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1 Introduction
Diffusion, i.e., mass transfer generated by thermal motion,
is among the fundamental phenomena in nature and
technology [1]. It occurs in all types of matter and may be
observed over timescales from femtoseconds up to ages.
Current Contents (Physical, Chemical, and Earth Sciences)
reports over 8000 publications per year concerning this topic,
and the number of publications continues to steadily increase.
In micro- and mesoporous materials, diffusion is the
decisive mechanism of mass transfer. Therefore, diffusion is
of crucial relevance for a large number of technical
applications. Fig. 1 provides a survey of the development of
the number of publications in the field of molecular diffusion
in porous solids over the past 10 years. The continuous
increase in papers published, may also be considered as an
expression of the great relevance of diffusion in the important
fields of industrial application of porous solids, viz. mass
separation and mass conversion.
In mass conversion, diffusion becomes the rate determining
step as soon as the rate of adsorption of the reactant molecules
and/or the rate of desorption of the product molecules become
smaller than the intrinsic reaction rate. Prominent examples
are the hydroxylation of phenol with H2O2 on TS-1 [2] for
diffusion limitation of the reactants and the MTO reaction [3]
for diffusion limitation of the products. Substantial differences
in the diffusivities may give rise to dramatically enhanced
selectivities (as either reactant- or product-form selectivities) and thus allow a sustainable productivity enhancement,
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techniques. Section 2 provides a classification of the different
measuring techniques. It emphasizes the particular relevance
of those techniques, which are able to directly monitor
molecular movement in the interior of the porous media
under investigation, and which are therefore referred to as
microscopic techniques. Section 4 provides examples of the
application of these techniques. The potential use of these
techniques for elucidating structural details is described in
Section 4. The particular correlations between structure and
diffusivity, which are brought about by the regular pore system
of zeolites, are discussed in Section 5.
DT
@c
@z
(1)
@ c
@z
(2)
(3)
In classical diffusion experiments (Fig. 2a), the concentration gradient gives rise to the formation of a diffusion flux,
whose intensity, via Fick's first law,
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Table 1. Classification of the Techniques for Measurement of Intracrystalline Zeolitic Diffusion.
Non-Equilibrium
Stationary
Equilibrium
Macroscopic Sorption/Desorption[10]
Frequency Response (FR) [11]
Zero Length Column (ZLC) [12]
IR-FR [13]
Positron Emission Prof. (PEP) [14]
Temporal Product Analysis (TAP)
[15]
IR Spectroscopy [16]
Transient
MembranePermeation [5]
Effectiveness
Factor during
Catalytic
Reaction [17]
Mesoscopic
IR Microscopy [18]
Single-Crystal
Permeation [19]
Microscopic
@ ln p
@ ln c
(4)
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(5)
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where d, g and t denote the width, amplitude and separation
of the gradient pulses. The gyromagnetic ratio c is a
characteristic quantity of the given nucleus. z denotes the
coordinate in the direction of the applied field gradients.
P(z,t) stands for the probability (density) that a nucleus
contributing to the NMR signal has been shifted over a
distance z during the time interval t. It is commonly referred to
as the propagator. In quasi-homogeneous systems, i.e. if the
diffusion paths are large in comparison with the pore sizes but
small in comparison with the particle sizes, the propagator
coincides with the solution of Fick's second law,
@ cz;t
@ 2 cz;t
D
@t
@ z2
(6)
(7)
With the given initial condition and negligible boundary effects, i.e. with c(z = ,t) = 0,
the solution of Eq. (6) is the Gaussian
expression,
1
z2
Pz; t p exp
4Dt
4pDt
(8)
(9)
(10)
Figure 3. The different patterns for concentration dependence of molecular self-diffusion in zeolites,
from [30,31].
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3.2 Interference Microscopy
The application of interference microscopy to diffusion
measurement is based on the fact that the refractive index of a
zeolite crystallite is generally a linear function of its
concentration. Thus, information about intracrystalline concentration profiles may be provided by determining the
optical density over a zeolite crystallite. In interference
microscopy, this is achieved by observing interference
between the light beam passing the crystallite and an adjacent
one, which remains unaffected by intracrystalline concentration changes. This procedure is schematically shown on the
right side of Fig. 4. The left side shows this central part as a
constituent of the whole device.
RL
nx; y; tdz
(11)
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concentration profiles are referred to, are situated in the
centre of the crystallite (left column, Figs. 9A, 9C and 9E) and
at about one quarter (right column, Figs. 9B, 9D and 9F),
respectively. It turns out that the measured profiles are in
satisfactory agreement with the simulations, if they are based
on the existence of internal transport resistances (Figs. 9C and
9D). Simulations under the assumption of fast mass transfer
along the interfaces, however, leads to completely different
patterns (Figs. 9E and 9F). Therefore, this possibility may
definitely be ruled out for the investigated system.
5 Structure-Mobility Relations
5.1 Correlated Diffusion Anisotropy
Figure 8. Dependence of PFG NMR diffusivities on the mean diffusion path for
n-butane in two different samples of silicalite-1 (open and filled symbols) at
213 K (s,d), 297 K (,,.), and 383 K (h,j) [34].
Dz Dx Dy
(12)
where a, b and c denote the extensions of the unit cell in the x-,
y- and z-directions, and Dx, y, z represents the corresponding
diffusivity. For a number of systems, the correlation formula
(12) is found to be in satisfactory agreement with the results of
MD simulations [36].
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Figure 9. Concentration profiles in the longitudinal extension of a zeolite crystallite of type silicalite-1 during
adsorption of iso-butane, as observed by interference microscopy (A, B) and comparison with the
corresponding results of dynamic Monte Carlo simulations by assuming that the internal interface (C, D)
exclusively acts as a transport barrier or (E, F) allows a fast uptake of sorbate from the surrounding atmosphere.
The left column (A, C, E) displays the values along a plane in the middle of the crystallite, the plane considered
in the right column (B, D, F) is shifted by about one fourth towards the external face [35].
2
p
z t 2F t
776
(13)
L2
D
(14)
Review
file system, however, subsequent displacements are correlated, since they are performed with a higher probability in
opposite directions than in the same direction. As a
consequence of this correlation, the mean square displacement increases only with the square root of the observation
time. Therefore, in finite single-file systems, molecular
displacements are very soon dominated by the other
mechanism. It may be described by an effective diffusivity
[39], which is inversely proportional to the length L of the
single-file system. With Eq. (14), this yields
sintra L3
(15)
Figure 10. Dependence of the ratio of the effective reaction rates in a system
subjected to Molecular Traffic Control and in the corresponding reference
system, on the number l of lattice points between adjacent intersections [41].
Acknowledgement
The novel concepts of mass transfer in porous media
presented, have been decisively promoted by the contributions of NMR spectroscopy to zeolite research. One of the
pioneers of this development is Professor Dr. Dr. Harry
Pfeifer, with whom we had the honour and pleasure to work
over many years. We are deeply obliged to him for advice,
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encouragement and sharing of ideas. Financial support of the
Deutsche Forschungsgemeinschaft (SFB 294 and Graduiertenkolleg Physikalische Chemie der Grenzflchen), Fonds
der Chemischen Industrie und Max-Buchner-Stiftung, is
gratefully acknowledged.
Received: April 24, 2002 [B 6092]
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