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Materials Chemistry and Physics 106 (2007) 187–192

Anatase/rutile TiO2 composites: Influence of the mixing ratio on the

photocatalytic degradation of Malachite Green and Orange II in slurry
A. Bojinova a , R. Kralchevska a , I. Poulios b , C. Dushkin a,∗
a Department of General and Inorganic Chemistry, Faculty of Chemistry, University of Sofia, Sofia 1164, Bulgaria
bLaboratory of Physical Chemistry, Department of Chemistry, Aristotle University, 54124 Thessaloniki, Greece
Received 9 September 2006; received in revised form 16 May 2007; accepted 20 May 2007

Abstract
The present study is directed to clarify the influence of the ratio of anatase to rutile phase, containing in the TiO2 samples, on their activity
as photocatalysts in slurry. A series of samples corresponding to different percentages of anatase is prepared from commercial anatase and rutile
TiO2 brands (KRONOS). The crystalline phase composition of the samples is characterized by X-ray diffraction. The photocatalytic action of the
mixtures is tested in photodegradation of the commercial organic dyes Malachite Green Hydrochloride and Orange II in aqueous solutions under
UV irradiation. Comparative tests with Degussa P-25 are performed. The apparent rate constants of the process are determined from the kinetic
curves using appropriate models. They generally increase with the anatase ratio, being always larger for Malachite Green than for Orange II.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Titanium dioxide; Photodegradation; Organic dyes; Slurry; Water purification

1. Introduction
The present study is aimed to investigate the influence of
the anatase/rutile ratio in TiO2 powders, prepared from KRO-
NOS brands, on the photocatalytic oxidation of organics in
water solutions. Malachite Green Hydrochloride (MGH) and
Orange II (OII) are chosen as the model pollutants. The kinetics
of photocatalysis of the composite powders is established and
compared to the photocatalytic behavior of commercial TiO2
Degussa P25.
Commercial colorants, like MGH and OII [1–7], dissolved
in water have become a focus of the environmental remedia-
tion efforts. A method, capable for waste-waters purification,
especially at low dye concentrations, is the heterogeneous pho-
tocatalysis in slurry. It comprises the UV-illumination of titania
aqueous suspensions for the destruction of the dye onto the
surface of TiO2 particles [8–12]. Previously published works
on advanced oxidation technology claim that the photocat-
alytic efficiency of TiO2 depends on its crystalline form. This
variability has been attributed to differences in the rates of
recombination, adsorptive affinity, or band gap between the
∗ Corresponding author. Tel.: +359 2 8161 387; fax: +359 2 962 5438.
E-mail address: nhtd@wmail.chem.uni-sofia.bg (C. Dushkin).
rutile and the anatase phases of TiO2 [13,14]. It has been compu-
tationally found that the anatase has a larger band gap (3.2 eV)
than rutile (3.0 eV), although both of them have similar ground-
state properties [15]. It has been pointed out that in anatase,
the Fermi level is higher with about 0.1 eV than that of rutile
[16]. The photocatalytic efficiency of TiO2 depends also on the
crystalline morphology and interfacial contact. The interplay
between these properties in titania, consisting of mixed rutile
and anatase, generally enhances the photocatalytic activity. For
this reason the best commercial photocatalyst Degussa P25 con-
sist of anatase 80% and rutile 20% [14]. However, Degussa P25
is rather expensive (about 26 D kg−1 ) for large-scale applica-
tion in slurry for water remediation. For this reason attempts
are made to replace Degussa with a blend of other TiO2 brands,
which can be better suitable in particular applications [7,9,12].
This is also our motivation in looking to utilize anatase and
rutile of KRONOS TITAN GmbH Levercusen, Germany (ca.
2.5 D kg−1 ).
In the allotropic forms, anatase and rutile, the coordination
of Ti is sixfold with O atoms forming a distorted octahedron;
the O atom is shared by three adjacent Ti atoms. The dis-
tortions of octahedra in these phases lead to crystallographic
differences and result in different arrangement of the Ti O and
Ti OH bonds on the surface of their particles. The titanium ions
in rutile and anatase are located on tetragonal sites, in which

