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71.Журнал Сибирского федерального университета. Сер. Химия №2 2008

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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Журнал Сибирского федерального университета
2008
Journal of Siberian Federal University
1 (2)
Химия
Chemistry
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Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Kirill S. Alexandrov
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Veniamin S. Sokolov
Editorial Board:
Editor-in-Chief:
Mikhail I. Gladyshev
Founding Editor:
Vladimir I. Kolmakov
CONTENTS / СОДЕРЖАНИЕ
Valentina V. Simonova, Tatyana G. Shendrik,
Vladimir A. Kucherenko, Nikolai V. Chesnokov
and Boris N. Kuznetsov
Study of Thermochemical Transformations of Hydrolytic Lignin
and the Properties of the Produced Active Carbons
? 107 ?
Valeri E. Tarabanko, Konstantin L. Kaygorodov
and Mikhail Yu. Chernyak
Polyesterification of Alpha-Angelicalactone
? 118 ?
Boris N. Kuznetsov, Vladimir I. Kovalchuk,
Nadezhda M. Mikova, Nikolai V. Chesnokov
and Liliya V. Naimushina
Formation
of
Iron
Nanoparticles
by
Transformations of Iron Carbonyls on Silica Surface
Thermal
? 124 ?
Viktoriya V. Sursyakova, Sergey N. Kalyakin,
Galina V. Burmakina and Anatoliy I. Rubaylo
Measurement of Ion Association Constants from Decrease of
Peak Areas by Capillary Electrophoresis Technique with Indirect
Spectrophotometric Detection
? 136 ?
Юрий Л. Михлин, Максим Н. Лихацкий,
Ирина А. Ярославцева, Зинаида В. Борисова
h?3???,? ,??%K,?,?%"=??/. C!%?3*2%" ?3??-,??%?%
"%??2=?%"???, 2?2!=.?%!=3!=2-,%?%"
? 142 ?
Managing Editor:
Olga F. Alexandrova
Executive Editor for Chemistry:
Boris N. Kuznetsov
???????? ?.?. ?????? ????????? ?.?. ??????????
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????????? ? ?????? 27.08.2008 ?. ?????? 19?27. ???. ???. ?. 10,6.
??.-???. ?. 10,1. ?????? ???. ?????? ????????. ????? 1000 ???. ????? 1/063.
?????????? ? ??? ???. 660041 ??????????, ??. ?????????, 79.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Editorial board for Chemistry:
Nikolai V. Chesnokov
Lubov? K. Altunina
Natalia G. Bazarnova
Vasiliy A. Babkin
Vicente Cebolla
Viktor M. Denisov
Zinfer R. Ismagilov
Sergey V. Kachin
Sergey D. Kirik
Wolfgang Klose
Vladimir I. Kovalchuk
Vladimir A. Likholobov
Yuri L. Mikhlin
Gennady L. Pashkov
Anatoly I. Rubailo
Tatyana V. Ryazanova
Vladimir A. Sobyanin
Valeri E. Tarabanko
Tatyana G. Shendrik
Maxim L. Shchipko
Jean V. Weber
????????????? ? ??????????? ???
?? ? ??77-28-726 ?? 29.06.2007 ?.
Светлана А. Кузнецова, Наталья Ю. Васильева,
Галина С. Калачева, Надежда М. Титова,
Евгения С. Редькина, Галина П. Скворцова
o%?3???,? ?,=??2=2= K?23?,?= ,? K?!??2/ *%!/ K?!??/ ,
,?3???,? ??% =?2,%*?,?=?2?%L =*2,"?%?2,
? 151 ?
Максим Л. Щипко, Анна О. Еремина,
Валентина В. Головина
`??%!K??2/ ,? 3???!%??%??!?=???% ?/!?
*!=
j!=??% !?*%?%
? 166 ?
Светлана А. Кузнецова, Владимир Г. Данилов,
Ольга В. Яценкова, Наталья М. Иванченко,
Наталья Б. Александрова
nC2,?,?=?, C!%????= ???,??,-,*=?,, ?!?"??,?/ %?,?/
3*?3??%L *,??%2%L " C!,?32?2",, C?!%*?,?= "%?%!%?= ,
??!?%-*,??%2?%?% *=2=?,?=2%!=
? 181 ?
Светлана С. Лалетина, Алексей М. Шор,
Елена А. Шор, Владимир А. Наслузов,
Анатолий И. Рубайло
h?3???,? *%%!?,?=?,, *=2,%?= ?,*=!K%?,?= !%?, (I) ?=
??%?,2? ??2%?%? DFT
? 190 ?
Тамара И. Когай
q,?2?? ??%??/. .-,!%" K?23?,?=
? 200 ?
Олег В. Белоусов, Роман В. Борисов,
Владимир А. Парфенов, Юрий В. Салтыков
n???*= 3?????%L C%"?!.?%?2, C%!%?*%" C=??=?, ??2%?%?
?,*?,???*%L "%??2=?C?!%??2!,,
? 206 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
Journal of Siberian Federal University. Chemistry 2 (2008 1) 107-117
~~~
??? 544.478.32
Study of Thermochemical Transformations of Hydrolytic Lignin
and the Properties of the Produced Active Carbons
Valentina V. Simonovaa, Tatyana G. Shendrika,
Vladimir A. Kucherenkoa, Nikolai V. Chesnokovb,c
and Boris N. Kuznetsovb,c*
a
Institute of Physical and Organic Chemistry and Coal Chemistry, NAS,
70 R. Luxemburg st., Donetsk, 831114 Ukraine
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
c
Institute of Chemistry and Chemical Technology SB RAS,
42 K.Marx st., Krasnoyarsk, 660049 Russia 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
There has been studied the influence of the conditions of heat treatment of hydrolytic lignin and its
mixtures with oil slime on the yield, structure and adsorption properties of active carbons (AC). With
the increase in the temperature of lignin processing from 400 to 900 ?C, the yield of active carbon
decreases, and its specific surface area and sorption activity reach the maximum values at 800 ?C.
The mutual influence of the components of the mixture of hydrolytic lignin and oil slime during the
thermochemical transformations, becomes apparent in the variation of the yield and the porous structure
of AC. As for the oil slime, it acts as a binding and structure forming component.
Keywords: hydrolytic lignin, oil slime, thermal transformations, active carbon, structure, adsorption
properties.
The technical lignin which is formed during
the chemical processing of wood at the paper and
pulp and hydrolytic plants, is the waste which
is the most difficult to utilize. The amount of
unutilized lignins in the Ukraine (that is the waste
of the yeast, forage and paper and pulp industries)
makes up, according to different data, from 5 to
15 million tons, whereas in Russia and Belarus
their number is greater [1]. At present there are no
exhaustive technical solutions on utilizing lignins,
although the survey of the scientific literature for
*
1
the past years is evidence of the great interest that
the researchers show in this raw material.
Lignin is a polymer of aromatic nature.
Its structural unit is presented mainly by
phenylpropane units [2]. The variety of
connections between the latter determines the
irregular molecule lignin structure [3]. Lignin is
a polyfunctional substance, containing phenolic,
alcoholic, carbonyl, acidic and methoxyl groups.
The number of these groups varies greatly
depending on the industrial hydrolysis conditions,
Corresponding author E-mail address: bnk@icct.ru
© Siberian Federal University. All rights reserved
# 107 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
which has a noteworthy effect on the lignin
reactivity [4].
Lignin in itself is used as an effective sorbent
of various organic and inorganic substances
including those used in medicine (like, for
example, an enterosorbent ? polyphepane) [5]. It
is also a precursor of activated carbons (AC), made
by combining thermolysis and steam activation.
The conditions of heat treatment to a great extent
determine the AC structure based on the hydrolytic
lignin [6, 7]. The survey of the scientific literature
on the thermochemical conversion of lignin into
AC, shows, that describing technological aspects
predominates over the information about the
physical and chemical regularities of transforming
the organic substance lignin, as well as forming
the porous structure and changing the adsorption
properties.
There is some information about getting AC
by means of combined carbonization of mixtures
of different kinds of the carbon containing raw
material [8 ? 12]. The interaction of the mixture
components in the processes of co-carbonization
develops in the non-additive yield change and
structural characteristics of the obtained carbonic
materials. During the co-carbonization of the
hydrolytic lignin with oil slimes, the latter can act
as a binding and pore forming reagent [10].
The aims of the given work are as follows:
1) the studies of the regularities of transforming
the lignin structure into the structure of activated
carbons depending on the temperature and
the time of steam activation; 2) the estimation
of the influence of structural changes on the
adsorption characteristics of AC obtained
during the thermolysis and the lignin steam
activation; 3) the studies of the peculiarities of
thermotransformations of mixtures of hydrolytic
lignin with oil slimes based on water emulsions of
oil heavy fractions.
Experimental
To obtain AC, there was used the hydrolytic
lignin of the Krasnoyarsk biochemical plant
(Russia) having the following characteristics
(%):
Wa ? 3,6; Ad ? 1,8; Vdaf ? 63,4; Cdaf ? 60,2;
daf
H ? 6,0; Odaf ? 33,0; (S+N)daf ? 0,8.
The example of the oil slime (OS) is the waste
products formed during the cleaning of the tanks
at the washing and steaming station of Luzanovka
(Odessa, the Ukraine). These are the aqueous
emulsion of oil heavy fractions (the water content
is ? 50 ± 10 %) including the admixtures of the
surface active substances. The organic mass of OS
is presented by alkanes (80 %) and arenes (18 %),
the average molecular mass is 750 ? 1100 a.e.m.
[10]. The emulsified oil slime was dehydrated by
settling the preheated (80 ?C, for 3 hours) waste
products [11].
The mixtures of lignin and oil slime were
made by mechanical mixing at a temperature of
20 ± 2 ?C for 5 minutes without the subsequent
forming. The content of the oil slime in the mixture
was 20 ? 50 % mass, which corresponds with the
most efficient interaction of the oil slime with the
solid carbon containing material [12].
The activated carbons (AC) were obtained
in the vertical tubular reaction vessel having the
volume of 50 cm3, which is put into the electrical
furnace providing the heating to the activation
temperature (ta) at a speed of 50 ± 5 degrees/
min. and providing the thermostatic control of the
reaction vessel with the accuracy of ± 5 ?C. The
sample of the dried lignin (5 g) was loaded into
the reaction vessel. Then the system was blown
by argon at a speed of 2 dm3/hr during 10 min.
And the reaction vessel was heated to 200 ?C.
After that the flow of the argon was switched over
to the steam generator (the productivity relative to
water was 60 cm3/hr). The heating was continued
to the activation temperature. On the expiry of
# 108 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
the given activation time (?a), there was carried
out the cooling of AC in the atmosphere of the
argon. There was determined the yield (Y, %) of
the activation product (the determination error
was ± 0,4 %).
The value of the specific surface area SBET,
m2/g) was estimated by two methods: the low
temperature argon desorption [13] and from the
isotherm of nitrogen adsorption ? desorption
using the installation ?Sorptomatic ? 1900?. The
determination error SBET made up ± 7 %.
The studying of the supramolecular
AC structure was carried out with the the
diffractometer DRON ? 1 UM (the emission of
CuK?, 40 kV, 20 mA). There was determined the
interlayer distance d002 (the measurement error
was ± 0,002 nm). There was also determined
the height Lc (± 0,02 nm), the average diameter
La (± 0,2 nm) and the number of the layers
n = Lc / d002 + 1 in the crystallite. The degree of the
crystallite space ordering was estimated as h / l,
which is the relation of the height (h) of the reflex
002 to its half width (l) [14].
