Colloids and Surfaces, 55 (1991) 163-171 163

Elsevier Science Publishers B.V., Amsterdam

Use of the t-plot-De Boer method in pore volume

determinations of ZSM-5 type zeolites

P. Voogd, J.J.F. Scholten and H. van Bekkum

Department of Applied Chemistry and Chemical Technology, Delft University of Technology,
Julianalaan 136,2628 BL Delft (The Netherlands)

(Received 30 January 1990; accepted 14 August 1990)

Abstract

Nitrogen adsorption isotherms at 77 K have been measured of H-ZSM-5 samples of different

crystal size and of moderate as well as of very low aluminum content. Dealumination of the latter
crystal samples caused the isotherms to change from type I to a new type related to type IV, in
which the hysteresis loop was located at very low relative pressure (p/p’=O.l). From t-plots,
derived from the isotherms, pore volumes as well as external crystal surface areas have been cal-
culated. Comparison of the results with densities determined by both helium pycnometry and
mercury displacement revealed that the sudden change in the adsorbed volume was caused by a
liquid-like to solid-like phase transition of adsorbed nitrogen inside the channels of the near-
silicalite crystals.
External areas derived from t-plots were much larger than calculated from crystal morphology
and size. Because of the fact that the ‘filled pore’ method, described in the literature, does indeed
give consistent results, from suggestions are made regarding nitrogen sorption on the external
surface of a ZSM-5 crystal.

INTRODUCTION

As part of an investigation into the effect of crystal size on the catalytic

properties of zeolite ZSM-5, pore volume determinations are of paramount
importance. The need for this particular zeolite characterization can be ex-
plained by considering the following.
The study of mass transfer phenomena in zeolites, i.e., intracrystalline dif-
fusion-limited conversion of reactants, can often be successfully performed by
measuring the effect of crystal size variation on conversion rates. Evaluation
of reaction data using theories on the role of diffusion in heterogeneous catal-
ysis [ 1 ] is possible, provided that the differently sized zeolite crystals are phys-
ically and chemically similar. It is merely this condition which ensures that
any effect may be ascribed to crystal size variation.
Two cases by which the demand stated above is not met are: (Case i) zeolite
crystals containing heterogeneously distributed active sites; and (Case ii)

0166-6622/91/$03.50 0 1991- Elsevier Science Publishers B.V.

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blocking of zeolitic channels caused by defects, intergrowths or non-lattice

material. Obviously, zeolite samples with mutually uneven concentrations of
active sites contribute substantially to the problem as well.
Particularly with regard to zeolite ZSM-5, Case i is known to occur. Surface
microanalyses of polished large ZSM-5 crystals [ 21 or comparison of bulk with
surface compositions [ 31 revealed significant differences between Al-concen-
trations at or near the external crystal surface and in the bulk of the ZSM-5
crystal.
As to Case ii, adsorption experiments can reveal effectively the degree of
accessibility of the ZSM-5 structure for penetrating compounds. Usually or-
ganic compounds like n-hexane, cyclohexane or benzene are applied at tem-
peratures below 373 K. It is common practice to express adsorption capacities
in liquid volume adsorbed per unit weight of zeolite, taking into account the
liquid hydrocarbon densities.
A determination of true zeolitic pore volumes should preferably involve at
least two measuring techniques resulting in consistent data. Recently, Nz and
Ar isotherm data at low temperatures on zeolite ZSM-5 revealed consistent
pore volumes when compared with apparent densities obtained from mercury
displacement and helium pycnometry [4]. It was concluded that nitrogen
reaches a solid-like state in the ZSM-5 channels at 77 K. In high silica ZSM-5
(Si/A1=400) a hysteresis was observed which, as was made plausible, was not
due to capillary condensation but to a liquid-like to solid-like phase transition
[ 41. The Gurvitsch rule was applied to calculate pore volumes using the density
of solid nitrogen (p= 1.026 g cmp3). The low pressure hysteresis was for the
first time reported by Carrott and Sing [5] who studied polycrystalline sili-
calite and ZSM-5.
The present work aims at showing that evaluating nitrogen adsorption data
on ZSM-5 type zeolites with the so-called t-plot method results in consistent
pore volumes. Batches of uniformly sized large crystals of moderate and of very
low aluminum ZSM-5 have been used. The effect of severe dealumination of
near-silicalite crystals on the adsorption of nitrogen at 77 K was studied as
well.
The t-plot method has been developed by De Boer et al. [ 61 and Sing [ 71
has suggested that this method offers a means for determining microporosities.
The technique has been practised in zeolite research by Mieville [ 81 and John-
son [9] to estimate zeolite contents in amorphous, mesoporous matrices. It
was found that a constant factor correlates the so-called BET surface area with
the pore volume determined by means of the t-plot method. Hudec et al. [lo]
used the t-plot method to characterise microporosity changes in zeolites after
various treatments. Al-extraction of Na- and H-mordenite to various degrees
using aqueous HCl, resulted in a decrease of the micropore volume and in an
increase of the mesoporous surface area.
 165