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188 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192

the two axial Ti O bonds are longer than the four equatorial
Ti O bonds [17]. The distortion of the TiO6 unit is greater
in anatase than in rutile. The structure of the most stable sur-
faces of TiO2 has been examined for the both modifications
[18]. The (1 0 1) surface of anatase and the (1 1 0) surface of
rutile exhibit twofold coordinate oxygen anions and fivefold Ti
cations, but the oxygen anions are more widely spaced on the
anatase surface. It is of interest to understand how the struc-
ture differences of TiO2 forms may affect the oxidative catalytic
processes.
As the first step, this investigation is focused on the influence
of the anatase and rutile content in the mixture on the photocat-
alytic oxidation of the organic dyes MGH and OII in aqueous
solutions. The results obtained from the composite samples by
variation of the anatase/rutile ratio are compared to those from
Degussa P25.

2. Experimental

2.1. Materials

The catalysts, used in the experiments are: Degussa P25 from Degussa
AG-Germany, anatase and rutile from KRONOS TITAN GmbH Levercusen,
Germany (referred to as KRONOS).
As model pollutants Malachite Green Hydrochloride (wavelength of
maximum absorbance λmax = 616 nm) from Sigma–Aldrich and Orange II
(λmax = 484 nm) from Fluka were used. The structural formulas of the organic
dyes are shown at Scheme 1.
The absorbance spectra of the dyes were determined by spectrophotometer
Jenway model 6400—see the insets to Fig. 1. In order to check the applicability
of the Lambert–Beer law for the dye in solutions, calibration lines were plotted
experimentally (Fig. 1).

Fig. 1. Calibration lines and change in the absorption intensity at the absorbance
maximum of the dyes Malachite Green Hydrochloride (a) and Orange II (b)
in water solutions. The insets represent the concentrations variations of the
absorbance spectra.