The values of the adsorption activity relative
to methylene blue (Amb) and iodine (Aiodine) were
determined based on GOST 4453-74 and GOST
6217-74. There was also calculated the surface
unit adsorption activity Amb/SBET and Aiodine/ SBET.
The thermogravimetric studies were
carried out with the help of the derivatographer
Q ? 1500 D of the Paulic ? Paulic ? Erdei with the
linear temperature rise (10 ?C/min.) from 20 ?C to
950 ?C, the sample is 300 mg, a ceramic crucible.
The processing of the derivatograms was carried
out according to the method [15].
The IR spectra of the diffuse reflection were
recorded on the spectrometer of the type BIORAD
FTS ? 185 having the attachment GRASEBY
SPACAC ?Selector?. The spectra were obtained
for the mixtures of the carbon sample (5 %)
with the powdery KBr (95 %) by the addition
of 256 scans in the range of the wave numbers
4000 ? 400 -1.
Results and discussion
The transformation of the lignin structure
with the rise in temperature
The lignin thermolysis conducted in the
range of 20 ? 950 ?C, is characterized by the
presence of the three maximums of the speed
of emitting volatile substances at 115, 240 and
370 ?C. The first one is caused by the removal
of the adsorbed gases and moisture from the
lignin. The maximum at 240 ?C is caused by the
decarboxylizing of COOH groups and, perhaps,
by the decomposition of the alkyl ? alkyl ethers.
The maximum at 370 ?C is caused by the
destruction of Calk?Calk., Calk?O and other bonds
between the aromatic rings with the formation of
active radicals and low-molecular products.
By means of using the methods of
IR spectroscopy, there were studied the
transformations of lignin into the AC structure
during its heat treatment. The spectrum of the
initial lignin is characterized by a set of absorption
bands [16]: 3385 cm?1 is the hydrogen bond,
2930, 2850 cm?1 are the valence vibrations of
the bonds C?H in methyl and methylene groups,
1710, 1667 cm?1 are the vibrations of the bonds
C=O in ?- and ?-carboxylic acids respectively,
1603 and 1512 cm?1 are the vibrations of the
bonds in the benzene ring, 1470, 1420 cm?1 are
the deformation vibrations of the bonds C?H
in groups CH2 and CH3 in the methoxyls, 1365
cm?1 are the vibrations of the bonds C?O in the
phenol ?OH group, 1220 cm?1 are the vibrations
of the bonds C?O?C and C?OH of the ethers and
phenols, 1132 and 1072 cm?1 are the vibrations of
C?O-bonds in methoxyl groups.
The heating of lignin to 370 ?C leads to
the appearance of the absorption bands at 3630
and 3510 cm?1, since as result of removing the
# 109 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
moisture, there increases the content of free
hydroxyl groups. One can also observe the
appearance of the absorption band 3050 cm?1 and
the strengthening of the intensity of the band at
1600 cm-1 corresponding to the vibrations of the
bonds in the aromatic ring. The strengthening of
the intensity of the band 1700 cm?1 takes place
apparently because of the oxidation of aliphatic
chains to forming carboxyls. The intensity of
the band 1370 cm?1 increases, possibly, due to
the formation of phenols. The intensity of the
absorption bands 1030, 1125 cm?1 decreases.
The band 1060 cm?1 disappears. This may be
connected with removing the methoxy groups and
breaking the ether bonds. In the solid thermolysis
products, produced at 800 ? 900 ?C, there partially
maintain oxygen and aliphatic fragments. And
in the IR spectrums, one can see the absorption
bands corresponding to these fragments. These
are included into the polyaromatic AC skeleton.
Thus, in the solid thermolysis product,
relatively speaking, one can point out two types
of structures. The type I structures (SI) ? are the
lignin fragments which were not fully subjected
to aromatization during the heating. They contain
aliphatic chains and oxygen in the form of
phenol, carbonyl and hydroxyl groups. The type
II structures (SII) are polyarene carbonic clusters
(graphenic blocks, that is crystallites). It is quite
evident that their reactivity when interacting with
steam, will be different.
The lignin steam activation
There were obtained the experimental data
about the influence of the conditions of heat
treatment of hydrolytic lignin by steam, on the
yield as well as on the structural characteristics and
the adsorption properties of the active carbons.
With the increase in the temperature from
400 to 900 ?C, the AC yield decreases from 46,7
to 10,3 % (Table 1). The value SBET rises reaching
the maximum value of 650 m2/g at 800 ?C and
then it drops. The adsorption activity relative
to MB and iodine, also increases reaching the
maximum value at 800 ?C (Amb = 199 mg/g and
Aiodine = 1001 mg/g). And with the further increase
in temperature, it decreases. The lignin which
was subjected to heat treatment at 800 ?C, has
the best porous system in the three?dimensional
framework, presented by polyarene clusters
(structures SII), which are connected by aliphatic
and oxygen ? containing fragments (structures
SI).
There was calculated the number of the
layers formed by the molecules of iodine or
methylene blue on the surface of the lignin, which
was activated in the temperature range 400 ?
900 ?C, as following from the adsorption activity
values (Table 1), and the areas of setting their
molecules [17, 18]. With the rise in the activation
temperature, the calculated number of the iodine
layers on the AC surface, decreases from 2,2 to
1,0 which corresponds to the monolayer (Fig. 1).
The absorption of iodine in the amount
greater than it is necessary to form a monolayer,
is caused, in our opinion, by reducing the iodine
molecules as a result of the transfer of electrons
from the lignin fragments, or by other chemical
interactions with the structural fragments of
organic macromolecules. These fragments are
rather reactive and they correspond to type I
structures.
As regards the second adsorbate ? MB
(methylene blue) ? the situation is guite the
opposite (Fig. 1): with the rise in the activation
temperature, the number of MB layers, set on the
surface of the produced AC, increases from 0,5 to
the monolayer. The obstacle to forming the MB
monolayer may be a great part of micropores,
whose surface is inaccessible for a large MB
molecule. There are also possible steric hindrances
during setting a molecule, which may be caused
by the fact that various functional groups and
heteroatoms are present on the surface.
# 110 #
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
Table 1. The temperature dependences of the yields, specific surface values and adsorption characteristics of
activated carbons (?a = 30 min)
ta, ?C
Y, %
SBET, m2/g
Adsorption activity
Aiodine,
Amb/ SBET,
mg/g
mg/m2
112
? 0,7
400
46,7
< 10
Amb,
mg/g
7
500
34,9
90
17
248
0,20
2,88
600
34,0
280
38
691
0,14
2,48
650
30,1
360
86
744
0,24
2,06
700
25,7
430
107
873
0,25
2,01
750
18,2
550
154
949
0,28
1,73
800
15,2
650
199
1001
0,30
1,53
850
12,4
610
183
907
0,30
1,50
900
10,3
540
161
824
0,30
1,52
Aiodine/ SBET,
mg/m2
? 11,2
Fig 1. The number of adsorbed iodine layers (1) and methylene blue (2) on the surface of lignin adsorbents,
obtained at different activation temperatures
# 111 #
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
As it was suggested earlier, during the
heating to 800 ?C, in the solid product of lignin
thermolysis, there are formed two types of
structural fragments (SI and SII) which differ
considerably in their chemical activity with
respect to steam. The change of the AC yield
depending on the activation time at 800 ?C,
is characterized by the two areas with quite
different gasification speeds. This allowed to
kinetically distinguish between the interactions
with the steam of the structures of types I
and II [19]. The change of the contents of SII
structural fragments corresponds to the change
of the activated carbons yield obtained in the
range of ?a = 30 ? 120 min and it is described
by the equation of the kinetics of I order
YII = 16,3 exp (? 0,0023 ?a), (the correlation
ratio r2 = 0,99). Based on this equation, one
can calculate the contents of the SII fragments
in the range ?a = 0 ? 30 min. It is also possible
to calculate the contents of the structural
fragments of SI in this area. The decrease of the
contents of these fragments is also described
by the equation of the kinetics of the first order
YI = 13,5 exp (? 0,0752 ?a), (r2 = 0,97). Judging
by the correlation of the effective constants
of the gasification speed k1 / k2, the reactivity
structural fragments of SI is 33 times higher
than SII [19].
Probably, the burning out of the structural
fragments of SI leads to the increase in the part
of the structures of SII, characterized by the lower
reactivity and more perfect space construction.
The decrease in the part of the structural fragments
of type I is apparently accompanied by the
considerable growth of the specific surface area
whereas the reaction of the structural fragments
of SII with the steam, leads to the decrease in the
surface area of AC. The purposeful creation of the
structures of the type SI in the thermolysis products
and their subsequent interaction with the steam,
are the effective methods of forming a porous
structure of AC having the given properties.
The thermal transformation of lignin
and oil slime mixtures
The general shape of the lignin IR spectrum
practically does not change after adding oil slime
(OS). Only the intensity of the absorption bands
increases in the area 2930, 2850 cm-1, because in
the oil slime, containing a great number of aliphatic
hydrocarbons, their intensity is very great.
According to the functional analysis data
(Table 2), the addition of oil slime to lignin, leads
to a considerable decrease in the content of phenol
and carbonyl groups in the mixture. This is,
probably, due to the fact that the OS components
decrease the accessibility of the lignin surface for
interacting with the reagents used in the functional
analysis. The contents of the lactone groups
increase, maybe, owing to the oil components,
that these groups contain. On the TGA curve of
oil slime (Table 3), there are three maximums of
the mass losses ? at 120, 320 and 430 ?C. The first
maximum corresponds to removing the moisture
and low?boiling hydrocarbons. The second
maximum corresponds to the decomposition of
oxygen?containing groups and the evaporation
of the more high-boiling hydrocarbons. The third
one corresponds to removing and the thermal
decomposition of the high-boiling aromatic and
aliphatic hydrocarbons.
According to thermogravometric data,
the addition of OS to lignin (1:1), leads to
the following changes in the properties of the
mixture thermal destruction: there increases
the temperature of the beginning (Tb), and there
decreases the temperature of the end (Te) of
the thermal decomposition area (TDA) and,
accordingly, there narrows the TDA maximum
from 210 to 148 ?C. There also considerably
increases the average decomposition speed (Vavg)
in the TDA maximum. It is noteworthy that
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
Table 2. The information about the functional analysis of lignin, oil slime and their mixtures
Functional groups
Sample
COOH
Lactones
OHphenol
H?C = O
Lignin (L)
2,45
0,50
1,2
1,10
Oil slime (OS)
0,20
0,27
0,23
0,36
L-OS
1,91
0,80
0,19
0,27
mg-eq/g
Table 3. The parameters of the thermal destruction of lignin, oil slime and their mixtures based
on thermogravimetric analysis
Sample
Parameters
Tmax2,
Tmax3,
?C
?C
240
370
L
TH20,
?C
120
Tb,
?C
195
Te,
?C
480
Tmax1,
?C
-
OS
115
345
500
-
320
L?OS
115
208
450
-
280
the maximum at 430 ?C characteristic for OS,
disappears on the derivatogram of mixture. At
280 ?C, there appears the maximum which gives
evidence of the interaction of the two components
(L and OS) during their joint thermal destruction.
