effective pores diffusivity De is assumed to be
lated according to De = Dap[e + (e  1)K]/e [12]. Here e is independent on concentration in narrow concentration
the porosity of the silica grains (e = 0.46 [3]) and K is the range of differential experiments. Here e is the grain poros-
local slope of adsorption isotherm K = dw/dc, which can ity, w is the adsorbate concentration in adsorbed phase, c is
be calculated from experimental isotherms. The obtained the adsorbate concentration in gas phase. If the step change
values of De are displayed in Table 2 (the error is ±0.5 · of concentration is small (from c0 to c0 + Dc, where
107 m2/s). For larger grains De = (3.7–4.7) · 107 m2/s Dc  c0), then the equilibrium relationship is expected to
and possesses a slight increase with temperature. This value be linear:
is close to the Knudsen diffusivity, calculated for apcylindri-
ffiffiffiffiffiffiffiffiffiffi ow oc
d ¼K ð4Þ
cal pore of diameter dp = 2.0 nm: Dkn ¼ 9700 2p T =M ¼ ot ot
4:1  107 m2 =s. In our opinion, this indicates the with K = K(c0) = const. Now Eq. (3) may be written as:
Knudsen diffusion as a rate limiting mechanism of water  2 
adsorption on Fuji RD silica instead of the surface diffu- oc eDe o c 2 oc
¼ þ ð5Þ
sion suggested in [8]. One more evidence in favor of this ot e þ ð1  eÞK oR2 R oR
mechanism is the very modest dependence of the pore dif- The relevant initial and boundary conditions for a step
fusivity on temperature (Table 2) that follows the theoret- concentration change at the external surface of the particle
ical dependence T0.5 (Fig. 9). at t = 0 are:
4. Conclusions cðRp ; 0Þ ¼ c0 ; wðRp ; 0Þ ¼ w0 ;
cðRp ; 1Þ ¼ c8 ; wðRp ; 1Þ ¼ w/ ;
 
The kinetics of water adsorption on loose grains of Fuji oc  ow
¼  ¼ 0;
Davison RD silica gel was measured by a TG differential oR R¼0 oR R¼0
step method at T = 29–64 C for grain sizes 0.355–
0.425 mm and 0.8–1.0 mm together with the water adsorp- where Rp is the particle radius. The solution of Eq. (5) is
tion isobars. The equilibrium uptake was described as a well known [9]:
linear function of the Dubinin–Polanyi adsorption mt w  w0
¼
potential. m1 w1  w0
It was found that the influence of particle size, tempera- eDe
!
6 X 1
1 n2 p2 eþð1eÞK t
ture and pressure on the adsorption kinetics can be well ¼1 2 exp 
described in terms of the Fickian diffusion model. The p n¼1 n2 R2p
!
apparent water diffusivity Dap was found to be an Arrhe- 6 X 1
1 n2 p2 Dap t
nius function of temperature with the apparent activation ¼1 2 exp  ð6Þ
p n¼1 n2 R2p
energy Ea = 41.5 kJ/mol and the pre-exponential factor
 Y.I. Aristov et al. / Microporous and Mesoporous Materials 96 (2006) 65–71 71

where w is the average water uptake in the sample which where pn is given by the roots of the equation 3bðpn cot pn 
depends on time, Dap is the apparent water diffusivity 1Þ ¼ p2n  a and non-dimensional parameters are defined
eDe R2 ow
Dap ¼ eþð1eÞK . Thus, this diffusivity depends on the pore by a ¼ Chap Dapp ; b ¼ DH .
C p oT p
diffusivity De, the grain porosity e and the shape of the
The limiting case of isothermal behavior (Eq. (6)) is real-
water sorption isotherm (the local slope of the isotherm
ized when either a ! 1 (infinitely rapid heat transfer) or
K = dw/dc). A simplified expression for the initial region
b ! 0 (infinite heat capacity).
of the uptake curve may be obtained as [12]:
rffiffiffiffiffiffiffiffiffi
mt 2S Dap t pffi References
 ¼A t ð7Þ
m1 V p
[1] H.T. Chua, K.C. Ng, A. Chakraborty, N.M. Oo, M.A. Othman, J.
where S/V is the ratio of external area-to-particle volume Chem. Eng. Data 47 (2002) 1177–1181.
(S/V = 3/Rp for a spherical particle). Eq. (5) can be used [2] M. Matsushita et al., Energy Conservation 39 (10) (1987) 96.
for determining the apparent diffusion time constant [3] Y. Yonezawa et al., Adsorption Refrigeration System, US Patent N
D 4881376, 1989.
k D ¼ Rap2 and after that the effective pore diffusivity De.
p [4] Adsorption refrigerator uses low-temperature waste heat, Newletters,
N1 (2000) 7–9.
Appendix B. Non-isothermal differential step method [5] NACC. PCX data for silica gel/water pair, Manufacturer’s Proprie-
tary Data, Nishiyodo Air Conditioning Co. Ltd., Tokyo, Japan, 1992.
Assuming intraparticle diffusion control with a constant [6] X. Wang, W. Zimmermann, K.S. Ng, A. Chakraboty, J.U. Keller, J.
Therm. Anal. Calorim. 76 (2004) 659–669.
micropore diffusivity, the response of microporous particle
[7] B.B. Saha, E.C. Boelman, T. Kashiwagi, ASHRAE Trans.: Res. 101
to a small differential step change in sorbate concentration (Part 2) (1995) 348–357.
at the external surface is described by the following set of [8] K. Chihara, M. Suzuki, J. Chem. Eng. Jpn. 16 (1983) 293–299.
equations [12,15–17]: [9] J. Crank, Mathematics of Diffusion, Oxford University Press,
8   London, 1975.
< ð1  eÞ ow þ e oc ¼ eD o2 c þ 2 oc [10] A. Sakoda, M. Suzuki, J. Chem. Eng. Jpn. 17 (1) (1984) 52–57.
ot ot e oR 2 R oR
[11] E. Glueckauf, Trans. Faraday Soc. 51 (Part 11) (1955) 1540–1551.
: ðDH Þ ow ¼ C dT þ haðT  T Þ [12] D.M. Ruthven, Principles of adsorption and adsorption processes,
ot p dt 0
Z Rp John Wiley & Sons, New York, 1984.
3 ow [13] M.M. Dubinin, Progress in Surface and Membrane Science, Aca-
¼ 3
w wr2 dr; wðr; 0Þ ¼ 0; ð0; tÞ ¼ 0 ð8Þ
Rp 0 or demic Press, New York, 1975.
[14] J.Y. Andersson, H. Bjurstroem, M. Azoulay, B. Carlsson, J. Chem.
where Cp is the heat capacity per unit volume. The expres- Soc. Faraday Trans. 1 81 (1985) 2681–2692.
sion for the uptake curve is [15] L.K. Lee, D.M. Ruthven, J. Chem. Soc. Faraday Trans. I 75 (1979)
2406.
mt X1
[16] Lee et al., AIChE J 26 (1980) 15–23.
¼1 [17] Lee et al., AIChE J 27 (1981) 654.
m1 n¼1

9½ðpn cot pn  1Þ=p2n expðp2n Dap t=R2p Þ

 ; ð9Þ
b1 þ 1:5½pn cot pn ðpn cot pn  1Þ=p2n þ 1

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