AASCIT Journal of Nanoscience
2016; 2(1): 1-5
Published online February 17, 2016 (http://www.aascit.org/journal/nanoscience)
ISSN: 2381-1234 (Print); ISSN: 2381-1242 (Online)
Keywords
Isotherm,
Heat,
Entropy of Adsorption,
Synthetic Nax Zeolite,
Carbon Oxysulphide
Received: December 11, 2015
Revised: January 14, 2016
Accepted: January 16, 2016
Adsorption of Carbon Oxysulphide
by Synthetic Zeolite NaX in a Wide
Range of Equilibrium Pressures and
Temperatures
Girat U. Rakhmatkariev, Firuza G. Rakhmatkarieva,
Vitaliy P. Guro
Institute of General and Inorganic Chemistry, Academy of Sciences, Tashkent City, Uzbekistan
Email address
vip.gairat@gmail.com (G. U. Rakhmatkariev)
Citation
Girat U. Rakhmatkariev, Firuza G. Rakhmatkarieva, Vitaliy P. Guro. Adsorption of Carbon
Oxysulphide by Synthetic Zeolite NaX in a Wide Range of Equilibrium Pressures and
Temperatures. AASCIT Journal of Nanoscience. Vol. 2, No. 1, 2016, pp. 1-5.
Abstract
The adsorption isotherm of carbon oxysulphide in zeolite Na are measured by
volumetric method at temperatures 0; 25; 60 and 100C. Isosteric heats and entropies of
carbon oxysulphide in zeolite Na adsorption are calculated. A mechanism of adsorption
of carbon oxysulphide in zeolite Na is revealed. It is established that the centers of
strong adsorption in the zeolite NaX are Na+ cations at SIII position with which the
molecules of the carbon oxysulphide do form monomeric complexes (S)/Na+ in the
amount of 2.7 localized in supercages. Less strong, reversible adsorption occurs on the
sodium cations at SII position in supercage in a number equal to amount of cations in a
current position being 4. The adsorption isotherms are completely described by two- and
three-term VMOT equations.
1. Introduction
Zeolites are wide used desulphurization of natural gases [1]. However at use of
zeolites for clearing natural gas with high concentration of carbon dioxide there is a
reduction of hydrogen sulphide sorption. Besides at presence of carbon dioxide the
zeolites can convert hydrogen sulphide into carbon sulfoxyde and water. This issue
attracts not enough attention because the opinion presents indicating that increase of the
maintenance of calcium cations should suppress successfully the process of formation
carbon sulfoxyde. However it works, when the content of carbon dioxide is not enough.
At its high concentration there is a full conversion of hydrogen sulphide on zeolites
surface [2, 3]. Formation of carbon sulfoxyde is explained by catalytic activity of
exchange cations and the active centers of structure. Besides it, the displacement of
reaction aside the formation of carbon sulfoxyde and water is caused by removal from a
reactionary mixture of water molecules which gather in sodalite cavities of zeolites [4].
The detailed analysis of this process has been carried out by Buhl with co-authors aiming
at suppression of this process [5, 6]; they have suggested the way of blocking sodalite
cavities with salts (calcium nitrite).
Carbon oxysulphide has a negative effect on the total sulfur content in gas and is a
highly toxic compound that dramatically worsens the environmental situation, and when
interacting with water drops is turning again to the hydrogen sulphide which causes
intense corrosion of pipelines and equipment.
Zeolites are of great interest due to the possibility to change their properties such as
texture and chemical, which, ultimately, affect their adsorption properties. Therefore, the
problem of localization and distribution of the extra-lattice cations in the zeolite systems
is important because it affects the distribution of electron density in the structure and,
2 Girat U. Rakhmatkariev et al.: Adsorption of Carbon Oxysulphide by Synthetic Zeolite NaX in a Wide Range of Equilibrium
Pressures and Temperatures
hence, on the interaction with adsorbed molecules, leading to
possible changes in the adsorption and separation properties
of zeolites.
The forms and sizes of zeolites pores are studied well and
with high precision using x-ray structural methods. Exchange
cations can actively interact with adsorbed polar small
molecules. Here the chemical nature of adsorbing pores plays
the main role while to geometric factor polar molecules are
not sensitive. Owing to these features we can study the
influence of chemical factors on adsorption energetic
characteristics of any other adsorbents.