2.2. Sample preparation and characterization

Scheme 1. Structural formulas of Malachite Green Hydrochloride (a) and
Orange II (b).
The composite samples were prepared from the commercial anatase and
rutile powders. The initial charge consists of a mixture of both allotropic forms,
precisely homogenized in glass mortar for 10 min. The composition of the sam-
ples corresponds to 25, 50, 60, 70, 75 and 80% anatase. A small quantity of
ethanol was used as mixing medium. The samples were thermally treated at
200 ◦ C for 2 h to assure complete removal of the ethanol and better contact
between the two phases.
The crystalline phase composition of the as-prepared catalysts was char-
acterized by X-ray analysis (Cu K␣ source radiation, diffractometer Siemens)
(Fig. 2).
The average crystallite size in the grains of Degussa P25 was calculated
from the peaks in Fig. 2a by the Scherrer equation to be 42 nm for the anatase
and 56 nm for the rutile phase. This is different from the literature data for the
average grain size obtained by TEM: 20–30 nm [7], 30 nm [19,20].
The X-ray diffractogramm in Fig. 2b illustrates smooth transition in the
intensity of the characteristic peaks for anatase and rutile, corresponding to the
change of the sample composition. In similar way, the average crystallite size for
KRONOS was calculated to be 40.7 nm for anatase and 40.9 nm for rutile [21].
The surface area of the dry powders, determined by BET analyses using N2
adsorption, is 57.6 m2 g−1 for Degussa P25. The literature data point 50 m2 g−1
[3,19,20], 44 m2 g−1 [4], 47 [7] and 48 m2 g−1 [22]. The respective values
for TiO2 of KRONOS, measured by us, are 11.69 m2 g−1 for anatase and
11.57 m2 g−1 for rutile.
 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192
Fig. 2. Comparative XRD patterns of Degussa P25 (a) and the prepared mixed
TiO2 samples (b).
2.3. Photocatalytic testing
The experiments were performed in a cylindrical glass reactor (length
14.5 cm, inner diameter 4 cm and outer diameter 7.2 cm) [23]. The source of
radiation was OSRAM DULUX DL18/71 UV lamp (length 22.5 cm, diameter
3.8 cm), emitting mainly in the range of 350–400 nm. The lamp is placed in a
Pyrex tube axially into the reactor. The volume of the water suspensions of TiO2
was 250 ml. The catalyst loading was 0.5 g l−1 . This concentration was chosen
to satisfy two requirements: first, to provide a diluted suspension with enough
transparency for penetration of the UV light in the liquid volume and second,
to assure enough catalysts particles for reliable destruction of the pollutant dye.
The initial dye concentrations in the TiO2 suspensions were 10 ppm MGH and
20 ppm OII, respectively, chosen to absorb measurable amount of light. The sus-
pensions were first stirred in the dark for 30 min to reach equilibrium sorption
of the dye. After that the UV illumination was started to carry out the photo-
catalysis. Aliquot samples of 6 ml were taken at determined time intervals (at
lamp switched of) and filtered through 0.22 ␮m membrane filters to remove the
TiO2 particles. The change in the dye concentration in each aliquot was then
determined spectrophotometrically at the maximum of absorbance. pH was also
determined for each aliquot tested. The dye degradation was carried out at pH
4.6–6 for MGH and pH 5.5–4.8 for OII. The temperature was 23 ± 2 ◦ C during
the experiments.
Stirring of and air bubbling in the suspension were kept constant along the
experiments to assure oxygen saturation, uniform illumination of TiO2 particles
by UV light and constant transfer rate of the pollutants to the catalyst.
Blank experiments with the pure dye solutions, illuminated with UV light
for 2 h, were conducted prior the photocatalytic experiments. No significant
decolorization of the solutions was observed indicating that the direct photolysis
of MGH and OII is negligible.
3. Results and discussion
MGH is a cationic dye with expected pronounced sorption
on the suspended TiO2 particles [4]. In contrast, OII is represen-
tative acid azo dye with low level of sorption. For this reason,
189
Table 1
Sorption values of the organic dyes (initial concentration 10 ppm for MGH
and 20 ppm for OII, TiO2 loading 0.5 g l−1 ) reached at the sorption–desorption
equilibrium of the suspensions without UV-illumination
Catalyst Sorption (%)
MGH OII
Degussa P 25 9 20
Anatase 22 0
Anatase 80% 21 –
Anatase 75% – 3
Anatase 70% 19 –
