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**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 ω(eq. 2). Based on the system dynamics, there will be a phase lag φ between

the volume perturbation and the pressure response. Based on Fick’s law of diffusion in zeolites

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].p cos(ωt + φ)] where v p cos φ .cos η (6) 1 sinh η . therefore.v cos(ωt)] (1) P= Pe [1 . Ruthven introduced the presence of a surface barrier that limits the uptake of sorbate on the surface of the particles[12]. Yasuda derived the characteristic functions for the in-phase (eq. 3) and outof-phase (eq.sin η for plain sheet η cosh η+ cos η 6 1 sinh η + sin η 1 for spheres η 2 cosh η.sin η for spheres η cosh η. V= Ve [1 . The functions that Yasuda derived are linear functions and. Nonlinear FR methods have also been used for investigation of gas adsorption: choice of the optimal mass of the adsorbent.cos η η (7) where η is the dimensionless length of the particles. 4) components of the pressure response to a sinusoidal volumetric variation. η= ωL2 2D 1 2ωa2 D 2 for plain sheet 1 2 (8) for spheres A number of researchers used Yasuda’s model to characterize and identify parameters for diffusion in gas-solid or liquid-solid systems[26-29]. can account for processes occurring at more than one characteristic time scale. frequency range and input amplitude[31].and mass balance. Teixeira and Qi [32] has integrated asymmetric .1 = K δc (3) v sin φ = K δs p K= δc = δs = (2) (4) R Te dB Ve dP e (5) 1 sinh η + sin η for plain sheet η cosh η+ cos η 3 sinh η .

2014). Over the course of last 40 years. However. 21]. the devices have developed better accuracy. They still lack the superior accuracy need during measurement in high frequency and smaller particle size regime. 34] are developed and improved based on Yasuda’s first developed apparatus in 1976[20. (I) Base model by Yasuda (II) Yasuda’s Surface resistance model (III) Ruthven’s surface barrier model (IV) Teixeira-Qi’s asymmetric surface barrier model The previous frequency response devices[4.. the underlying assumptions (Fickian diffusion. (I) (II) (III) (IV) Keq Keq Ks K-s A D Slow diffusion Slow diffusion D D Slow diffusion Surface barrier Ks Slow diffusion Fast Adsorption Fast Adsorption ption Kd Des or n Keq Ka tio Adsorp Fast Adsorption X Gas Asymmetric Surface barrier B D Porous particle C Figure : Schematics of available transport models in porous particles (adapted from Teixeira. only temperature-dependent parameters) are yet to be justified to be appropriate in a broad range of particle characteristics and frequency range. Moreover. and exact reproducibility and have eliminated a lot of sources of possible discrepancy in obtaining data. faster response time. 30. 33. even though the latest devices [32.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. 34] are capable of measuring a frequency range . A et al. However.

