Diffusion is an important step of mass transport through porous structures and is of significant

importance in shape-selective catalysis and separation technology [1]. While bulk gas-phase
diffusion in large pores is fast and Fickian, mass transfer slows within mesopores and
micropores at low pressures, since guest-host interacts occur more frequently, Knudsen
diffusion dominates and diffusivity becomes a function of pore diameter [2, 3]. Often there are
multiple diffusivities in a single system ranging over few orders of magnitude [4]. While bulk
mass transport in zeolites is widely studied, little is known with regard to fundamental
understanding of transport limitations at or near the surface of zeolites[5, 6], which differ
considerably

due

to

internal

grain

boundaries

and

defects[7-10],

surface

adsorption/desorption[6, 10], pore geometry and dynamics[11-13] etc. These secondary and rate
limiting mass transfer phenomena have been studied by quite a number of experimental
methods i.e., Zero Length Chromatography [13], Constant Pressure [14] and Constant Volume
Sorption[15], and transient response methods (Step, pulse or Frequency Response Method).
The Frequency Response method measures the pressure response of a closed sorption system to
a periodic volume change over a spectrum of frequencies [16]. In this method, the pressure
response of a closed sorption chamber under periodic volume perturbations with different
frequencies is recorded and fit to a theoretical adsorption/diffusion model. Due to the wide
range of the perturbation frequencies available, the frequency response method is able to
measure diffusion coefficients that span several orders of magnitude. Frequency response (FR)
techniques have been used to measure thermal transport properties in metal rods[17], adsorption
of hydrogen on a nickel catalyst[18], and mass diffusion of ethane in polyethylene [19]. Yasuda
extended similar technique formulated by Naphtali and Polinski[18] for adsorption-desorption in
1981 [20, 21] and diffusion in 1982 [22] in gas-solid systems. He also detected a contribution of
surface resistance in a gas-solid adsorption system[23]. Similar models were used for
investigating diffusion within zeolites[24, 25].
If a closed sorption system in equilibrium (denoted by subscript e) is perturbed by a sinusoidal
change in volume V(t)(eq. 1), the vapor pressure (also the total pressure, P(t)) of the adsorbate
diffusing into and out of the porous material will eventually reach a periodic steady state with
angular frequency (eq. 2). Based on the system dynamics, there will be a phase lag between
the volume perturbation and the pressure response. Based on Ficks law of diffusion in zeolites

and mass balance, Yasuda derived the characteristic functions for the in-phase (eq. 3) and outof-phase (eq. 4) components of the pressure response to a sinusoidal volumetric variation. The
functions that Yasuda derived are linear functions and, therefore, can account for processes
occurring at more than one characteristic time scale.
V= Ve [1 - v cos(t)]

(1)

P= Pe [1 - p cos(t + )]


where

v
p

cos - 1 = K c

(3)

v
sin = K s
p
K=

c =

s =

(2)

(4)

R Te dB
Ve dP

(5)

1 sinh + sin
for plain sheet
cosh + cos
3 sinh - sin
for spheres
cosh - cos

(6)

1 sinh - sin
for plain sheet
cosh + cos
6 1 sinh + sin 1
for spheres
2 cosh - cos

(7)

where is the dimensionless length of the particles.

L2
2D

2a2
D

for plain sheet

1

(8)

for spheres

A number of researchers used Yasudas model to characterize and identify parameters for
diffusion in gas-solid or liquid-solid systems[26-29]. A thermal frequency response technique
(TFR) has been used to study the diffusion of benzene in NaX zeolite by Malka-Edery and
Grenier in 2001[30]. Nonlinear FR methods have also been used for investigation of gas
adsorption: choice of the optimal mass of the adsorbent, frequency range and input
amplitude[31]. Ruthven introduced the presence of a surface barrier that limits the uptake of
sorbate on the surface of the particles[12]. Teixeira and Qi [32] has integrated asymmetric

surface barrier dynamics (different uptake and release kinetics at surface) with the Yasuda model
and evaluated the relative contributions to mass transfer of cyclohexane in MFI Zeolites.
However, the underlying assumptions (Fickian diffusion, only temperature-dependent
parameters) are yet to be justified to be appropriate in a broad range of particle characteristics
and frequency range.

(I)

(II)

(III)

(IV)

Keq

Keq

Ks

K-s

Slow diffusion

Slow diffusion

Slow diffusion

Surface
barrier

Ks

Slow diffusion

Fast Adsorption

Fast Adsorption

ption

Kd

Des
or

Keq

Ka

tio
Adsorp

Fast Adsorption

Gas

Asymmetric
Surface
barrier

B
D

Porous particle

Figure : Schematics of available transport models in porous particles (adapted from Teixeira, A et
al., 2014). (I) Base model by Yasuda (II) Yasudas Surface resistance model (III) Ruthvens
surface barrier model (IV) Teixeira-Qis asymmetric surface barrier model
The previous frequency response devices[4, 30, 33, 34] are developed and improved based on
Yasudas first developed apparatus in 1976[20, 21]. Over the course of last 40 years, the devices
have developed better accuracy, faster response time, and exact reproducibility and have
eliminated a lot of sources of possible discrepancy in obtaining data. However, They still lack the
superior accuracy need during measurement in high frequency and smaller particle size regime.
Moreover, even though the latest devices [32, 34] are capable of measuring a frequency range

spanning over three orders of magnitude, the accuracy in data acquisition and noise-free
operation is not guaranteed. In addition to that, all the previous models had the assumption of
Fickian diffusion inside the pores, which often is invalid to hierarchical materials and very small
particles sizes, where anomalous and nonlinear diffusivities are prominent[35].
The aim of the proposed research is to make use of FR method for a theoretical investigation of
nonlinear/anomalous diffusion through hierarchical zeolite and other complex structures. A new
frequency response device will be constructed using state-of-the-art technology to operate over
the desired frequency range and time-series data will be collected for analysis. Comprehensive
mathematical models based on the principals of fractional differential calculus will be derived
and the raw data will be analyzed to identify the transport parameters of microporous,
hierarchical and organometallic particles.

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