According to the IR spectroscopy, the
heating of the L?OS mixture (4:1) to 240 ?C (the
temperature of the first maximum of the mass
loss on the TGA curve) is accompanied by the
disappearance of the absorption bands of ?OH
groups connected by hydrogen bonds (3350 cm?1)
and the appearance of uncombined hydrogen
bonds and the ?OH groups combined by one
bridge (3630, 3530 cm?1), which is caused by
removing the moisture. Besides, there appears
the absorption band at 3050 cm?1 and the bands
866, 815 and 760 cm?1 are strengthened which
testifies to the increase of the content of aromatic
structures in the thermally treated mixture. There
is also observed a drastic drop in the intensity of
the absorption bands in the area 2960, 2870 cm?1,
corresponding to the vibrations of the bonds in the
methyl and methylene groups which is caused by
the removal of low-molecular hydrocarbon gases.
The band 1370 cm-1 is strengthened, perhaps, due
Vavg,
mg/g·c
0,19
V2max,
mg/g·c
0,18
V3max,
mg/g·c
0,29
430
0,40
-
0,77
385
0,28
0,29
0,41
to the increase in the contents of the phenol ?OH
groups. The absorption bands 1170, 1120, 1060
cm-1 disappear, which may be connected with
removing the methoxy groups and destroying the
ether bonds.
The heating of the mixture to 370 ?C (the
temperature of the second maximum of mass loss
on speed on the TGA curve) leads to increasing the
intensity of the band 3630 cm?1 (it corresponds to
the free hydroxyl groups) and to strengthening the
absorption bands intensity corresponding to the
vibrations in the aromatic ring (3055, 1600, 866,
815, 760 cm?1), which is the result of increasing the
contents of the aromatic structures in the mixture.
It also leads to the considerable strengthening of
the intensity of the band 1720 cm?1, which may be
connected with oxidizing the aliphatic chains to
form carboxyl groups. The disappearance of the
band 1370 cm?1, may indicate the destroying the
phenols. And finally, there appearance of the band
1170 cm?1 may serve as evidence of new ether
bonds formations
The thermolysis of the L-OS mixture at 400 ?C
carried out for 3 hours, leads to the substantial
increase in the intensity of the absorption bands
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
relating to the vibrations of the bonds in the
aromatic ring (3055, 1600, 866, 815, 760 cm?1).
It also leads to the decrease in the intensity of
the absorption bands relating to the vibrations
of the bonds in the aliphatic CH2, CH3 groups
(ACL) and that of the activated carbon made from
the L?OS mixture (ACM) are approximately the
same. Till the activation temperature of 800 ?C
is reached, there is observed the increase in the
specific surface of AC (to 650 and 760 m2/g for
(2960, 2870 cm?1), as well as in carboxyls and
carbonyls (1700 cm?1), in phenol and ether groups
(1200, 1420, 1070 cm-1). These data which testify
to the fact that there occur the reactions of the
thermal destruction of aliphatic hydrocarbon and
oxygen-containing fragments with the subsequent
carbonization of the material.
The mixing of the lignin with the oil
slime leads to the following changes of the
supramolecular structure (Table 4). The value of
the interlayer distance d002 remains the same as
with the lignin. The extent of the crystallites in the
longitudinal direction La decreases considerably
ACL and ACM, respectively). And in the range 800
? 900 ?C one can see its insignificant decrease. At
the activation temperatures over 700 ?C, the value
SBET of the product ACM is substantially higher
than ACL. In agreement with the value SBET,
the adsorption properties of AC change (Fig. 2
and 3). The sorption activities based on MG (Amb)
and iodine (Aiodine) increase reaching the
maximum value at 800 ?C: Amb = 200 mg/g and
Aiodine = 1000 mg/g for ACL and Amb = 220 mg/g
and Aiodine = 950 mg/g for ACM. Under these
conditions, there is formed the AC supramolecular
structure which has the same sizes of the
polyarene layers in the crystallite both of ACL
as compared to lignin. And the crystallite size in
the cross-sectional direction Lc and the degree of
the ordering h/l increase not so substantially.
The number of ?-bands does not change.
The activation of the L?OS mixture leads to the
formation of active carbons having the yields,
whose value decreases with the rise in the
activation temperature. The oil slime alone in
the temperature range of 400 ? 900 ?C, forms
a non-porous product with the yield of ? 0,5 %
mas. So, the yield of AC from OS in the range of
measurement errors, may be neglected.
The character of the temperature dependence
SBET for the activated carbon made from the lignin
and of ACM. It should be noted that the interlayer
distance between the layers in the crystallite ACM,
is considerably greater, and the crystallite height
and the ordering degree are smaller as compared
to ACL (Table 4).
The character of activating the L?OS mixture
and the properties ACM differ greatly from the
lignin activation. The yield of the activated
carbon from the L?OS mixture is lower than
from the lignin. Since the AC yield from OS is
very low, it may be assumed that the precursor
of the activated carbon in the L?OS mixture is
only lignin. As following from this, the calculated
Table 4. The X-ray diffraction characteristics of the initial and activated samples
Parameters
Sample
Lignin (L)
D002,
nm
0,446
La,
nm
4,7
Lc,
nm
1,50
2,69
4,4
The number of
?-bands
2
Oil slime (OS)
0,477
5,8
2,40
2,65
9,2
0
L ? OS
0,446
1,8
1,71
2,85
4,8
2
L, 800 ?C, 30 min
0,340
6,6
3,27
1,04
10,6
2
L ? OS, 800 ?C, 30 min
0,384
6,8
1,95
0,73
6,1
2
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h/l
n
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
Fig. 2. The influence of activation temperature on the adsorption activity relative to methylene blue
of the activated carbons from lignin (1) and the lignin ? oil slime mixture (2) (ta = 30 min)
Fig. 3. The influence of activation temperature on the adsorption activity relative to iodine of the activated
carbons from lignin (1) and the mixture lignin ? oil slime (2) (ta = 30 min)
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
yield of ACM, makes up half of the yield of the
activated carbon from lignin at the selected ratio
of the mixture components. The real yield of
ACM is higher than the calculated one owing to
the chemical interaction of the lignin components
and the oil slime. The similar non-additivity
effect was discovered earlier [20] for the system
brown coal?OS. The value of the effect depends
on the activation temperature and it is the most
significant in the range of 800 ? 900 ?C, when the
AC yield from the mixture is approximately equal
to the yield of AC from lignin.
Under these conditions, the OS components
are involved at a maximum degree in forming
the AC porous structure. And the specific surface
of the activated carbon from the mixture is
substantially higher than AC from the lignin.
Thus, the interaction of the lignin components
and the oil slime develops in the non-additive
change of the functional groups composition, as
well as in the shift of the temperature range of
the thermal decomposition and in increasing the
speeds of thermal transformations as compared to
the initial lignin and oil slime.
One can also observe the changes of the
supramolecular structure already at the stage of
mixing the hydrolytic lignin with the oil slime
which progress during the heat treatment of the
mixture.
The effect of the mutual influence of the
mixture components during the thermochemical
transformations develops in the non-additive
change of the yield of the carbonized material and
its textural characteristics. The value of the effect
depends on the activation temperature and it is the
most significant in the range 800 ? 900 ?C, when
the yield of the active carbon from the mixture
is approximately equal to the AC yield from the
lignin.
On the basis of the established regularities,
there have been worked out the methods of
obtaining cheap carbon sorbents having a rather
great specific surface area (to 750 m2/g), and
having the high adsorption activity relative to
iodine and methylene blue (to 1060 and 230 mg/g
respectively).
The obtained porous carbon materials may be
used in various technological processes of cleaning
and separation in gaseous and liquid mediums, and
also for the purpose of environmental protection.
References
1.
2.
3.
4.
Velichko Yu.M., Zhitar I.N., Protsko A.A. The Burning of Low-grade Carbons, Carbon Waste
in Boilers and at Steam and Gas-driven Installations with the Help of Precombustion Chambers.
Proceedings of the Materials of the Scientific and Practical Conference ?The Waste and Worked
out Gases of Industrial Enterprises as an Important Potential of Energy Resources in the National
Economy?, the settlement Partenit, the autonomous republic of the Crimea, 1-5 October 2001,
Kiev: the society ?Znannya? (Knowledge), 2001. P. 14-15.
Ponomaryov D.A. The Forming of Quinonemethides as an Alternative Direction of the Thermal
Destruction of Some B-O-4-Ethers ? the Pattern Compounds of Lignin. Russian Journal of Applied
Chemistry. 1997. V. 70, ? 5. P. 864-866.
Korolyov Yu.M., Gagarin S.G. The X-ray Diffraction Studies of Cellulose and Lignin
Transformations during the Carbonification. Chemistry of Solid Fuels. 2003. ? 3. P. 13-20.
Kovalyenko E.I., Popova O.V., Alexandrov A.A., Galiken T.G. The Electrochemical Lignin
Modification. Russian Journal of Electrochemistry. 2000. V. 36, ? 7. P. 796-802.
# 116 #
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Valentina V. Simonova, Tatyana G. Shendrik? Study of Thermochemical Transformations of Hydrolytic Lignin?
5.
6.
7.
8.
9.
10.
11.
12.
13.
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15.
16.
17.
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Babkin V.A., Levanova V.P., Isayeva L.V. Medical Preparaions from the Hydrolytic Production
Waste. Chemistry for the Sustainable Development. 1994. V. 2. P. 559-581.
Kuznetsov B. N., Shchipko M. L. The conversion of wood lignin to char materials in a fluidized
bed of Al-Cu-Cr oxide catalysts. Bioresource Technology. 1995. V 52. P. 13-19
Baklanova O.N., Plaksin G.V., Drozdov V. A., Duplyakin V.K., Chesnokov N. V., Kuznetsov
B.N. Preparation of microporous sorbents from cedar mutshell and hydrolytic lignin. Carbon.
2003. V. 41. P. 1793-1800.
Pokonova Yu.V. The Carbon Absorbents from the Brown Coal Resin with the Additions of Coal.
The Chemistry of Solid Fuels. 2000. ? 1. P. 15-19.
Sindh H., Srivastava M., Singh I. D., Prasada T.S.R. Petroleum feedstocks as a source for production
of high value industrial carbons. Proc. Confer. of Science and Technology of Carbon, Strasbourd
(France), 5-9 July, 1998, Strasbourg. 1998. V. 1. P. 247.
Shendrik T.G., Pashchenko L.V., Khabarova T.V. et al. Porous carbon materials from wood wastes
and blends. Proc. 4th Int. Symp Catalytic and Thermochemical Transformations of Natural Organic
Polymers. Krasnoyarsk (Russia) May 30 ? June 14, 2000. P 104-113.
Shendrick T.G., Kucherenko V.A., Pashchenko L.V., Khabarova T.V. The Problems of Processing
the Carbon-containing Industrial Waste to Form Adsorbents. The Problems of Collecting,
Processing and Utilizing the Waste. Proceedings, Odessa: TsNTEPI, 2003. P. 167-171.
Yatsenko A.M., Prokopick Z.V., Chebenko Yu.N., Vorobyov A.A. Using the Waste of Petrochemical
and Petroleum Processing Productions // Ecotechnologies and Resources Saving. 2000. ? 3. P.