Anatase 60% 20 2
Anatase 50% 24 –
Anatase 25% 23 5
Rutile 0 1
MGH and OII are pollutants.
the two dyes would have different saturation of the adsorption
on the TiO2 , which will affect the photocatalytic degradation.
To eliminate this stage we let the suspension with the dye stay
without illumination for 30 min prior the photocatalysis (stirring
and bubbling are on). The results for the sorption are shown in
Table 1 as the ratio of the decrease in absorbance during the
dark period to the initial absorbance. As expected, the sorption
of MGH on various TiO2 blends is more significant than the
sorption of OII. The only difference is for Degussa P25 which
might be due to different charging of the catalyst surface.
The results from the photocatalytic degradation of both pollu-
tants are shown in Fig. 3. The zero irradiation time corresponds
to the end of sorption period (30 min stirring without any illumi-
nation). In case of MGH (Fig. 3a) the best results are observed
with the pure anatase sample, followed by that of Degussa P25.
The photocataytic behavior of our mixed samples expresses a
tendency of increasing the photocatalytic activity with raising
the anatase content. As expected, the deviations are more sig-
nificant in case of MGH as basic dye, due to its higher sorption
onto the catalyst samples (Table 1). Also, MGH exhibits higher
slopes meaning stronger degradation than OII dye.
Degussa P25 is the best performer in the photodegradation of
OII (Fig. 3b). This fact can be explained with its higher initial
sorption on TiO2 in this case (Table 1). Similar tendency can be
observed for the composite samples—the photodegradation of
OII is more effective with raising the anatase content. As seen
from the data presented in Fig. 3, the deviations in case of OII
are minimal (like for typical acid dye with much lower sorption
on TiO2 than MGH).
From the presented data one can see, that the performance of
the anatase allotropic form of KRONOS is always comparable
to that of Degussa P 25.
To quantify the observed trends in Fig. 3, we first compared
the experimental data with a single exponential equation [24]:
C(t) = C0 exp(−kt) (1)
Here C(t) is the actual dye concentration, while C0 is the ini-
tial dye concentration (at the end of sorption period); k has the
meaning of apparent rate constant related to the adsorption and
reaction properties of the solute in the frames of the Langmuir
190 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192
Fig. 3. Kinetics of water photopurification from the pollutants MGH (a) and
OII (b) with the different catalyst samples. The experimental data points are the
average from two or three independent measurements; the error bars represent
the respective deviations. The solid lines are theoretical fits of the data with Eq.
(2).
model at 1  k1 C (k1 is the adsorption constant) [24]. The appar-
ent rate constants for the experiments with the different TiO2
samples are plotted in Fig. 4. The k values are independently
obtained by a linear fit of the quantity ln(C/C0 ). Only the exper-
imental data obtained during the first 10 min illumination are
Fig. 4. Influence of the anatase percentage in the TiO2 mixture on the rate
constants, k, obtained from linear fits of the respective logarithmic plots of the
experimental data up to the tenth minute (open figures). The rate constant values
for Degussa P25 are presented as asterisk (in case of MGH) and cross (in case
of OII). The closed figures present the results for the reverse characteristic time,
τ R , of the photodegradation process (in min−1 ).
used in calculating the rate constants k, in order to minimize
variations as a result of the competitive effects of the interme-
diates, pH changes, etc. It is well known that the intermediate
products formed during photodegradation furthermore undergo
photocatalytic oxidation, while the simultaneous release of H+
influences the pH of the solution, thus resulting in a change of
the initial conditions [25].
Let us try to analyze now the complete set of experimental
data plotted in Fig. 3 up to the end of the process (40 min).
In many cases they deviate from the simple picture of single-
exponential decay described by Eq. (1). The most pronounced
deviations are observed with pure anatase in MGH solution and
with P25 in OII solution. To combat this problem we utilized a
more sophisticated model of double exponential equation [26]:
    