We have not found the researhes devoted to the
experimental study of the adsorption energy of COS in
zeolites, published in the recent decade. Apparently, this is
due to the high toxicity of the adsorbate. Theoretical work in
which the effects of cations of zeolite for the adsorption of
organosulfur compounds were investigated by using the
density functional theory calculations is presented in [7]. The
binding energies of tetrahydrothiophene (C4H8S, THT),
dimethyl sulfide (C2H6S, DMS), tert-butylmercaptan
(C4H10S, TBM), hydrogen sulfide (H2S), and carbonyl sulfide
(COS) on the zeolite model clusters [X(HO)3SiOAl(OH)3, X
= H+, Na+ and Ag+] were obtained and compared with those
of H2O, CO2, and C1C3 light hydrocarbons. Compared to
the H+ and Na+ cations, the Ag+ cation induces much stronger
binding of THT, DMS, TBM, and H2S over H2O suggesting
great enhancements in the adsorption selectivity. The order of
binding energies of these sulfur compounds is THT > DMS >
TBM > H2S > COS, and it does not depend on the cation
types. These results agree well with the adsorption uptake
and selectivity properties of AgNaY zeolites for organosulfur
compounds.
The energy of sorption processes is the major
characteristic of any adsorbents system. The most high-
grade information of macroscopical (thermodynamic) and
microscopic (molecular-structural) characteristic offers
adsorption calorimetry. Due to it now new methodological
direction of adsorbents study and the superficial phenomena
called adsorption-energetical stoichiometry now develops.
High informativeness of calorimetric methodology of
researches with reference to the basic structural types of
adsorbents has been demonstrated by the example of not
porous rutile [8], layered porous muscovite [9] and
microporous zeolite [10].
Zeolite micropores in terms of adsorption-energetic factor
are discrete-homogeneous adsorbents; i.e. in adsorbing
zeolite cavities and channels there are few groups of
homogeneous in terms of energetic centres. Exchange cations
are such centres relative to polar small molecules. More
narrow fragments of porous structure are such centres
relative to nonpolar molecules. Thermodynamic adsorption
function (enthalpy, free energy, entropy, heat capacity) and
time required for adsorption equilibrium versus degree of
zeolite micropores volume filling curves demonstrate distinct
points in which they have stepwise drops and fractures which
correlate with crystallochemical structures of the surface of
adsorbing spaces of zeolites.
High informativeness of adsorption-calorimetric method is
revealed by numerous experiments. Isosteric method
appreciably concedes the calorimetric method; however,
having raised the accuracy of adsorption measurements and a
dosage of adsorbate, we have tried to approach the accuracy
of the second method to the first one and to obtain the data,
suitable for carrying out of correlations by the method of
adsorption-energetical stoichiometry. The objective of this
study was to measure adsorption isotherms (a) of carbon
oxysulphide in Na in the range of temperatures from 0 to
100C, on the basis of isotherms measured at different
temperatures, calculation of isosteric heats (Qd) and entropy
(Sd) of adsorption, as well as identification of the adsorption
mechanism.
2. Objects and Methods of Research
We used Na zeolite with the composition of the unit cell
(uc): Na86(AlO286)(SiO2)106. The chemical composition of the
fully dehydrated zeolite NaX has been verified by elemental
analysis. The method of sample decomposition of synthetic
zeolites with simultaneous determination of moisture content
and organic impurities, followed by atomic absorption
determination (Perkin - Elmer 3030B) of exchangeable
cations Na content has been developed. It eliminates the
influence of structure forming elements (Al, Si) and
fluctuations in the moisture content of the probes on the
analysis results.
Zeolites transferred by us for the analysis in the
International research centers yielded inconsistent results on
ion-exchange cations Na, and Ba, as well as on basic
elements Si and Al from which the structure of molecular
sieves is constructed. In this connection one of the tasks was
to develop a reliable and exact technique of definition of ion-
exchange elements, not only sodium, but also calcium and
barium in synthetic zeolites of various structures and cationic
composition which were investigated and should be
presented in the subsequent publications.
Studying of the published [11, 12] methods of atomic
adsorption spectroscopy (AAS) analysis applied to alumna-
silicate materials has shown, that they are connected to a
number of difficulties, in particular, with necessity of
elimination of interelement influences during carrying out of
definitions. Techniques of definition of the content of ion-
exchange elements (Na, Ca and Ba) in synthetic alumna-
silicate materials (zeolites) of various structure and cations
composition are developed. To get this purpose the ardent
variant of a AAS method has been chosen characterized with
high sensitivity and selectivity. On the basis of the
comparative analysis of the known techniques used for
processing of analyzed samples of silicate materials into a
solution two variants of the zeolites samples decomposition
have been offered, as follows: decomposition by a mixture of
hydrochloric and hydrofluoric acids (at heating) with the
subsequent AAS definition of the content of Na in propane-
air flame in a liquid part of a solution, and Ca in another a
liquid part at presence of spectral chemical buffer (5% LaCl3)
in an air - acethylene flame (for samples of zeolites such as A
and X types) on one hand; decomposition of samples by the
way offered by Belt and Thompson for the analysis of silicate
breeds and AAS definition of Ba in obtained solutions (with
 AASCIT Journal of Nanoscience 2016; 2(1): 1-5 3

the additive of La salt) in regenerative N2O-C2H2 flame (for
molecular sieves such as Y).