47-50.
Phenelonov V.B. Porous Carbon. Institute of Catalysis SB RAS, Novosibirsk, 1995 ? 518 p.
Saranchuck V.I., Airuny A.T., Kovalyov K.E. The Over molecular Composition, Structure and
Properties of Carbon. Naukova Dumka, Kiev. 1988. ? 192 p.
Belyayev E.K. The Calculation of Kinetic Parametrers Based on the Data of Derivatographic
Measurements. Russian Journal of Physical Chemistry. 1976. V. 50. ? 3. P. 790-793.
Kin G. Lignina chemia I wykorzystane. Wydawnictwa Naukowo-Technicze. Warscawa, 1971. ?
295 p.
Pittman C.U., Jiang W., He G.-R., Gardner S.D. Oxygen plasma and isobutylene plasma treatments
of carbon fibres: Determination of surface functionality and effects on composite properties.
Carbon. 1998. V. 36, ? 1-2. P. 25-37.
Marsh H., Yan D.S. Formation of active carbons from cokes using potassium hydroxide. Carbon.
1984. V. 22, ? 6. P. 603-611.
Shendrick T.G., Simonova V.V., Kucherenko V.A., Pashchenko L.V., Khabarova T.V. The
Adsorption Properties of Activated Carbon from Lignin. Chemistry of Solid Fuels. 2007. ? 1.
P. 44-50.
Shendrick T.G., Kucherenko V.A., Tamarkina Yu.V., Khabarova T.V. The Thermolysis of the
Mixtures of Brown Coal and Oil Waste. Coal Chemical Journal. 2005. ? 1-2. P. 45-49.
# 117 #
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Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
Journal of Siberian Federal University. Chemistry 2 (2008 1) 118-123
~~~
??? 542.952 + 547-314
Polyesterification of alpha-Angelicalactone
Valeri E. Tarabanko*, Konstantin L. Kaygorodov
and Mikhail Yu. Chernyak
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
alpha-Angelicalactone can be polymerized by two ways: as the substituted ethylene and as lactone.
Polyesters of alpha-angelicalactone are obtained on alkali based catalysts. The obtained polymers are
light yellow resins or solid, water-insoluble and soluble in polar organic solvents. Molecular weight
of the obtained polymers is up to 2000 amu. The structure of the polymers is studied by 1? NMR
spectroscopy. It is shown, that the part of polyester intermonomeric bond is more than 68 %.
The obtained polymers are exposed to full biodegradation by microorganisms Sacharomices cerevisae
during 5 - 15 day, and by Streptomy?es lividans and Streptomy?es chrysomallus - during 20 - 30 day.
Keywords: angelicalactone, anionic polymerization, polyangelicalactone, biodegradation.
Introduction
The amount of production of naturallyindestructible petrochemical-based polymers and
plastics are immense and annually increase by
approximately 28 million tons. At that the major
part of these plastics is stored on landfills, since
their recycling in developed countries is just
amount to 16-20 %. Now amounts of production
of synthetic plastics have reached 200 million
tons per year. Projects of possible methods of
chemical plastics re-use are non-optimistic.
Therefore the problem of a ?polymeric dust?
solving is to develop of the new polymers able to
natural degradation to the harmless components.
The amount of degradable synthetic polymer in
use today is negligible, probably under 1%. This
*
1
could conceivably be increased to a few percent,
which would have a minor effect on landfill
growth but which could be important if applied to
critical situations [1-3].
?-angelicalactone (5-methyl-2(3?)-furan1-one) is attractive substance to research of new
material syntheses, therefore it can be obtained from
renewable natural materials (I). The molecule of
?-angelicalactone has two polymerizable groups:
an ester group is joined to a double bond. Thus,
there are two possible ways of polymerization: disclosing of an olefinic linkage with formation of
a polyfuranone (II) and disclosing of the lactone
cycle with formation of a polyester (III).
Corresponding author E-mail address: veta@icct.ru
© Siberian Federal University. All rights reserved
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Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
O
O
HO
CH3
D-Angelicalactone
O
O
O
O
O
O
HO
O
O
O
(I)
CH3
H
O
CH3
CH3
Levulinic acid
Hexoses
H3C
O
O
C6H12O6
CH3
n/2
(II)
OH
O
CH3
n
CH3
(III)
Disclosing of double bond is carried on in
presence of Lewis acids with the formation of
oligomeric (n=2-8) polyfuranone [4,5].
Polyesterification of angelicalactone is the
most interesting, but data on this problem are
absent [6,7]. Products of such reactions can be
biodegradable or biologically compatible [7-9].
Inorganic and organic bases [7,8], organometallic
compounds [9] are preferable catalysts for the
lactone polymerization.
In this paper polyesterification of alphaangelicalactone and polyesters ability to
biodegradation are studied.
Experimental
alpha-Angelicalactone was obtained by
vacuum still of a levulinic acid (~25 mmHg,
340-345 K) and purified by fractional melt
crystallization. A levulinic acid was synthesized
according to [10]. Sodium butylate was
synthesized according to [11]. Solvents (dioxane,
ethyl acetate, diethyl ether, dichloroethane,
n-butanol, and benzophenone) were purified by
fractional distillation in vacuum.
Molecular weights of the obtained polymers
estimated by viscosimetry (Ostwald viscosimeters,
diameter 0.12 and 0.56 mm, benzophenone) and
cryoscopy (benzophenone).
The chain-length distribution was determined
by phase-reversal chromatography. The column
is Nova-Pak CIS (Waters Corporation, USA);
sorbent is octadecyl-coupled silica gel; vaporizing
light scattering detection device, model 500
(Alltech Corporation, USA); eluent ? acetonitrile/
tetrahydrofuran (MeCN/THF = 58/42), flow rate
1 ml/min.
Products purity was confirmed by gas-liquid
chromatography and 1? NMR spectroscopy
(spectrometer Bruker DPX-200W). The NMR
spectroscopy also has been involved for research
of polymers structure.
Biodegradation ability of the obtained
polymers was estimated by liveweight gain
of cultures of microorganisms Sacharomices
cerevisae, Streptomy?es chrysomallus and
Streptomy?es lividans and by observing of
polymers mass decreasing.
Polymerization of alpha-angelicalactone by
the sodium butylate. ? To three spot series of 3
g (~0,031 mol) of a-angelicalactone were added:
(1)152 mg (~1,7Ї10? 3 mol), (2) 138 mg (~1,6
? 10-3 mol), (3) 83 mg (~9,3 ? 10-4 mol) of the
sodium butylate. Samples in glass ampoules were
placed to thermostatic system at 291±5 K up to
two weeks. The viscous yellow polymer layer
was washed by decantation with several portions
of diethyl ether, and freed of volatile matter by
heating slowly (one and a half hours) to 80°
at 2 mmHg. There remained 2.8 ? 2.94 g. of a
slightly yellow solid, tacky, but showing no cold
flow. It was readily soluble in acetone, dioxane,
ethyl alcohol and butyl alcohol, ethyl acetate,
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Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
slowly soluble in aqueous sodium hydroxide,
insoluble in water, ether, and benzene.
Mol. wt. (amu): (1) 986, (2) 1072, (3) 1742.
Fig. 1 shows 1? NMR spectrum of a sample of
the resin obtained at interaction of angelicalactone
with 5 mol. % of sodium butylate at ?~395 K. The
sample had molecular weight 1072, polydispersity
- 1,8.
The molecular weight grow are presented at
Fig. 2.
The
chain-length
distribution
of
polyangelicalactone
depends
on
catalyst
8.0
7.0
6.0
concentration. The dependence is presented on
Fig. 3.
Polymerization of alpha-angelicalactone by
the sodium hydroxide. ? 15 mg of the sodium
hydroxide powder were added to two spot series of
3 g (~0,031 mol) of a-angelicalactone. The samples
in glass ampoules were placed to thermostatic
system at: (1) 295 ± 4 K, (2) 312 ± 4 K, up to
three weeks. Then, the lactone had polymerized
to a very viscous orange liquid. Polymer layer
was washed by same method as sodium butylate
catalyzed polymer. There remained up to 2.6 g
of a very viscous yellow liquid. The liquid had
5.0
4.0
3.0
2.0
1.0
(ppm)
Mw, amu
Fig. 1. The 1? NMR spectrum of a product of angelicalactone polymerization in the presence of sodium butylate
(5 mol. %) at ? = 395 K (238 hours)
1800
1600
A
1400
1200
1000
800
600
400
3 mol.% ButONa, T = 291+5 K
5 mol.% ButONa, T = 291+5 K
200
0
0
50
100
150
200
250
300
Time, h
Fig. 2. Time dependence of average molecular weight of the sodium butylate catalyzed polymer
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Fraction
Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
0,20
3
0,15
2
1
0,10
0,05
0,00
0
500
1000
1500
2000
2500
M, amu
Fig.3. Chain-length distribution of polyangelicalactone in the presence of catalysts: 1 ? 5,5 mol.% ButONa
(Mw=986 D); 2 ? 5 mol.% ButONa (Mw=1072 D); 3 ? 3 mol.% ButONa (Mw=1742 D)
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
(ppm)
Fig. 4. The 1? NMR spectrum of polymerization products of ?-angelicalactone at presence NaOH at ? = 290 K
(210 hours)
the same solubility characteristics as the sodium
butylate catalyzed polymer.
Mol. wt. (amu): (1) 928, (2) 893.
Fig. 4 shows the 1? NMR spectrum of a
sample of the polymer obtained at polymerization
angelicalactone in the presence of sodium
hydroxide at ?~290 K. The obtained substance has
molecular weight 893 and size of polydispersity
1,05.
The grow of molecular weight of the sodium
hydroxide catalyzed polymer are presented in
Fig. 5.
Estimation
of
polyangelicalactone
biodegradation ability. ? Microbiological
culture (0,5 g, ~107-108 colony-forming units)
was added to a shot of polymer (3 g) and 2 ml of
the water solution containing 1,45 M of sodium
chloride, 1,19 M of ammonia phosphate , 0,48
M of magnesium sulphate, or 2 ml of distilled
water for estimation of polymer biodegradation in
non-mineralized medium. The prepared samples
were maintained at 308±1 K during 5 - 30 day.
Completeness of polymer degradation was
estimated by full dissolution of resin samples. The
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MW, amu
Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
1000
B
800
600
400
5 mas.% NaOH, T = 295+4 K
5 mas.% NaOH, T = 312+4 K
200
0
50
100
150
200
250
300
Time, h
Fig. 5. Time dependence of average molecular weight of the sodium hydroxide catalyzed polymer
Table 1. Results of biodegradation of the obtained polymers by actinomycetes and yeast
Spieces of microorganisms
Sacharomices cerevisae1
Streptomy?es chrysomallus
2
Streptomy?es lividans
3
The increment of weight* or optical density**
A
24 -30 %*
22-25%**
-
B
101-184 %*
138-143%**
50-52%**
-
38-41%**
Time of full
degradation, day
5-7
19-28
24-30
1 - a set of strains (GOST 171-81); 2 - strain VKM 1332 ?-2; 3 - strain TS-64.
* - gravimetric determination of an incremental value of dry weight of microorganisms in accordance with GOST 171-81 on
substrate from a sample of polymer with ?w=1120 amu.