EXPERIMENTAL

Synthesis and characterization

A ZSM-5 sample, viz. ZSM-5 (l), and a silicalite sample, viz. Sil( 1) were
synthesized by adapting an alkaline-free synthesis method by Ghamami and
Sand [ 111, employing ammonium cations to obtain large crystals. Calcination
of washed and dried crystals by heating slowly (1 K min- ’ ) in air to 823 K,
maintaining this temperature for at least 8 h and then cooling slowly, yielded
products to be analyzed.
A second ZSM-5 sample, viz. ZSM-5 (2 ), was prepared following the patent
literature [ 121. After calcination, conversion to H-ZSM-5 took place by ion
exchange (3 times) with a 1 M NH4N03 solution. Finally, the sample was
calcined again. A second silicalite sample, viz. Sil(2 ), was prepared according
to a patent procedure [ 131. Washing, drying and calcining produced the sam-
ple to be analyzed.
Because the silicalite samples contained some aluminum they were dealu-
minated with HCl/steam at 1073 K for 4 days. Next, the samples were mixed
with 2 A4 HCl at 295 K, washed with water and dried. The procedure was then
repeated once. The product samples, viz. Sil(lD) and Sil(2D), were calcined.
Characterizations were performed according to methods published in detail
earlier [ 141. These methods comprise infrared spectroscopy and powder X-ray
diffractometry as methods for global structure verification and atomic adsorp-
tion spectrometry and X-ray fluorescence for elemental analysis. Further-
more, scanning electron microscopy (SEM ) and image analysis have been ap-
plied to study crystal morphology and to determine the crystal size
(distribution), respectively.

Adsorption and densities

The nitrogen adsorption measurements were performed with a Digisorb 2600

(Micromeritics) at 77 K. The samples (400 mg) were pretreated by heating in
vacua at 673 K. After cooling down to 77 K, N,-isotherms were measured. They
were transformed into t-plots by converting relative pressures (p/p’) into t-
values via Eqn (1) [6]:
t= [ 13.99/ (log(pO/p) + 0.034) 10.5 (1)
Adsorption of n-hexane (Fluka, > 99.5% ) was carried out in a gravimetric
balance (C.I. Electronics). A zeolite sample (100 mg) was activated in flowing
nitrogen at 823 K for 16 h, cooled at 298 K and contacted with a flowing gas
(13.3 kPa n-hexane in nitrogen at atmospheric pressure). The total increase
in weight was taken as the n-hexane adsorption capacity of the sample.
The apparent densities, excluding the zeolitic pores, dHe, were determined
166

by helium pycnometry applying an Autopycnometer 1320 (Micromeritics). The

anhydrous framework densities, including pores, were taken from the litera-
ture, viz. c&= 1.77 g cmP3, as determined by mercury displacement [ 151.

RESULTS AND DISCUSSION

All zeolite samples (by SEM analysis) were composed of ‘twinned’ hexago-
nal prism-like crystals, except for the ZSM-5 (2) crystals, which involved mul-
tiple ‘twinnings’, having a sphere-like appearance. Although some crystal ag-
glomerates occurred in samples ZSM-5 ( 1) and ZSM-5 (2 ) , they still could be
observed as being composed of individual crystals. Both silicalite samples did
not contain any agglomerates. Table 1 contains geometrical and chemical char-
acteristics of the zeolite samples as well as n-hexane adsorption results. Deal-
uminated silicalite samples still contained some aluminum. Nevertheless, the
steam/HCl treatment diminished its concentration significantly. From stan-
dard deviations of length and height it can be concluded that the large crystals
have a narrow particle size distribution. All zeolite samples have virtually the
same n-hexane adsorption capacity, close to the literature values [ 12,151.
Figures l-3 show adsorption and desorption isotherms of nitrogen and the
corresponding t-plots of adsorption data for the zeolite samples. The nitrogen

TABLE 1

Geometrical and chemical data of ZSM-5 and silicalite samples used in the adsorption experiment”

Sample ZSM-5(l) ZSM-5(2) Sil(l) Sil(2)

Mean crystal length,

c-direction (pm)b 150 5 89.3 5”
Standard deviation of
length (pm) 2.1 - 3.4 -
Mean crystal height,
a- or b-direction (pm)d 66 - 39.7 -
Standard deviation of
height (pm) 2.7 - 5.0 -
Si/AI 54 49 400/500’ 150/400
Occurrence of crystal
agglomerates? yes yes no no
n-hexane adsorption
(wt%), 0.1% error 10.94 10.72 10.75/10.72’ 10.66/10.83’

