Research Article

Received: 14 August 2009 Revised: 12 March 2010 Accepted: 15 March 2010 Published online in Wiley Interscience: 30 April 2010

(www.interscience.wiley.com) DOI 10.1002/sia.3474

Determining the surface acidic properties

of solid catalysts by amine titration using
Hammett indicators and FTIR-pyridine
adsorption methods
Yazc and C. Bilgic
D. Topaloglu
Surface acidity of solids (ZSM-5 zeolites, Y zeolite, mordenite and Ca-bentonite) were investigated with Fourier transform
infrared spectroscopy (FTIR) and Hammett acidity functions; the n-butylamine titration method. In the amine titration method,
acid strength of solids were found. The total acid amount of Y zeolite has the highest value among all others. The IR spectrums
of all samples were recorded using diffuse reflectance infrared Fourier transform (DRIFT) technique. Pyridine adsorption and
desorption processes have given some clues about the surface acidity of solids. Copyright
c 2010 John Wiley & Sons, Ltd.

Keywords: surface acidity; FTIR; modified Hammett method; zeolite; bentonite

Introduction introduced by Benesi[11] was used to quantitatively study the acid

The acid, or basic properties of solid surfaces, are interesting
aspects of surface structure, and important in the fields of
ion exchange and heterogeneous catalysis. Acid/base catalyzed
reactions belong to the technologically most important classes
of heterogeneous catalytic conversions.[1,2] Acid/base properties
seem to be important in many organic reactions[3] A variety
of physiochemical techniques have been developed for the
characterization of type, strength and numbers of acid sites on
solid catalysts. One of the oldest techniques for measuring acidity
is based on proposal by Hammett[4] for ordering strengths of
solid acids on the basis of amine titrations. Other physiochemical
techniques used to characterize surface acidity and basicity include
the adsorption of acidic and basic gas-phase probe molecules
combined with spectroscopic measurements (IR) and calorimetric,
gravimetric or thermal desorption measurements. The use of
these different techniques is closely related, and in combination,
can provide a characterization of type, number and strength
of acid/base sites on surfaces. Infrared is the most powerful
technique for the study of zeolitic acidity. Pyridine is a widely
used probe for acidity of solid oxides, zeolites and zeolite-like
materials[5,6] IR spectroscopy of pyridine attached to Bronsted acid
sites (acidichydroxyls), Lewis centers (e.g. Al-containing entities)
and cations (such as alkaline metal, alkaline earth, rare earth or
transition metal ions) is very popular because of the rather sharp
bands which can be observed in the deformation region. The
positions of the bands are typical of the respective adsorption
sites. For instance, Bronsted acid sites give rise to bands around
1540 cm1 . Bands around 1450 cm1 are indicative of true
Lewis sites (in the case of zeolites, extra-framework Al-containing
species).[7]
Traditional method of Hammett indicator was widely used for
measuring the acid strength of solid acids or superacid and ionic
strength of zeolite.[12]
Consequently, the acidity of zeolites has been extensively
studied and, generally, researchers have concentrated on the
kinds of acid sites, the acid amounts and acid strength of
zeolites for their catalytic performance.[6,10,12 22] A traditional
method and a spectroscopic method of dynamic inspection of
adsorptiondesorption processes were used to investigate the
surface acidities of two ZSM-5 zeolites with different Si/Al ratios,
NH4 -Y zeolite, mordenite and bentonite as a local clay.
Experimental
ZSM-5 zeolites (CBV8014, CBV 3024), mordenite (CBV21A) and NH4 -
Y (CBV 500) was directly supplied by Zeolyst International. Calcium
bentonite (Ca-bentonite) was supplied from Amcol Minerals in
Turkey. The Hammett Indicators used were neutral red, methyl
red, p-dimethylaminazobenzene, thymol blue and pKa values of
them are as; 6.8, 4.8, 3.3 and 2.8, respectively. Acid colors of these
are red and basic colors are yellow. Other chemicals like benzene,
petroleum ether, n-butylamine were supplied from Merck and
Fluka reagent grades.
In the amine titration method using indicators, the color of
suitable indicators adsorbed on the surface will give the measure
of its acid strength. Acid strength measurements and acid amount
determination was made according to the literature[10] adapted
Correspondence to: D. Topaloglu Yazc, Department of Chemical Engineering,
Faculty of Engineering and Architecture, Eskisehir Osmangazi University, 26480
Eskisehir, Turkey. E-mail: demett@ogu.edu.tr
Paper published as part of the ECASIA 2009 special issue.
Department of Chemical Engineering, Faculty of Engineering and Architecture,
959