D. 1993. vol. Xu. Vasenkov. C. Baylet. 216-222. Kärger. vol. J. "Catalytic membrane materials with a hierarchical porosity and their performance in total oxidation of propene. J. P. vol. D. "Morphology-dependent zeolite intergrowth structures leading to distinct . 89. 29-35. 2010. V. 16. vol. References [1] [2] [3] [4] [5] [6] [7] [8] [9] J." The Journal of Physical Chemistry B. 2010. "Influence of Defects on the External Crystal Surface on Molecular Uptake into MFIType Zeolites. where anomalous and nonlinear diffusivities are prominent[35]. all the previous models had the assumption of Fickian diffusion inside the pores. J. In addition to that. Ayral. A. pp.spanning over three orders of magnitude. pp. 2004/09/01 2004. Shen and L. 9. 2010/12/01 2010. R." Chemistry of Materials. D. 336. 156. Karwacki. 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. vol. A. K. 511-514. vol. pp. Meeldijk. F. E. D. vol. 2003/03/01 2003. pp. 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. pp. van den Bergh. et al. S. "Measurement of Diffusion in Zeolites—A Never Ending Challenge?. Gascon. A. Julbe. X. K. pp. 3552-3558. Jun 29 2012. 361-387. M. Liu. H. C. Rees. 2006/11/01 2006. Yacou. A." Journal of the Chemical Society. and F.. 110. and A. S. Wloch. 22681-22689. "Synthesis of self-pillared zeolite nanosheets by repetitive branching. L. pp. Ruthven. Agrawal." Science. Faraday Transactions. Drury. V." Catalysis Today. A. 1063-1065. Asahina. Cychosz. 1684-7. et al.. Chmelik. and J. D. Kox. D. "Molecular Dynamics Simulations of Mass Transfer Resistance in Grain Boundaries of Twinned Zeolite Membranes." Adsorption. pp. Sholl. C. the accuracy in data acquisition and noise-free operation is not guaranteed. Kapteijn. "Frequency response technique measurements of p-xylene diffusion in silicalite-1 and -2. D. M. Newsome and D. 16. Kortunov. Ruthven." Adsorption. "Diffusion in zeolites – impact on catalysis. Matthijs de Winter. Stavitski. Kärger. which often is invalid to hierarchical materials and very small particles sizes. 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. Zhang. "Diffusion in zeolites—a continuing saga. S. D. Giroir-Fendler. hierarchical and organometallic particles." Zeolites and catalysis. J. M. A.

W. "Frequency Response Method for Investigation of Various Dynamic Phenomena Occurring Simultaneously in a Gas/Zeolite System. R. J." The Journal of Physical Chemistry. J." The Journal of Physical Chemistry. Yasuda. pp. . C. Yasuda. M. M. o. 2011/03/09 2011. pp." Nat Mater. [13] A. M and P. J." Ann. 219. ""Multi-temperature" method for high-pressure sorption measurements on moist shales. Snurr. vol. "The Nature of Surface Barriers on Nanoporous Solids Explored by Microimaging of Transient Guest Distributions. K. S. p. Pramanik. "Neue methode. pp. Fan. 8. [23] Y. 114. "TRANSPORT IN MICROPOROUS SOLIDS: AN HISTORICAL PERPECTIVE Part I: Fundamental Principles and Sorption Kinetics. "Simultaneous measurement of vapor diffusion and solubility coefficients in polymers by frequency response techniques. pp. Anderson. [22] Y. 25545-25555. "A study of pore blockage in silicalite zeolite using free energy perturbation calculations." J Phys Chem B. Y. pp. 1822-33. An Ethylene-on-Zinc Oxide System. Feb 10 2005. [11] A. R." Bulletin of The Chemical Society of Japan. 84. [21] Y. "Frequency Response Method for Investigation of Gas/Surface Dynamic Phenomena. 1987-1997. Kendall. vol. J. pp. [19] S. vol. "Detection of Surface Resistance in a Gas/Porous-Adsorbent System by Frequency Response Method. [16] S. J. M. M. Li. 085116. C." Heterogeneous Chemistry Reviews. vol. 954-961. pp. Catalysis: Royal Society of Chemistry. "Determination of Vapor Diffusion Coefficients in Zeolite by the Frequency Response Method. Evnochides and E. Hibbe. L. 513-530. 64. Chemistry. Ghanizadeh. Gasparik. vol. K. 1870-1875. 117. ed: Springer Netherlands. 2013/12/05 2013. "Dominance of Surface Barriers in Molecular Transport through Silicalite-1. vol. ANGSTROM. 1913-1917. Chmelik. Yasuda." Journal of the American Chemical Society. 1982. Coogan. D." The Journal of Physical Chemistry C. Chem. [12] F. pp. pp. [15] A. 109. vol. vol. "Means and method of catalyst analysis. vol.-C. A. Heinke. 1. 1994. "Frequency Response Method for Study of the Kinetic Behavior of a Gas-Surface System." Journal of Polymer Science Part A-2: Polymer Physics. "THERMODYNAMICS OF CONSTANT-PRESSURE AND CONSTANT-VOLUME SORPTION PROCESSES IN CLOSED-CYCLE SOLIDDESICCANT SYSTEMS. Yasuda. pp. 84. Gupta and R. 9-39. Conner and J. Yasuda. vol. S. Dauenhauer. Fraissard." The Journal of Physical Chemistry. 12//print 2009. [17] A. W. [10] D. 1976. Teixeira. vol.. et al. J. Agarwal." Rev Sci Instrum. pp. T. pp. vol. L. 1991. 2. [18] N. 1. [24] Y. vol. 8. 1861. vol. Hajji and W. and P. pp. 1991/04/01 1991. Henley." Chemical Engineering Communications. 2006. Worek. 3-24. Krooss. 80. das warmeleitungsverm ogen der korper zu bestimmen. 133. 1970." Studies in Surface Science and Catalysis. C. Q. 1994. Ruthven. "Frequency Response Method for Study of the Kinetic Behavior of a Gas-Surface System. 1965. Chang. Ruthven. J. 104. Phys. M. 2140. and B." in Fluid Transport in Nanoporous Materials. [20] Y. Theoretical Treatment.internal and outer-surface molecular diffusion barriers. 1331-1338. Aug 2013. Eds.. Yasuda." ed: Google Patents. R. pp. 959-965. vol. 80. 2804-2807. Gensterblum. 86. 1976. Spivey. and P. 1994. [25] Y. 1867-1869. L. [14] M.