t t
C(t) = C0 (1 − B) exp − + B exp − (2)
τA τR
It considers the entire photocatalytic process as composed of two
stages: (i) adsorption of the dye, modeled as reversible chemical
reaction of first order and (ii) degradation of the dye expressed
as irreversible chemical reaction of first order. This is a simpli-
fication taking into account the transportation of the organics
from the solution volume to the TiO2 surface and next destruc-
tion of the absorbed molecules. Due to the appreciable sorption
(in Table 1) and the pronounced degradation ability (nearly 80%
of pollutant from Fig. 3a), the two processes are of comparable
rates at least in the case of pure anatase.
The quantity τ A has the meaning of characteristic time of
adsorption, which is kept constant equal to 1.25 min during the
data fits for both dyes. According to the model proposed in
deriving Eq. (2), τ A should be determined by studying the dark
sorption kinetics over the catalyst. However our experimental
data during the dark period are insufficient to perform such a
fit. That is why the two time constants, τ A and τ R have been
determined simultaneously assuming that in some experiments
the dye adsorption is appreciable also during the photocatalysis.
The characteristic time of photocatalysis (reaction) τ R is var-
ied between ca. 9 and 333 min for MGH and between 16 and
1000 min for OII. For comparison, in Fig. 4 we have plotted the
quantity 1/τ R ∼ k. It is seen, that they are rather close to the val-
ues for k obtained by Eq. (1). Regarding the matching constant
B, in many cases it has a value close to unity (0.9–1). The case
B = 1 transfers Eq. (2) into Eq. (1)—prevailing photocatalysis.
However, B = 0.6 in the case of pure anatase and MGH, which
shows appreciable contribution from the adsorption of dye.
As seen, the rate constant, k or 1/τ R , is always increasing
with the anatase content. Also, the rate constants in the case of
MGH are appreciably higher than those for OII, which means
more efficient MGH-dye degradation. This is due to the higher
sorption ability of MGH.
Finally, the data for Degussa P25 lay always higher than
those for the mixtures with similar anatase content. The supe-
riority of TiO2 P25 may be attributed to the morphology of
crystallites, which was proposed to be one of the most criti-
cal properties for the photocatalytic efficiency of P25 among
various grades of TiO2 . Crystallographic studies show that it
 A. Bojinova et al. / Materials Chemistry and Physics 106 (2007) 187–192
consists of multiphases of amorphous, anatase and rutile forms.
The close proximity of these phases and in some cases the over-
lapping of forms makes it difficult to differentiate and it has been
documented to be the reason for long lasting excitation of elec-
trons from the valence band to the conductive bands, allowing
for efficient and effective degradation of organic compounds
[19,20]. Recently, Harum et al. had shown that in the case of
TiO2 P25 a transfer of the photogenerated electrons from rutile
to anatase particles takes place leading to stabilization of the
charge separation and therefore lowering the recombination of
the photogenerated carriers, which determine the efficiency of
most photocatalysts. Additionally the small size of the rutile
particles in this formulation and their close proximity to anatase
particles are crucial to enhancing the catalyst activity [14].
Degussa P25 represents the most active commercial catalyst,
concerning the photodegradation of various pollutants, while
there are cases were the pure anatase appears to have better pho-
tocatalytic properties than Degussa P25 [27]. According to refs.
[27,28], Degussa P25 owes its high photoreactivity to a slow
electron/hole recombination rate, whereas the high photoreactiv-
ity of the anatase form is due to a fast interfacial electron-transfer
rate. Taking into account this fact we can hypothesize that in
our case, where the TiO2 anatase is more efficient in compar-
ison to Degussa P25, the photocatalytic oxidation of MGH is
limited more from the electron transfer reaction than from the
electron/hole recombination.
The considerations made above are based on the assump-
tion that the reaction rate does not depend on the intensity of
UV irradiation reaching the photocatalyst surface. In a more
realistic model the light intensity should be taken into account
as described for a thin-film slurry photocatalytic reactor [29].
Furthermore, this intensity depends on the coefficients of light
scattering, extinction and absorption as shown for water sus-
pensions of different brands of TiO2 powders [30]. In addition,
the apparent rate constant k in Eq. (1) is also a function of
the local volumetric rate of photon absorption, which in turn
depends on the optical properties of the suspension. These facts
imply that the degree of photon absorption and scattering will
also affect the photocatalytic performance of different com-
positions used in our experiments. More specifically, Degussa
P25 shows always appreciably higher coefficients than the other
commercially available photocatalysts in the wavelength range
270–410 nm. Therefore, we can assume that this effect will be
not so high comparing one mixed photocatalyst of KRONOS to
the other one while the biggest change is expected in comparison
with Degussa P25.
4. Conclusions
Here we consider the photocatalytic activity of mixed TiO2
powders, anatase plus rutile of KRONOS, in slurry with respect
to two model dye pollutants. The obtained results illustrate that
the increase of the anatase content always leads to an increase of
the photocatalytic activity of the TiO2 samples. The efficiency
of photodestruction of Malachite Green Hydrochloride is higher
than that with Orange II, which is also accompanied with a higher
adsorption of the dye MGH onto the TiO2 surface. Degussa
191
P25 is of higher ability to destroy the organics than the mixture
with respective composition. Nevertheless, the mixed KRONOS
catalysts can be used in large-scale applications where important
is the cost of material.
The influence of other factors, such as the synthesis tempera-
ture and the gas atmosphere of annealing, on the photocatalytic
properties of the mixed TiO2 powders will be object of short-
coming study [31].
Acknowledgements
This research is financially supported by NATO Project SfP
977986. The authors are also thankful to Prof. D. Mechandjiev
from the Institute of General and Inorganic Chemistry, Bulgarian
Academy of Sciences, for the BET analysis of the samples and
to Dr. A. Apostolov from the Faculty of Chemistry, University
of Sofia, for the X-ray spectra.
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