liquids.[8 10] The method of nonaqueous butylamine titration Eskisehir Osmangazi University, 26480 Eskisehir, Turkey

Surf. Interface Anal. 2010, 42, 959962 Copyright

c 2010 John Wiley & Sons, Ltd.
 D. T. Yazici and C. Bilgic

method of antititration, inserting method and using ultrasonic

oscillator. In this titration procedure, the influence of moisture and
overlap of the indicators were reduced to minimum compared
with traditional n-butylamine titration method.
The FTIR spectra of solids were recorded on a Perkin Elmer
100 FTIR spectrometer in the 4000400 cm1 wave number
range using diffuse reflectance infrared Fourier transform (DRIFT)
technique. A spectrum of the solid sample was obtained using
KBr dilution and finely powdered KBr as reference. For acidity
determinations by FTIR, sample was heat treated at 400 C
overnight, followed by evacuation at ca. 105 Torr for 2 h and
at the same temperature. Pyridine adsorption was performed
at room temperature until saturation (60 min). The sample was
then evacuated for 10 min at the 100 C and cooled to room
temperature before recording the spectrum. The desorption of
the probe molecule was successively monitored stepwise, by
evacuating the sample for 10 min at 150, 200, 300 and 400 C and
cooling to room temperature between each step, to record the
spectrum.

Results and Discussion

FTIR spectroscopy is used to probe the structure of zeolites
and monitor reactions in zeolite pores. Specifically, structural Figure 1. FTIR spectrum for pyridine desorption on ZSM-5 zeolite
information can be obtained from the vibrational frequencies (CBV8014) at 100, 150, 200, 300 and 400 C.
of the zeolite lattice.[13] Lattice termination silanol groups are
mainly located on the external surface. For zeolites in the
H-form, the hydroxyl groups bridging a Si and an Al atom
possess strong Bronsted acid properties. The type (Bronsted or
Lewis acidity), concentration and accessibility of surface acid
sites can be determined by the adsorption ammonia, pyridine or
substituted pyridine.[14] Zeolites possess two kinds of acidity. The
most important from the catalytic point of view are the Bronsted
acid sites known as structural hydroxyl groups. Lewis acid sites
in zeolites, some authors believe, that Lewis acidity is associated
with three-coordinated framework aluminum, but more recently
it has been suggested that it is associated with extra-framework
Al, O species.[15]
Figures 15 show the stepwise desorption spectrums of the
ZSM-5 zeolites, NH4 -Y zeolite, mordenite and Ca-bentonite at 100,
150, 200, 300 and 400 C. All figures clearly reveal the pyridine
adsorbed on strong Lewis (1620, 1590 and 1445 cm1 ) acid
sites.[23,24] Only for ZSM-5 (CBV8014) and NH4 -Y weak Lewis acid
sites (1577 cm1 ) were observed.[25] The band around 1530 cm1
which is attributed to pyridine adsorption on Bronsted acid
sites were observed in all figures, and an additional band at
1645 cm1 attributable to Bronsted acid sites was also observed
in mordenite.[26]
The band around 1445 cm1 which is attributed to pyridine
adsorption on Lewis acid sites, did not change significantly with
increasing evacuation temperature up to 400 C. The spectrum
inspection indicates that pyridine is strongly bound to the surface
Lewis acid sites and is not removed by N2 . The behavior observed Figure 2. FTIR spectrum for pyridine desorption on ZSM-5 zeolite
(CBV3014) at 100, 150, 200, 300 and 400 C.
as a function of temperature confirms the high strength of
the pyridine- Lewis acid sites bond and did not complete the
pyridine desorption.[27] The intensity of Bronsted acid site bands
decreased only slightly at temperatures below 400 C throughout is much stronger than those desorbed on Bronsted acid sites,
all of the runs, but it disappears at 400 C for ZSM-5 (CBV8014). and the molecules cannot be easily removed. It has long been
On the other hand, for Ca-bentonite, the intensity of all bands recognized that Lewis acid sites are an important part of the
decreased sharply after evacuation at 400 C (Fig. 5). It appears total on silicaalumina catalysts.[28] The third strong band around
960