V. Sep-Oct 1991. . 684-689. pp. 22166-22180. "A frequency-response study of the diffusion and sorption dynamics of ammonia in zeolites. pp. Petkovska. M. C. 5. 666-671. and T." Microporous and Mesoporous Materials. 1. Onyestyak. "Mathematical modeling of anomalous diffusion in porous media. 1-28. Sep-Oct 1991. Rees. McDougall. 293-303. and W. Feb 8 2000." Journal of Physical Chemistry C. Capron. "On Asymmetric Surface Barriers in MFI Zeolites Revealed by Frequency Response. Rees and G. P. "Adsorption and Diffusion of N-Butane and 2-Butane in Silicalite-1. vol. and Nax Determined by Frequency-Response Techniques. pp. W. Chang. Rees. and L. pp. Fan." Zeolites. L. V. 62-72. V. Harkness. W. vol. C. I. Brzic and M. Laurence. pp. "The design and construction of a frequency response apparatus to investigate diffusion in zeolites." Zeolites. S. 11. 135-143. pp. Silicalite-1. D. Conner. Fomin. vol. "Some practical aspects of nonlinear frequency response method for investigation of adsorption equilibrium and kinetics. R. vol." Fractional differential calculus. C. S. and P.[26] [27] [28] [29] [30] [31] [32] [33] [34] [35] D. and V. 82. M. D. C. D. Cavers. Chugunov. Sep 25 2014. 2001. Valyon. M." Langmuir. Dauenhauer. pp." Physical Chemistry Chemical Physics. Teixeira. Sep 12 2012. vol. Rees. 16. 2003. C. R. Grenier. "Diffusivities of Benzene in Hzsm-5. Apr 1999. V." Adsorption-Journal of the International Adsorption Society. Shen and L. vol. 2011. pp. 72. 4708-4717. vol. 118. Shen and L. Hashida. A. 5. vol. "Simultaneous determination of diffusion and adsorption properties of microporous sorbents under continuous flow conditions by frequency response methods: propane in silicalite-1. L. A. X. G. J. Onyestyak. R. pp. 4424-4433. L. Conner. and G. J. 13311336. Turner. Qi. D. C. vol. M. "Frequency-response characterization of acid sites in zeolite catalysts using NH3 as the probe molecule. V. Malka-Edery. C. C." Chemical Engineering Science. 11." Review of Scientific Instruments. pp. "A temperature frequency response method for adsorption kinetics measurements. vol. 28. Bourdin. Mar 1999.

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