** - nefelometric determination of dynamics of propagation of microbiological cultures on substrate from a sample of polymer
with ?w=1120 amu.
microorganisms liveweight gain was estimated by
increasing of suspended cultures dry weight and
culture liquids optical density (?= 540 nm, cell
thickness = 1 cm, nephelometric method).
These experiments have shown, that
the obtained polymers are exposed to full
biodegradation by microorganisms Sacharomices
cerevisae during 5 - 15 day, and Streptomy?es
lividans and Streptomy?es chrysomallus - during
20 - 30 day (Table 1).
Discussion
From the results obtained using these
catalytic systems, the fist time obtained polyesters
of alpha-angelicalactone [12] had a low values of
molecular weights, theirs polymerization degree
reaches values n = 9 - 20, and has tendencies to
increase at catalyst concentration and temperatures
decreasing. Assessed value of polymerization
degree is
n
k
>M @0 ,
>cat @0
where [M]0 is initial monomer concentration, [cat]0
- initial catalyst concentration, k - proportional
coefficient. k is temperature and reaction
conditions depending and consist of 0.58 to 1.74
and, probably, up to 2 under low temperature
(about 200 K).
Signals of olefinic protons in 1? NMR
spectra of the obtained samples are brought into
correlation with intensive signals at 4 - 6 ppm.
Integrated intensity of signals of area 4,0 - 6
ppm is come to 0,113 and 0,134 for spectra of
polymerization products on sodium hydroxide
and sodium butylate, accordingly. Therefore, 68
and 80 % initial contents of olefinic protons in
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Valeri E. Tarabanko, Konstantin L. Kaygorodov, Mikhail Yu. Chernyak. Polyesterification of alpha-Angelicalactone
monomer are kept in polymer. Thus, under action
of the basic catalysts intermonomeric bonds of
polymer are formed basically by disclosing the
lactone cycle (68 - 80 % of bonds in polymer).
Conclusions
The polymer prepared by the action of basic
catalysts on alpha-angelicalactone has been
shown to be a polyester having the ?head to tail?
structure. The part of polyester intermonomeric
bonds in the obtained products of polymerization
to biodegradation by the microorganisms during
5 - 30 days.
Key properties of homopolyesters from
angelicalactone are its biodegradability, possible
biocompatibility, and its manufacture from
renewable resources. Primary application area in
which these features meet some needs is medical:
polyangelicalactone?s biocompatibility coupled
with its slow hydrolytic degradation lead to
potential in reconstructive surgery and controlled
release fields.
reaches 68 - 80 %. The obtained polymers give in
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Lactone. J. Am. Chem. Soc. 1939. V.61. P.1682.
5. Luke? R., Syhora K. O dimerisaci lactonu ?-angelikoveho. Chem.listy. 1954. V. 48. ? 4. P. 560.
6. Sazanov Yu. N. Polimerizaciya laktonov. Uspekhi khimii. 1956. V. XXXVII. N 6. P. 1084.
7. Matsushita Teruki. Production process for organometallic fine particle and catalyst for
polymerization. US patent 6084059, 2000.
8. Loshadkin D.V. Biodegradiruemye plastiki: tipy materialov, osnovnye svoystva i perspektivy
ispolzovaniya v promyshlennosti. Plasticheskie massy. 2002. N 7. P. 41.
9. Still J. Monomery dlya polykondensacii. Moskva. Nauka. 1976. 632 p.
10. Tarabanko V. E.; Chernyak M. Ju.; Kuznetsov B. N.; Kozlov I. A. RU patent 2174509, 2001.
11. Dyhanov N.N., Skripkina V.T. Butilat natriya. Metody polucheniya khimicheskikh reaktivov i
preparatov. 1964. N. 9. P. 28.
12. Tarabanko V. E., Kaygorodov K.L. RU patent 2309163, 2006.
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
Journal of Siberian Federal University. Chemistry 2 (2008 1) 124-135
~~~
??? 544.478.32
Formation of Iron Nanoparticles by Thermal Transformations
of Iron Carbonyls on Silica Surface
Boris N. Kuznetsova,c, Vladimir I. Kovalchukb,
Nadezhda M. Mikovac, Nikolai V. Chesnokova,c*
and Liliya V. Naimushinad
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Pittsburg University, PA 15261 USA
c
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
d
Krasnoyarsk State Institute of Economics and Trade,
2 L. Prushinskaya st., Krasnoyarsk, 660075 Russia 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
There have been determined some regularities of thermochemical transformations of supported on
silica iron carbonyls containing from 1 to 6 metal atoms. There have been selected the conditions of
iron carbonyls thermal decomposition which provides the formation of metallic particles having the
size of 0,5 -1,0nm.
Keywords: iron carbonyls, silica, thermal transformations, nanoparticles.
Introduction
The nanoparticles of transition metals are
finding an increasing application in producing
the functional materials of various purposes.
In particular, the systems on the basis of
iron nanoparticles on solid supports present
great interest for the industrial catalysis and
electronics. To obtain metallic nanoparticles on
the supports surface, various methods are used
? from evaporation in vacuum to the thermal
decomposition of the supported metalloorganic
compounds [1, 2, 3]. For this purpose, it is possible
to apply carbonyl iron clusters having a strictly
given number of atoms and a metallic frame
*
1
structure. When being heated, the carbonyl groups
are easily removed forming iron nanoparticles.
In the scientific literature, there is described
the use of only a restricted number of iron
carbonyls (mostly Fe(CO)5 and Fe3(CO)12) for
supporting them to the oxide surface for the
purpose of their further thermal decomposition to
forming metallic particles [4-6]. Besides, there is
no information about the influence of the initial
iron carbonyls composition on the size of the
metallic particles which are formed during their
heat treatment. During the process of the thermal
transformations of the iron carbonyls on the oxide
supports, it is possible for them to chemically
Corresponding author E-mail address: cnv@icct.ru
© Siberian Federal University. All rights reserved
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
interact with the surface functional groups (for
example, OH?groups), which leads to oxidizing
metal atoms. One can expect that the reactivity
of the supported iron carbonyls to the oxidation
during the thermal treatment, will decrease as
the number of metal atoms increases. And the
size of the formed metal particles will depend on
composition the initial carbonyl compound.
The aim of the given work is to carry out
a systematic physical and chemical study of the
peculiarities of forming iron nanoparticles during
the thermal transformations of the iron carbonyls
supported to the porous silica. The number of the
atoms in the iron carbonyls varies from 1 to 6.
Experimental
The carbonyl compounds [TEA][HFe(CO)4]
[7], Fe2 (CO)9 [8], [TEA]2[Fe2(CO)8] [7], Fe3(CO)12
[9], [TEA][HFe3(CO)11] [8], [TEA]2[Fe4 (CO)13]
[10], Fe5C(CO)15 [11], [TEA]2[Fe5C(CO)14] [12],
[TEA]2[Fe6C(CO)16] [12] (TEA ? (C2H5)4N+),
were synthesized according to the well-known
methods.
As a carrier, there was used the silica
dehydrated at 773 K (its specific surface was
250 m2/g, the contents of Na and Fe were less than
0,01 mass %, the fraction was 0,5-0,25 mm).
The supporting of the carbonyls to the
silica surface was carried out by impregnating
SiO2 with their solutions in acetone (for anion
carbonyls), or in hexane (for neutral carbonyls).
All the operations on synthesizing, supporting the
clusters on SiO2, their transformations in various
gaseous mediums were performed under the
conditions excluding contact with air.
The thermal stability of the supported
clusters was studied by using the method of IR
spectroscopy (spectrometer ?Specord ? 75 IR?)
in the range of 1300-4000 cm-1. For carrying out
the studies, there was used a special vacuum cell
having the windows from NaCl, which allowed to
prepare samples, providing their high-temperature
treatment in various gaseous mediums as well as
the spectra recording without contacting the air.
In a typical experiment, the solid carrier was
pressed to form plates (8-10 mg/cm2). Then it was
fixed in the holder, put into the cell and trained
in the vacuum at 873 K for an hour to remove
the water. After that the plate was cooled to
room temperature, and the cluster solution in the
corresponding organic solvent was poured in. The
excess of the solution was decanted. The solvent
remaining in the carrier?s pores, was removed
by freezing with liquid nitrogen followed by the
vacuum evaporation at 298 K to reaching the
residual pressure of 10-5 torr.
The study of the transformations of the
supported iron clusters at raised temperatures,
was carried out by using the method of
IR-spectroscopy,
the
thermoprogrammed
decomposition and the electron microscopy of
high resolution.
The thermoprogrammed decomposition
of the supported iron carbonyls was performed
in a flow-type installation by using a gaschromatographic analysis of the products. The
samples were put into a glass reaction vessel not
contacting the air. The samples were blown off by
helium at room temperature till the solvent traces
disappeared. The decomposition of the supported
carbonyls was carried out in the flow of the carrier
gas (helium) in the conditions of the programmed
temperature rise (4K/min.).The analysis of the
decomposition products was accomplished
by using the katharometer (CO, CO2) and the
flaming and ionizing detectors (hydrocarbons) on
the columns filled with porapack?Q and Al2O3.
The quantitative interpretation was implemented
according to the calibration obtained by measuring
the area of the chromatographic peak CO2 or
CH4 when introducing a strictly dosed adsorbate
volume into the current of the carrier gas.
The electron-microscopic studies of the
Fe/SiO2 systems were carried out by using the
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
electron microscope «EBM ? 100B» having the
limiting resolution on points 3Е. The samples were
prepared under by means of mechanical grinding
the ethanol followed by the ultrasound dispersion.
The suspension was put on the carbon supports on
copper grids. The electron-microscopic study was
carried out in a light field mode at the accelerating
voltage of 75 kV and the objective lens aperture
of 6?10-3 rad. according to the methods described
in [13]. To exclude the influence of the carbon
support on the contrast range of the picture, there
were studied the sample parts which were in the
holes of the carbon support. The microscope
magnification made up 106 ± 5 %.The area-mean
particle size was calculated from the differential
granulometric composition diagrams of the
particle distribution according to their size which
was obtained by way of the statistical processing
of the photomicrographies.
Results and discussion
During the supporting of carbonyls on
SiO2 surface at room temperature, only their
physical adsorption occurs, and the carbonyl
compounds may be washed off by the excess of
the corresponding solvent in the initial form.
The results of the studies of the thermal
stability in the H2 atmosphere of the clusters
[HFe3(CO)11] [TEA], [Fe4(CO)13] [TEA]2,
[Fe5C(CO)14]
[TEA]2,
Fe5C(CO)15
and
[Fe6C(CO)16] [TEA]2 supported on SiO2 surface
which was carried out by using the method IR
spectroscopy, are given in Table 1. In the spectra
of the supported compounds, there are only the
most intensive absorption bands (a.b.) ?CO of the
carbonyl clusters. And there are not registered
the bridge CO-groups and the high ? frequency
a.b. ?CO, which are present in the IR spectra of the
clusters in the solutions. Evidently it is caused by
the insufficiently high clusters concentration on
the carrier surface, because the indicated bands
have relatively small intensities. It is noteworthy,
that the supporting of the clusters on the SiO2
tablet placed in the IR-cell, was performed by
the single ? stage impregnation, and the cluster
concentration on the carrier surface, was limited
by its solubility.