Focusing on exception of influence of tested samples
fluctuations of humidity on results of the analysis
simultaneously with samples decomposition the definition of
moisture and organic impurities in them were carried out.
The offered techniques have been approved on samples of
zeolites of known structure (NaA, NaX, BaY) and yielded
good results.
Studies were conducted on a universal high vacuum
setting, allowing the dosage of the adsorbate as gas-
volumetric and volumetric-liquid methods, with an accuracy
of 0.1% [9, 13]. Adsorption unit is a vacuum glass apparatus
with capillary microburette and mercury seals. The
installation consists of ampoules with the adsorbent,
measuring parts, storage, dosage the liquid and gases and
pumping system (zeolite and roughing pumps). The
installation allows the dosage of the adsorbate as gas-
volumetric and volumetric-liquid methods. With the help of
cathetometer V-630 with an accuracy of 0.01 mm the level of
mercury in a U-shaped manometer with an inner diameter of
12 mm could be measured.
In this paper, we investigated adsorption isotherms S in
the NaX zeolite at temperatures of 273, 298, 333 and 373 K.
Before the water steam inlet the sample was heated and
subjected to high-vacuum pumping at 623 K for 10 hours.
The procedure for describing the sum a0i fi (A) entails the
following. A value for n1 is initially taken such that the
isotherm plotted as ln a vs. An1 is linear over the maximum
range of occupancies, starting from the first measurements of
lowest occupancies a; n1 is taken such that a01 a0. Then, the
partial isotherm a01 f1 (A) is subtracted from the experimental
isotherm and the search procedure for the value of n2 is
repeated for the residual isotherm until the experimental
isotherm is fully described.
Adsorption isotherms of S on the zeolite are
satisfactorily describes by two-term equations VMOT (Fig.
1). Below the equations of adsorption isotherms measured at
temperatures 0, 25, 60 and 100C are offered:
0C: a = 3,98exp[-(A/19,41)7] +1,03exp[-(A/10,66)4];
25C: a = 1,62exp[-(A/21,50)6] +2,90exp[-(A/14,00)5];
60C: a = 2,06exp[-(A/19,31)4] +2,15exp[-(A/15,01)5];
100C: a = 0,30exp[-(A/22,95)7] +4,23exp[-(A/12,92)3].
On the basis of adsorption isotherms the isosteres - lines
dependences of equilibrium pressure on temperature at
constant values of adsorption are calculated (Fig. 2). Isosteres
in the coordinates lgP-T-1 are lines, their slope to the axis of
temperature changes with increasing of surface coverage of
the adsorbent. By the slope of the isosteres the isosteric heats
of adsorption are calculated (Fig. 3). Fig. 4 shows the
differential entropy of adsorption, Sd, of S in NaX
zeolite as a function of the amount of adsorbed molecules.

3. The Results and Discussion

Faujasite are of anionic aluminosilicate regular
microporous structure [14]. Structure of zeolites X consists
of supercages with almost spherical symmetry with a
diameter of ~1.25 nm and window size of ~0.74 nm. Each
cavity is connected to four other cavities, arranged
tetrahedrally. The structure also contains sodalite cavities,
connected to each other with double six-membered rings.
Monovalent extra-lattice cations mostly occupy
crystallographic positions I, I, II and III. Intracrystalline
environment of the host structure is modified by cation
exchange and guest molecules usually differ in polarizability,
Fig. 1. Adsorption isotherms of COS in NaX zeolite at: 1- 0C; 2- 25C; 3-
dipole or quadrupole moments, shape and size.
60C; 4- 100C. White points experimental data; black points calculated
In Fig. 1 COS adsorption isotherms in NaX at different using VMOT.
temperatures (0, 25, 60 and 100C) are presented. Adsorption
capacity of NaX to S is on 12% higher than in A type
zeolite.
The major theory of the volumetric micropore theory
(VMOT) express the dependence of the micropore
occupancy = a/a0 on the adsorption energy A = RT ln Po/P,
a = a0 /exp (A/E0)n, where a0 is the limiting adsorption, P/P0
is the relative pressure, and E0 and n are constants [15]. The
experimental isotherm is usually described by the term
VMOT equation better than by the one term equation
proposed by Izotova and Dubinin [16]. However, in practice,
this two-term equation also proves inadequate for the
complete description of the isotherm with satisfactory
precision.