that the pyridine molecules desorption bands on Lewis acid sites wave number 1490 cm1 is due to physisorbed pyridine,[16] as

www.interscience.wiley.com/journal/sia Copyright

c 2010 John Wiley & Sons, Ltd. Surf. Interface Anal. 2010, 42, 959962
Determining the surface acidic properties of solid catalysts

Figure 3. FTIR spectrum for pyridine desorption on mordenite (CBV21A)

at 100, 150, 200, 300 and 400 C. Figure 4. FTIR spectrum for pyridine desorption on NH4 -Y (CBV 500) at
100, 150, 200, 300 and 400 C.

some investigators stated that this peak is a contribution of both

Bronsted and Lewis acid sites.[17,29] Conclusion
In the amine titration method using indicators, the color of
The activity and selectivity of the solid in usage areas can be
suitable indicators adsorbed on the surface will give a measure of
restricted by solid surface acid-base property. The reliability and
its acid strength. If the color is that of the acid form of the indicator,
practicability of the methods that are used for determining the
then the values of the H0 function of the solid is equal to or lower
surface acid-base property gain a great importance. DRIFT method
than the pKa of the conjugate acid of the indicator. Color test
promises for these by recording the dynamic process of adsorption
were made by transferring of dried, powdered solid to a test tube,
and desorption. In this study using DRIFT and amine titration
adding a solution of indicator in benzene. From the results of such
methods together, the surface of solid catalysts were determined
tests, it was easy to decide whether the solid under study was basic
as acidic. DRIFT adsorption and desorption of pyridine method
to all indicators, acid to all indicators, or had an H0 lying between
indicated that there are strong Lewis acid sites and weak Bronsted
two adjacent indicator pKas. We used indicators for acid strength
acid sites of solids. Amine titration method exposed that the total
from H0 +7.2 to H0 8.2. The limits of the H0 of samples acidity increased as the Si/Al ratio decreased. The lowest total acid
were established by observing the color of the adsorbed form amount was obtained for Ca-bentonite by amine titration method
of the Hammett indicators. The acid strengths of solids changed and evacuation at 400 C by DRIFT decreased the intensity of the
between +2.8 and +6.8 (Table 1). The summation of acid sites bands of Ca-bentonite.
with strengths gives the total acid amount of solid surface. In
amine titration method, the total acidity increased as the Si/Al
Acknowledgements
ratio decreased, as expected.[8,10] Similar results for zeolites with
different Si/Al ratios were obtained by FTIR which agree well with This study is a part of a project (200715029) supported by the
this study, reported in the literature.[18 21] Research Fund of Eskisehir Osmangazi University.

Table 1. Acid strength distribution

Acid amount (mmol/g)

Solids Ho +2.8 Ho +3.3 Ho +4.8 Ho +6.8 Total acid amount (mmol/g)

CBV8014 (ZSM-5) 0.5 0.2 0.3 1.0

CBV3024E (ZSM-5) 0.3 0.1 0.3 0.4 1.1
CBV21A (Mordenite) 0.6 0.3 0.2 1.1
CBV 500 (NH4 -Y) 0.2 0.2 0.7 0.3 1.4
Ca-bentonite 0.2 0.2 0.2 0.6
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Surf. Interface Anal. 2010, 42, 959962 Copyright

c 2010 John Wiley & Sons, Ltd. www.interscience.wiley.com/journal/sia
 D. T. Yazici and C. Bilgic

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c 2010 John Wiley & Sons, Ltd. Surf. Interface Anal. 2010, 42, 959962