The infra-red spectrum of the cluster
[HFe3(CO)11]- which is supported on SiO2, contains
two a.b. ?CO at 1980 and 2002 cm-1. In the range
of the supported [Fe4(CO)13]2? and [Fe5(CO)14]2?,
there is present only one absorption band (at 1955
and 1965 cm-1) respectively. These bands are a
little displaced as compared to their position in the
clusters spectra in the solutions. The treatment of
the supported carbonyls by hydrogen for an hour
at 373 K, leads to the complete disappearance of
the mentioned a.b. ?CO and appearing the intensive
a.b. at 1635 cm-1 (Table 1). The low-frequency
a.b. at 1635 cm-1 whose appearance is observed
for all the studied clusters after their treatment
in the hydrogen atmosphere at a temperature of
? 373 K, is considered to be the antisymmetric
valence vibrations of CO2 molecule adsorbed on
the SiO2 surface in accordance with [14].
In the spectrum of the neutral cluster
Fe5C(CO)15, supported on SiO2, there are a.b.
?CO at 2050, 2098 cm-1. There is also a greatly
displaced, as compared to the spectrum in the
solution, a.b. at 1973 cm-1. After treatment the
sample by hydrogen at 373 K, these absorption
bands ?CO disappear, but new a.b. appear at 1635
cm-1 (table 1).
In the carbonyl area of the cluster IR spectrum
[TEA]2[Fe6C(CO)16], which is dissolved in
acetonitrile, there are present a.b. at 1769 (weak),
1930 (arm), 1957 (arm), 1969 (very strong), 2029
(weak) cm-1 (table 1).
After carbonyl supporting on SiO2 surface at
room temperature, one can observe a displacement
of a.b. at 1969 and 2029 cm-1 to 1975 and 2036
cm-1 respectively. The holding of the sample
[TEA]2[Fe6C(CO)16] / SiO2 in the hydrogen at the
temperatures of 298 ? 473 K leads to decreasing
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
Table 1. Absorption bands in the carbonyl area of dissolved and supported on SiO2 iron carbonyl clusters
?
1
Sample
[TEA][HFe3(CO)11]
(a solution in the chlorine
methylene)
[TEA][HFe3(CO)11] / SiO2
2
[TEA]2[Fe4(CO)13]
(a solution in acetonitrile)
[TEA]2[Fe4(CO)13] / SiO2
3
[TEA]2[Fe5C(CO)14]
(a solution in acetonitrile)
[TEA]2[Fe5(CO)14] / SiO2
4
Fe5C(CO)15 (a solution in
cyclohexane)
Fe5C(CO)15 / SiO2
[TEA]2[Fe6C(CO)16]
(a solution in acetonitrile)
Absorption bands
?CO, cm-1
Treatment
-
1740 (bridge), 1933 (arm), 1953 (arm),
1981 (very strong), 2001 (strong), 2068 (mean)
-
1980 (strong), 2002 (strong)
H2, 373 K, 1 hr
H2, 373 K, 1 hr
H2, 373 K, 1 hr
H2, 373 K, 1 hr
-
5
[TEA]2[Fe6C(CO)16] / SiO2
1635 (strong)
1615 (bridge, weak), 1896 (arm), 1949 (strong),
2021 (weak)
1955 (strong)
1635 (strong)
1755 (bridge, weak) 1890 (arm), 1940 (arm),
1969 (very strong), 2027 (weak)
1965 (strong)
1635 (strong)
1760 (very weak), 1991 (mean), 2012 (arm),
2031 (strong), 2050 (very strong), 2098 (weak)
2050 (strong), 2098 (weak)
1635 (strong)
1769 (bridge, weak), 1930 (arm), 1957 (arm),
1969 (very strong), 2029 (weak)
1975 (very strong), 2036 (weak)
H2, 473 K, 1 hr
1635 (mean), 1975 (very strong), 2036 (strong)
H2, 523 K, 1 hr
1635 (mean)
the relative intensity of the absorption bands ?CO.
After treatment this sample by H2 at 373 K, there
appears an absorption band at 1635 cm-1, whose
intensity increases with the rise in temperature.
The indicated a.b. disappears only after treatment
the supported cluster by hydrogen at 523 K.
To get some additional information about the
nature of the surface carbonyl iron compounds,
there was carried out a study of the composition
of the Fe carbonyls, extracted from the surface
of the samples [Fe6C(CO)16][TEA]2 / SiO2 and
[Fe5C(CO)14][TEA]2 / SiO2 heated in argon at
various temperatures. The carbonyl clusters
extracted from the carrier surface, were identified
by comparing their IR spectra with the spectra of
individual compounds and by using the data of the
element analysis. It is determined that after being
supported on SiO2, the anion cluster [Fe6C(CO)16]
[TEA]2 remains unchangeable. What testifies to
that is practically the complete correspondence
between the IR spectra of the carbonyl compound
extracted from the SiO2 surface with acetonitrile
(Fig. 1, curve 1) and the initial carbonyl carbide
cluster (see Table 1) in the area of the valence
vibrations of the carbonyl CO?groups.
The results of the studies of the behaviour of
silica supported [Fe6C(CO)16][TEA]2 during the
thermolysis in the argon atmosphere, allowed to
conclude that the supported cluster retained its
initial composition after being heated at 423 K for
two hours. The increase of the treatment duration
to 4 hours leads to appearing alongside the main
absorption band of the initial cluster at 1968 cm-1,
also the a.b. of small intensity at 2051, 2035, 2020
and 1990 cm-1 (Fig. 1, curve 2). The latter can be
referred to the neutral carbonyl iron compound,
the identification of which is difficult due to its
small quantities and not high stability.
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
When the treatment duration is 6 hours, on
SiO2 surface there is formed the cluster having
the composition [Fe5C(CO)14][TEA]2, which was
extracted with the yield to 30 % as calculated for
the iron content (Fig. 1, curve 3). The discovered
partial fragmentation of the octahedral carbide
cluster [Fe6C(CO)16]2- to the pentanuclear carbide
carbonyl dianion [Fe5C(CO)14]2-, agrees with the
described in [12] the probable scheme of thermal
transformation of the metal frame Fe6C to Fe5C:
[Fe6C(CO)16]-
423 K
[Fe5C(CO)14]2- + {Fe(CO)2}
(1)
As the temperature of heating the sample
[Fe6C(CO)16][TEA]2/SiO2 increases to 450 K, the
number of the iron clusters extracted from the
carrier?s surface, decreases. After this thermal
treatment, one can see a clearly marked arm at
1948 cm-1 which indicates the further progress
of the chemical transformations of the supported
carbonyl clusters (Fig. 1, curve 4). After treatment
the sample [Fe6C(CO)16][TEA]2/SiO2 in argon
at a temperature of 473 K, there takes place the
complete decarbonylating of the supported cluster,
because in the IR spectrum of the acetonitrile
extract, there are absent the a.b. of the valence
vibrations of the CO groups.
When heating the cluster [TEA]2[Fe6C(CO)16]
supported on SiO2, in the atmosphere of a synthesis
gas at 423 K for 2 hours, one could not observe
any substantial changes in the IR spectrum which
indicates that the initial cluster composition was
retained. The longer heating (6 hours) of this sample
under the given conditions, leads to forming some
amount (about 7 %) of the carbonyl compound,
whose IR spectrum in the area of the valence
vibrations of CO is similar to the range of the
neutral carbide cluster Fe5C(CO)15. The reason for
forming the uncharged Fe5C cluster on the surface
of the dehydrated silica, may be the oxidation of
the cluster Fe6C and Fe5C ? dianions of which such
oxidizing transformations in solutions are quite
typical. So, the neutral Fe5C(CO)15 was obtained
Fig. 1. The IR spectra of the acetonitrile solution of
the cluster [TEA]2[Fe6C(CO)16] extracted from the
SiO2 surface (1), and also of the solutions, obtained
by extracting the sample [TEA]2[Fe6C(CO)16]/SiO2
by acetonitrile, after its being heated in the argon
atmosphere at temperature of 423 K for 4 hr. (2), at 423
K for 6 hours (3), at 448 K for 6 hours (4)
by oxidizing [Fe6C(CO)16]2- with the salts Ce4+,
Fe3+ or the concentrated H2SO4 [11]. The same
result is achieved when [Fe5C(CO)14]2- is oxidized
with the salt Ce4+ in the acid medium [12]. In our
case, the oxidizer nature is not determined. But
one can suppose that as the latter, there may be the
surface OH-groups of SiO2.
Based on the obtained data, one can come to
the conclusion, that the iron carbonyls with the
nuclearity from 1 to 4, have a not high threshold of
thermal stability. Already at 373 K, one can observe
their practically complete decarbonylating. The
clusters with 5-6 iron atoms, containing a carbide
carbon atom, are characterized by a higher thermal
stability.
The obtained results testify to the fact that
despite the structural changes of the cluster frame
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
and the corresponding carbonyl surrounding,
the included carbon atom is preserved inside the
metallopolyhedron up to the full destruction of the
surface molecular clusters raising their thermal
stability.
In Fig. 2-4 and in Table 2, there are given
the results of studying the thermoprogrammed
decomposition (TPD) of the iron carbonyl
compounds supported on SiO2. The products of
their thermal degradation in the flow of the inert
gas, are CO, CO2, saturated and unsaturated
hydrocarbons C1 ? C6. With some exceptions,
the material balance on carbon is tabulated
satisfactorily (Table 2). It is noteworthy, that
among the products of the clusters thermolysis, on
the surface of SiO2, there may also be hydrogen
formed, probably, during the oxidation of iron
atoms with the surface hydroxyl groups, or as a
result of the conversion of water gas.
The emission of hydrogen was observed
earlier during the decomposition of Fe3(CO)12/
SiO2 [15]. During the thermal decomposition of
the charged carbonyl iron clusters, in addition to
ethylene, there may also be formed ethylamines
and ammonia. In the given work, no attempts
were made to register hydrogen, alkylamines
or ammonia. It is also necessary to note that the
formation of ethylamines during the thermal
programmed decomposition of the supported
clusters can be thought of only in the experiments
where there was an unsatisfactory balance
on the carbon, that is for the samples [TEA]
[HFe(CO)4]/SiO2, [TEA]2[Fe4(CO)13]/SiO2 and
[TEA]2[Fe5C(CO)14]/SiO2.
The curves of the CO emission during the
thermal programmed decomposition of iron
carbonyls, confirm the conclusion made on
the basis of the IR spectroscopy data about the
comparatively not high stability of the Fe carbonyl
clusters on the surface of SiO2. In Fig. 2 there is
given the composition of the products emitting
during the thermoprogrammed decomposition of
the uncharged clusters Fe3(CO)12 and Fe5C(CO)15
supported on SiO2. On the graphic dependence of
the amount of the emitted products on temperature,
there are two maxima of CO emission, which differ
in their intensity. For Fe3(CO)12/SiO2, the first
maximum at the temperature of 363 K, corresponds
to the emission of approximately 9,5 moles of CO
per mole of the initial cluster, the second, at 423 K
? 0,6 moles of CO. In the temperature range 393533 K, there was registered the CO2 emission in
the amount of about 0,8 mole. On the curve of the
termoprogrammed decomposition of the sample
Fe5C(CO)15/SiO2, one can observe two maxima
? at 348 K and at 423 K. The first maximum
corresponds with emitting of about 1,7-1,8 moles
of CO / cluster mole, the second one corresponds
with the emission of about 3 moles of CO / cluster
mole. In the temperature range 348-373 K, there is
observed the emission of about 3,5 moles of CO2 /
mole of cluster. So, with the rise in the temperature
of the thermoprogrammed decomposition to 373
K, the supported cluster Fe3(CO)12 loses, on the
average, more than a third of the initial quantity of
the CO molecules coordinated with iron.