In principle, it would appear that any adsorption isotherm
should be precisely described from zero occupancy to
saturation by the sum of partial VMOT-type isotherms: a = Fig. 2. Isosteres of COS adsorption in Na zeolite at different values of
adsorption a(mmol/g): 1-0,5; 2-1,0; 3-1,5; 4-2,0; 5-2,5; 6-3,0; 7-3,5; 8-4,0.
a0i/exp (A/E0i)ni.
4 Girat U. Rakhmatkariev et al.: Adsorption of Carbon Oxysulphide by Synthetic Zeolite NaX in a Wide Range of Equilibrium
Pressures and Temperatures
Fig. 3. Differential isosteric heats of adsorption of COS in NaX zeolite.
Fig. 4. Differential molar entropy of adsorption, Sd, of COS in NaX zeolite.
Entropy of liquid COS is taken as zero.
Isosteric curve of heats of S adsorption in NaX (Fig. 3)
at the range of small fillings sharply reduces from 48 down to
34 kJ/mol, passing minimum at a = ~1.5 mmol/g, then - the
maximum - 39 kJ/mol and falls down to 34.5 kJ/mol at 4
mmol/g.
Totally 4 mmol/g COS are adsorbed that in terms of the
number of COS molecules per 1/8 of the unit cell (uc) is 6.7.
The unit cell of NaX zeolite contains 86 Na+ cations. In
terms of 1/8 uc it reaches 10.7 Na+. The cations are
distributed as follows: 4 in SII and SI in supercages and
small cavities, respectively, and the remaining 2.7 are in
supercages in the position of the SIII [14]. The most
preferred adsorption centers are cations at open SIII
position. The area with higher heat of adsorption on the Qd
curve (0-1.55 mmol/g or 2.7 COS/(1/8) uc) we refer to
adsorption at these centers, since the number of adsorbed
COS molecules is equal to the number of these centers.
Further, the heat of adsorption are growing, passing through a
maximum and decrease, reaching 4 mmol/g or 6.7 S
/(1/8) uc. If from the total number of S molecules 2.7
could be subtracted, 4 of S /(1/8) uc would be remain, i.e.
as many as the number of cations Na+ at position SII or SI
is. Given the fact that the molecules of carbon oxysulphide
do not penetrate into the sodalite cavity for steric reasons,
and therefore can't interact with cations at position SI, it can
be argued that they interact with cations at position SII. The
increase of heat with filling indicates the overlay of energy of
the adsorbate-adsorbate interaction over the total energy of
the adsorption.
The molar differential entropy of adsorption of S in
NaX (Fig. 4) was calculated from the data of heats and free
energy of adsorption. The entropy of adsorption is deferred
from the entropy of liquid carbon oxysulphide. The entropy
starts from negative values (-16 J/mol*K), increases, crosses
the zero line, then passes through a maximum (+14
J/mol*K), decreases again, crosses the zero line passes
through the minimum (-14 J/mol*K), and stabilizes at a level
-12,8 J/mol*K. The carbon oxysulphide, adsorbed on the
cation in the SIII position obtains some degree of freedom
that causes the growth of entropy. At adsorption on the Na+
cations in the SII position the adsorbate is associated with
preadsorbed S molecules, which leads to a decrease of
entropy and its transfer into the region of negative values. In
general, the mobility of the molecules of carbon oxysulphide
is below of their mobility in a liquid adsorbate.
4. Conclusion
The study of adsorption of carbon oxysulphide vapors in
zeolite NaX is performed at temperatures 0; 25; 60 and
100C. Values of the molar differential enthalpy, free energy
and entropy of adsorption are calculated which served as the
basis for molecular-structural and thermodynamic
correlations of adsorption properties of NaX.
It is established that the centers of strong adsorption in the
zeolite NaX are Na+ cations at SIII position with which the
molecules of the carbon oxysulphide do form monomeric
complexes (S)/Na+ in the amount of 2.7 localized in
supercages. Less strong, reversible adsorption occurs on the
sodium cations at SII position in supercage in a number equal
to amount of cations in a current position being 4. Molecules
of carbon oxysulphide adsorb on cations at the SII position
do associate with early preadsorbed molecules, which leads
to an increase of heat of adsorption due to the energy of
interaction of adsorbed molecules with each other. One
eighth of the unit cell or supercage holds 6.7 molecules of
carbon oxysulphide. The mobility of the molecules of carbon
oxysulphide in zeolitic matrix is inhibited.
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