“All four samples were phase pure according to X-ray analysis (Guinier-De Wolff).
bMean crystal sizes and particle size distributions of the samples were determined by image anal-
ysis of some 200 crystals.
‘Spherical diameter determined from SEM photographs.
dCrystal breadths (a-axis) were equal to heights (b-axis).
‘Before dealumination/after dealumination.
 167

80 ’ A 80 h-
0.0 0.2 0.4 0.6 0.8 1.0 0 4 8 12 16 20

P/P,

0.0 0.2 0.4 0.6 0.6 1.0 0 2 4 6 8 10 12

P/P, t, A

Fig. 1. Nitrogen isotherms at 77 K and corresponding t-plots of samples ZSM-5 (1) (large crystals)
and ZSM-5 (2) (small crystals). Adsorption (closed symbols) and desorption (open symbols).
See text for explanation of straight lines.

isotherms for ZSM-5 (1) and ZSM-5 (2) are of type I and IV in the Brunauer
classification, respectively, the difference being capillary condensation result-
ing in a hysteresis loop atp/p0=0.4-1.0. However, the crystals of sample ZSM-
5(2) have a diameter of 5 ,um, so it appears that the intercrystalline space is
too large too cause capillary condensation. Probably, the individual crystals
are aggregates of crystallites, with inbetween mesopores.
The pore volume was taken from the positive intercept of the straight line
through t-plot data with the y-axis. Conversion of VA (cm3 STP g-i) into a
pore volume, V,, (cm3 g-’ ), was done assuming that nitrogen reaches a packing
density in the channels of ZSM-5 at 77 K which is more close to the solid
(p= 1.026 g cm-3) than to the liquid state (p=O.8081 g cmh3) [4,5]. Table 2
shows specific volumes from both helium pycnometry/mercury displacement
and nitrogen adsorption. Unlike mercury, helium penetrates the ZSM-5 chan-
nels, wherein it is believed not to condense at 295 K. Therefore, the difference
in specific volume, V,, - V,,, is equal to the pore volume.
In the isotherms of untreated silicalite samples, viz. Sil(1) and Sil(2), the
adsorption branch coincides with the desorption branch. However, dealumi-
nation of the samples was found to exert a strong influence on their sorption
168

0123456

120 +

0.0 0.1 0.2 0.3 0.4 0.5

P/P,

Fig. 2. As Fig. 1 for samples Sil( 1) and Sil( 1D ) (large crystals). ( n , 0, 0 )Untreated silicalite.
( V, v, + ) Dealuminated silicalite. ( - - * * ) Straight line through Sil( 1) data; (---- ) straight lines
through Sil(lD) data.

behaviour. In Figs 2 and 3 [ Sil ( 1D ) and Sil(2D ) ] two plateaus are observed
in both cases. The t-plots corresponding to these isotherms show two plateaus
as well. Two straight lines were, somewhat arbitrarily, drawn through the t-
plot data at t = 2.8-3.8 A and at t = 5.0-6.0 A, respectively. We here assume that
the zeolite pores are completely filled with liquid-like and solid-like nitrogen
at p/p” = 0.015 and p/p” = 0.28, respectively. A contradiction exists between
this assumption and the proposition made by Sing et al. [ 16,171 on micropore
filling. This proposition has it that slit-shaped micropores (d,, < 2 nm) are
completely filled with the adsorptive at p/p” = 0.01 when the ratio of the pore
width to the molecular diameter (d/a) is in the range 1 to 2. This is called
primary pore filling. Secondary pore filling takes place over the pressure range
p/p”=0.02-0.2. Adsorptives taken up in this range are adsorbed in wider mi-
cropores in the range d/0=2-5. It is said to be a form of quasi-multilayer
adsorption.
Another explanation is that up top/p’= 0.2 a densification occurs inside the
zeolitic pores. At aboutp/pO=0.2 the nitrogen adsorbate has turned solid-like.
Contrary to the dealuminated silicalite samples, a sharp increase in the ad-
sorbed amount of nitrogen in the untreated silicalite samples is not measured.
Likewise, a hysteresis loop is not observed.
From the slopes of the straight lines through the respective t-plot data in
Figs l-3 external crystal surface areas and mesoporous areas have been cal-
culated (A ( m2 g- ’ ) = slope* 15.47) [ 61. In Table 3 these results are given com-
 169

0123456
t, A
130,

0.0 0.1 0.2 0.3 0.4 0.5

P/P,
Fig. 3. As Fig. 1 for samples Sil(2) and Sil(2D) (small crystals). (0, 0) Untreated silicalite.
( V , V ) Dealuminated silicalite. ( * *- . ) Straight line through Sil(2) data; (----) straight lines
through Sil(2D ) data.