It is discovered that for the supported iron
carbonyls of low nuclearity Fe1-Fe3 practically
the complete loss of carbonyl ligands takes place
at the temperatures of ? 423 K. The four-nuclei
cluster [TEA]2[Fe4(CO)13] loses in this temperature
range, approximately half of the coordinated COgroups. The supported clusters of high nuclearity
Fe5-Fe6 in the indicated temperature range, retain
about two thirds of the CO molecules coordinated
with the atoms of Fe (Fig. 2-4).
On the curve of the CO emission, during the
thermoprogrammed decomposition of the cluster
[TEA]2[Fe6C(CO)16] supported on SiO2, there are
present two maxima (Fig. 4B). One of them (390
K) corresponds to the emission of ~ 2 moles of CO
/ mole of cluster. And as distinct from the other
clusters in this temperature range, practically no
emission of any other decomposition products
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
Fig. 2. The composition of the thermoprogrammed destruction products Fe3(CO)12/SiO2 (A), Fe5C(CO)15/SiO2
(B): 1 ? CO; 2 ? CO2; 3 ? C2H4; 4 ? C2H6; 5 ? C3H6
? ? is the area corresponding to 5·10-1 moles of the product
Fig. 3. The composition of the thermoprogrammed destruction products Fe3(CO)12/SiO2 (A), Fe5C(CO)15/SiO2
(B): 1 ? CO; 2 ? CO2; 3 ? C2H4; 4 ? C2H6; 5 ? C3H6
? ? is the area corresponding to 5?10-1 moles of the product
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
Fig. 4. The composition of the thermoprogrammed destruction products: [TEA]2[Fe4(CO)13]/SiO2 (A),
[TEA]2[Fe5C(CO)15]/SiO2 (B), [TEA]2[Fe6C(CO)16]/SiO2 (C): 1 ? CO; 2 ? CO2; 3 ? CH4
? ? is the area corresponding to 1?10-1 mole
Table 2. The composition of the termoprogrammed destruction products of the iron carbonyls with various
nuclearity (mole of carbon / mole of cluster), supported on the silica.
Sample
The decomposition products of the supported clusters
CO
CO2
CH4
C2H6
C2H4
C3H8
C3H6
C4+
?
2,3
0,1
4,5
< 0,1
< 0,1
-
0,8
1,5
9,3
[TEA]2[Fe2(CO)8H]/SiO2
2,8
0,9
0,2
1,4
12,4
-
< 0,1
1,6
19,3
Fe3(CO)12/SiO2
10,0
0,8
-
-
-
-
1,0
-
11,8
[TEA]2[Fe(CO)4H]/SiO2
[TEA][HFe3(CO)11]/SiO2
4,1
1,8
2,0
0,3
0,2
1,1
1,3
7,2
18,0
[TEA]2[Fe4(CO)13]/SiO2
4,5
0,7
4,5
3,9
3,0
< 0,1
3,5
4,9
25,1
Fe5C(CO)15]/SiO2
4,9
7,2
<0,1
1,2
2,5
-
-
-
15,8
[TEA]2[Fe5C(CO)14]/SiO2
12,5
2,3
1,3
1,2
1,2
-
0,1
7,1
25,7
[TEA]2[Fe6C(CO)16]/SiO2
13,0
2,4
0,3
2,0
3,7
1,0
1,5
8,5
32,4
TEA ? is tetraethylammonium
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
takes place. It is not excluded that under these
conditions, there occurs the transformation
of cluster [Fe6C(CO)16]2- into Fe5C(CO)14]2-,
described above in the scheme 1. And the unstable
fragment {Fe(CO)2} is decomposed or oxidized
by the surface carbonyl groups with the emission
of two molecules of CO per each molecule of the
initial cluster.
The temperature ranges of the emission
of both CO and CO2 as well as the intensities
of the corresponding peaks on the curves of the
thermoprogrammed decomposition, differ greatly
for the supported anion iron carbonyls of various
composition. And it is difficult to reveal any
regularities when analyzing the obtained data
(Fig. 3-4).
During
the
thermoprogrammed
decomposition of the supported clusters
[Fe2C(CO)8]2-, [Fe5C(CO)14]2- and [Fe6C(CO)16]2-,
reaction of CO conversion. What testifies to the
fact that this supposition is true is the information
concerning the catalysis of the reaction of
converting CO with steam using iron carbonyls in
solutions [15].
The thermoprogrammed decomposition of
the neutral clusters Fe3(CO)12 and Fe5C(CO)15
taking place on the SiO2 surface, leads to the
formation, alongside the carbon oxides of
propylene (in case of a three-nuclei cluster), of a
mixture of ethane and ethylene for the pentanuclei
carbonyl, when there are tracing amounts of
methane (Table 2). Let us note that propylene
is formed during the hydrogenation of CO on
the supported catalysts obtained with using the
carbonyl Fe3(CO)12 [15]. As regards methane, it
is most likely the product of hydrogenating the
coordinated CO, as the hydrogenolysis or the
cracking of hydrocarbons C2+ on iron occurs only
the emission of CO2 starts practically with
room temperature. For the supported clusters
[HFe(CO)4]- and [Fe4(CO)13]2-, the emission of
CO2 is observed only at temperatures of ? 420 K.
In case of the supported cluster [HFe3(CO)11]- on
the curve of the CO2 emission, one can observe
two maxima ? at 330 K (corresponding to 0,6
mole of CO2 per mole of the initial cluster), and at
643 K (1, 2 moles per mole of the initial cluster).
The formation of CO2 may happen, for
example, in the way of the reaction of converting
CO with steam
at the temperatures ? 573 K [16].
Besides the reaction of converting CO with
steam, the source of hydrogen may also be the
surface hydroxyl groups, since it is known, that
the iron-containing carbonyl clusters, supported
on SiO2, may be oxidized with them forming
hydrogen already at room temperature [17, 18].
In case of charged clusters, the source of
hydrocarbons C2-C6 may be a tetraethyl ammonium
ion. So, the formation of the hydrocarbons C2+
during the thermoprogrammed decomposition of
the anion clusters, was not discussed.
To measure the size of the iron particles
formed on the SiO2 surface, during the thermal
treatment of the supported iron carbonyls,
there was used the method of transmitting
electron microscopy of high resolution. The
electron microscopic study of the samples
[TEA]2[HFe(CO)4]/SiO2,
[TEA]2[Fe2(CO)8]/
SiO2,
Fe3(CO)12,
[TEA][HFe3(CO)11]/SiO2,
[TEA]2[Fe4(CO)13]/SiO2, treated with the synthesis
gas at the temperatures 423-623 K, showed that
the iron particles size on the carrier surface, does
CO + H2O ? CO2 + H2
(2)
also, as a result of the disproportionation of carbon
monoxide (Buduar reaction):
2CO ? CO2 + C
(3)
Since the Buduar reaction is carried out only at
higher temperatures, the most probable route of
the CO2 formation during the thermoprogrammed
decomposition of the supported carbonyls (at
least in the range of moderate temperatures), is the
# 132 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
A
B
Fig. 5. The electron microscopic pictures of the sample [TEA]2[Fe4(CO)13/SiO2 treated with the mixture of CO
and H2 at 523 K (A) and the sample [TEA]2[Fe6C(CO)16]/SiO2 treated with H2 at 623 K (B)
not exceed 2 nm. So, in the electron microscopic
picture of the sample [TEA]2[Fe4(CO)13]/SiO2,
treated with the sythesis gas at 523 K, one can
clearly see homogeneous metallic particles
of the size 1-2 nm and a small number of twodimensional particles having a somewhat large
size (Fig. 5 A).
A higher dispersity is typical of the
thermally treated samples Fe5C(CO)15/SiO2,
[TEA]2[Fe5C(CO)14]/SiO2, [TEA]2[Fe6C(CO)16]/
SiO2. For example, in the electron microscopic
pictures of the reduced sample [Fe6C(CO)16]2-/
SiO2, which was thermally treated at 623 K, there
are present the particles having the size of the
order of 0,5 nm, which is close to the size of the
Fe6 cluster frame (Fig. 1 B). These data confirm
the conclusion about the stabilizing influence of
the carbide atom of the carbon, included into the
metal frame of carbonyl clusters.
For comparison, let us note, that according to
the data of the work [15], the size of the metallic
particles, obtained by the thermal decomposition
in the hydrogen of the cluster Fe3(CO)12 supported
on SiO2, made up 1,4 nm, whereas according to
the data of [19], it made up 14 nm. The smallest
particles (0,5 nm) were obtained by the thermal
decomposition in the vacuum at 310 K of the
cluster Fe3(CO)12 which was supported on Al2O3
[6].
So, on the basis of the determined regularities
of the thermochemical transformations of the
iron carbonyls supported on silica, differing in
the number of the metal atoms, there has been
carried out the selection of conditions of their
thermodestruction, with supply the formation of
the metallic particles having the size from 0,5 to 1,0
nm. They are distributed in a rather homogeneous
way along the surface of the support.
These systems may be used as functional
nanomaterials and as model catalysts when
studying the effects of the size in the catalysis
with iron nanoparticles.
# 133 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
References
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Phillips J., Dumesic J.A., Production of supported metal catalysts by the decomposition of metal
carbonyls (review). Appl. Catal. 1984. V. 9, N 1. P. 1-30.
Ichikawa, M. Surface-supported metal cluster and their catalysis in ??-based reactions. D. Rudel
Publisihg company: Tailored Metal Catalysts. 1986. P. 183-263.
Kou Y., Wang H.-L., ?? M.R., Tanaka ?., Nomuraet M. Preparation and EXAFS studies of highly
dispersed iron catalyst derived from Fe3(CO)12 precipitated on alumina. J. Catal. 1993. V. 141. P.
660-670
Case J.R., Whitiner M.C.J. The Organic Chemistry of the Transition Metals. Part II. A Spectroscopic
Investigation of Polynuclear Iron Carbonyls and Derived Anions. J. Amer Chem Soc. 1960. V. 80,
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Braye E. H., Hubel W. Rausch M.D., Thomas M., Wallace T.M. Diiron Enneacarbonyl. Inorg.
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Hieber W., Brendel G. Uber Metallcarbonyle. 77. Entstehung mehrkerniger Carbonylferrate aus
mehrkernigen Eisencarbonylen Z. Anorg. Chem. 1957. V. 289. P. 324-337
Hieber W., Werner R., Vierkernige Carbonylferrate. Chem. Ber. 1957. B. 90. S. 286.
Stewart R.P., Anders U, Graham W.A.G. A novel synthesis of Fe5C(CO)15 from the [Fe6C(CO)16]2anion. J. Organometal. Chem. 1971. V. 32. P. 49-51.
Lopatin V.E., Mikova N.M., Gubin S.P. Synthesis and reduction ? oxidation of iron clusters.
Izvestiya Akademii Nauk, the USSR, Seriya Khimicheskaya. 1981. N 8. P. 1925.