TABLE 2

Specific ( V,, and V,,) and pore volumes (if,,- V,, and V,, ) of ZSM-5, silicalite and dealu-
minated silicalite samples

Sample VHg vHg - vH, V,, (solid)

(cm3 gg’) (cm” g-l) (cm3 gg’)

ZSM-5(l) 0.423 0.565 0.142 0.132

ZSM-5(2) 0.423 0.565 0.142 0.134
Sil(1) 0.417 0.565 0.148 0.127
Sil(2) 0.419 0.565 0.146 0.126

bined with external crystal surface areas calculated from the sample morphol-
ogy and the size of the sample crystals. A roughness factor of 2 was assumed.
As to the dealuminated samples, Sil(lD ) and Sil(2D ), it can be concluded that
values taken from the first and from the second plateau are equal. These values
are, however, much greater than calculated crystal surface areas. The possi-
bility that the samples contain a certain amount of amorphous material must
be ruled out as judged from the n-hexane adsorption capacities, which are con-
sistent with the patent literature [ 12,131. Furthermore, SEM analysis did not
give evidence for any significant amounts of a non-crystalline phase.
A possible reason for the discrepancies in external surface areas is that the
170

TABLE 3

External crystal and mesoporous surface areas determined with the t-plot method

Sample External Calculated external

surface area surface area
(m2 gg’)” (m* gg’)b

ZSM-5(l) 4.41f3.1 0.08

ZSM-5(2) 28.5 k 1.4 1.4
Sil(1) 24.1 k 7.9 0.15
Sil(lD) 24.9 k 2.0 0.15
Sil(2) 30.5 k 3.3 1.4
Sil(2D) 39.2 * 1.9 1.4

“From the t-plot.

bFrom sample morphology and crystal size.

roughness of the external crystal surface of ZSM-5 does not correspond to a

factor of 2 but to a much greater value. The crystal surface is in this respect
highly complicated, consisting of all kinds of mesoporous regions. These orig-
inate from the hydrothermal zeolite synthesis, or from some treatment during
product recovery. Results of scanning tunneling microscopy experiments on
silicalite crystals were remarkable in this respect [ 181. However, it cannot be
ruled out that the high values in Table 3 point to an internal rather than an
external surface. The results would then suggest that the large crystals [ ZSM-
5 ( 1) and Sil(1) ] form aggregates containing mesopores or that the individual
crystals are aggregates in themselves. SEM analysis did not point to the first
suggestion so that the second suggestion stands as a possible explanation.
In the literature other methods of external surface area determinations have
been described. Besides electron microscopy these are the BET method, using
large molecules [ 191, an adsorption kinetic method [20,21], and the ‘filled
pore’ method [ 21-231. In the latter methods, as in the t-plot method, nitrogen
is used to determine the external surface area. The difference lies in the com-
pound adsorbed in the zeolitic channels as in this method it is (preferably)
benzene. In this way results have been obtained which agreed well with cal-
culations based on scanning electron micrographs [22]. As judged from the
experiments the external surface was already covered with a layer of the hy-
drocarbon before nitrogen was adsorbed, so external mesopores were obscured
using this method. Thus, the mechanism of nitrogen adsorption on the exter-
nal surface of ZSM-5 differs in the ‘filled pore’ method from the t-plot method.
Further investigations may shed some light on the important matter of outer
surface dimensions and texture.

CONCLUSIONS

The pore volume of ZSM-5 type zeolites is + 0.13 cm3 gg ‘. Nitrogen adsorp-
tion isotherms on zeolite ZSM-5 are of type I in the Brunauer classification.
 171

The shape of the isotherms changes profoundly on very high silica ZSM-5 [in
this work the silicalite samples Sil(lD) and Sil(2D) 1. Hysteresis is observed
at low pressures (p/p’=O.l). Two plateaus in the isotherms are ascribed to
zeolite channels filled with liquid-like and with solid-like nitrogen, respectively.
External crystal surface areas determined by means of the t-plot method are
substantially higher than calculated from crystal geometrical considerations.
A possible explanation is given.

ACKNOWLEDGEMENTS

The authors would like to thank Th.W. Verkroost from the Department of
Mining Engineering for performing the X-ray fluorescence measurements and
J. Padmos for the AAS analyses. E.J.A. van Dam and J.F. van Lent from the
Laboratory of Metallurgy are thanked for SEM analysis and X-ray diffraction
analysis. J. Teunisse and N. van Westen from the Laboratory of Chemical
Technology are acknowledged for the adsorption and density measurements.

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