Zaikovsky V.I., Ryndin Yu.A., Kovalchuk V.I., Plyasova L.M., Kuznetsov B.N., Yermakov Yu.I.
The electron microscopic investigation of platinum catalysts prepared by the decomposition of
metals complexes supported on the suface of SiO2. Kinetics and catalysis. 1981. V. 22 N. 2. P.
443-451.
Davydov A.A. The infrared spectroscopy in the chemistry of oxides surfaces. Novosibirsk, Nauka,
1984. 246 p.
Basset J.M., Besson ?., Choplin A., Hugues F., Leconte A., Rojas D., Smith A.K., Zanderighi
G.M. Supported cluster and Mechanism of CO Reduction, in Fundam. Res. Homogeneous Catal.
New-York - London. 1984. V. 4. P. 19-53.
Vannice M.A. The Catalytic Synthesis of Hydrocarbons from H2/CO Mixtures over the Group VIII
Metals. V. The Catalytic Behavior of Silica-Supported Metals. J. Catal. 1977. V. 50. P. 228-236.
Kovalchuk V.I., Mikova N.M., Chesnokov N.V., Naimushina L.V., Kuznetsov B.N. Mixed ironrhodium carbidocarbonyl clusters on oxide supports: chemistry and catalysis of syn-gas reactions
J. Mol. Catal. 1996 V. 107. P. 329-337.
# 134 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk? Formation of Iron Nanoparticles by Thermal Transformations of Iron?
18. Kovalchuk V.I., Mikova N.M., Savitskii A.F., Chesnokov N.V., Kuznetsov B.N. Chemical
transformation of SiO2 supported [Fe5RhC(CO)16]- cluster and catalysis of propylene
hydroformylation. Russ. Chem. Bull. 1995. V.44, N 4. P. 611-620.
19. Brenner, A. Synthesis of highly dispersed catalysts of supported iron. J. Chem. Soc. Chem.
Commun. 1979. ? 6. P. 251.
# 135 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktoriya V. Sursyakova, Sergey N. Kalyakin? Measurement of Ion Association Constants from Decrease of Peak Areas?
Journal of Siberian Federal University. Chemistry 2 (2008 1) 136-141
~~~
??? 543.545 : 544.353.2
Measurement of Ion Association Constants from Decrease
of Peak Areas by Capillary Electrophoresis Technique
with Indirect Spectrophotometric Detection
Viktoriya V. Sursyakovaa,b*, Sergey N. Kalyakina,
Galina V. Burmakinaa and Anatoliy I. Rubayloa,b
a
Institute of Chemistry and Chemical Technology SB RAS,
42 ?. Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
The new method to determine association constants using capillary electrophoresis technique with
indirect spectrophotometric detection was investigated. An association constant was calculated
from decrease of corrected peak area. The equations for correction of peak areas and calculation of
association constants were examined using zone mathematical model of electrophoretic ion motion.
This method was used to measure association constant of calcium - ions with sulfate - ions: lg Kass
(??SO4) = 2,39±0,09.
Keywords: ion association, capillary electrophoresis.
Introduction
The capillary electrophoresis technique
(CE) is used for measurement of ion association
constant from elctrophoretic mobility changes
[1-10]. However if association constant has
low value it is difficult to divide contribution in
electrophoretic mobility changes ion association
and electrostatic interactions because of the
estimation of electrostatic interactions in solution
containing of several ions is a problem. But then
we observed that on real electropherograms for
case of indirect spectrophotometric detection the
decreases of peak areas were occurred for system
in which the ion association takes place. This
decrease of peak area will be bound to fraction
*
1
of nonassociated ions. In present study the new
method to determine the association constants
using capillary electrophoresis technique with
indirect spectrophotometric detection from
decrease of corrected peak area was investigated.
Experimental
All experiments were carried out on a
capillary electrophoresis system Agilent 3DCE
G1600A (Agilent Technologies, USA) equipped
spectrophotometric diode-array detection system
(DAD). Fused-silica capillary of 64,5cm total
length (effective length 56 cm) and 50 ?m inner
diameter was used. The measuring wavelength of
the DAD system was 220 nm with reference 400
Corresponding author E-mail address: viktoria_vs@list.ru
© Siberian Federal University. All rights reserved
# 136 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktoriya V. Sursyakova, Sergey N. Kalyakin? Measurement of Ion Association Constants from Decrease of Peak Areas?
nm. Analytical data signals processing and system
control were handled by HP ChemStation software
(Rev.A.10.02). The temperature held at 25 0?.
Samples were injected in the hydrodynamic mode
by applying an external pressure 50 mbar for 4 s.
To measure electroosmotic flow velocity a neutral
marker was injected to outlet by hydrodynamic
pressure 50 mbar for 2 s. The capillary was
washed daily for 10 min with 0,1 M NaOH, two
times for 10 min with doule destilled water, for 10
min with run buffer and for 20 min with keeping
under voltage. Between injections capillary was
washed too in 10 min with run buffer.
All chemicals used were of analytical grade
or better. Sodium chloride and sodium sulfate
were dried at 300° ?. Solutions were prepared
using double distilled water with conductivity
less 1?10-6 Ohm-1cm-1. As background electrolyte
5 ?? calcium nitrate was employed. To measure
electroosmotic flow velocity used 0,1 mM benzyl
alcohol solution. Chloride ?ion was employed as
internal standard.
The equations for correction peak areas
and calculation association constants
Indirect detection in capillary electrophoresis
technique is based on decrease of concentration of
background electrolyte ions in zone of separated
ions. This decrease is frequently recorded by
spectrophotometric method and depended on what
fraction of ions is ionized. To compare peak area of
nonassociating ions with peak area of associating
ions we may calculate association constant with
background electrolyte ions. In addition the peak
areas in capillary electrophoresis with indirect
detection depend on concentration of ions but also
on their electrophoretic mobility, velocity of ion
motion past detector, nature and concentration of
background electrolyte [11-13].
In cases where indirect spectrophotometric
detection is used on the ground of equations relating
optical density change with ion concentration [13]
we suggested the equation for correction peak
areas relative to peak area of internal standard:
§ 1 P M / P st z st · S ic
,
S icc ЁЁ
� ёё �
© 1 P M / P i z i № S stc
(1)
where ?M, ?st and ?i are electrophoretic mobility of
background electrolyte cation, internal standard
ion and studied ion; z is charge of ions. Si?
calculated from
Si
,
ti
S ic
(2)
where Si is peak area found from electropherogram,
t is migration time or using equation
S ic
¦
j
'A j
tj
,
(3)
where ?Aj is optical density change ? j point, j
corresponds to reading number in data set of
electropherogram. Corrected area depends on
only ion concentrations and association.
To calculate electrophoretic mobility of
anions ?ep from experimental data we used folow
equation:
P ep , i
P tot ,i P EOF P ?
l § leff l leff
Ё
U Ё© ti
t mark
·
ё, (4)
ё
№
where ?tot,i is total electrophoretic mobility of ion,
?EOF and ?? are contribution into electrophoretic
mobility electroosmotic flow velocity and
hydrodynamic pressure flow, l and leff are total and
effective capillary length (distance from inlet to
detector), U is voltage, tmark is migration time of
neutral compound.
Relation between concentration of studied
ion Ci and concentration of internal standard ion
?st is follow:
Ci
k i � S icc � C st .
(5)
If ions doesn?t absorb in range
spectrophotometric detection and doesn?t
associate to ions of background electrolyte the
correcting coefficient ki must be equal 1.
# 137 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktoriya V. Sursyakova, Sergey N. Kalyakin? Measurement of Ion Association Constants from Decrease of Peak Areas?
If studied ion produced with background
electrolyte cation the neutral ion pair then
the decrease of peak area prorated fraction of
associated ions. And association constant Kass
concentrations in each zone calculated from
principle of electroneutrality. Then the change
of anion concentration in i zone 'Cit and their
concentration in time ? Cit W equal:
calculated from equation:
'Cit
ki 1 1
�
,
[ M z ] J r2
K ass
(6)
where ki deduced from eq. (5), [Mz+] is
concentration of background electrolyte cation,
?± is mean ionic activity coefficient. Because of
all chemical equilibria influence on peak area
decrease a background electrolyte will not contain
electroosmotic flow modifier (salts of quaternary
ammonium bases) which as is known associated to
anions [8]. Because of the hydrodynamic pressure
is used for suppression electroosmotic flow [14].
Zone mathematical model of electrophoretic
ion motion
To examine deduced equations we used
zone mathematical model of electrophoretic ion
motion. As model system the section of capillary
consist of 4000 zones was taken. Each zone is
theoretical step of separation. Velocity of ion in i
zone describes by equation
Xi
Pi
0
0
U � ? BGE
� P BGE
,
l � ¦ C j,i � P j, i
(7)
j
where ?0BGE and ?i are initial concentrations of
background electrolyte and concentration of
studied ions in i zone respectively, ¦ C j , i � P j , i
j
is sum of products ion concentrations and its
electrophoretic mobility for all ions being in i
zone.
On the basis of eq. (7) shift of each anions
in each zone ?xi in equal time interval ? was
calculated:
'xi
X i �W .
Cit W
'xi
,
l zone
Cit 'Cit1 'Cit ,
(9)
(10)
where lzone is zone length, Cit is anion concentration
in i zone in point of time t.
Ion association was taken into account by
follow:
Pep ( A )
1
� Pep0 ( A ), (11)
1 K ass? ( MA) � [ M ]
Ci , nonass
1
� Ci , tot , (12)
1 K ass ( MA) � [ M ]
where ?ep and ?0ep are electrophoretic mobilities
of studied ion with accounting and without
accounting association, 1/(1+Kacc·[M+]) is mole
fraction of ion form, ?i,nonass ? ?i,tot are concentration
of nonassociated anions and total concentration of
the studied anions in i zone.
It is assumed that shape of the studied ion
range in initial point of time is trapeziform.
The mathematical model allows to calculate
concentration of studied ion in each of 4000 zones
at any point of time. The peak area was calculated
from model electropherogram - concentration
background electrolyte anion in detector area
versus time. Calculations were performed
by programme on basis of Visual Basic for
Applications. Adequacy of mathematical model
is proved that regulating Kohlrausch function is
constant all over capillary [15]. Asymmetry of
peaks giving by model was proved experimentally
too.
(8)
Time interval ? was taken so that ions from i zone
haven?t time to move more than one zone. Cation
'Cit �
Results and discussion
Due to electromigration dispersion the peaks
in capillary electrophoresis are asymmetrical and
each peak has proper asymmetry coefficient (see
# 138 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktoriya V. Sursyakova, Sergey N. Kalyakin? Measurement of Ion Association Constants from Decrease of Peak Areas?
Fig.). Since the corrected peak areas using eq. (1)
for ions with different electrophoretic mobility
and equal concentration may be distinguished.
Because of the eq. (1) was examined with using
zone mathematical model of elctrophoretic ion
motion. As can be seen in table 1 for conventional
anions with electrophoretic mobility from 40·10-9
to 80 ·10-9 m2·s-1·V-1 the calculated corrected
peak areas agreed to the extent of 2,3 %. If S?
calculated from eq. (3) better results were turned
but recalculation of real electropherograms is
too hungus. Deviation in 2,3 % can be induced
both asymmetry of peaks and discreteness of
mathematical model.
Zone mathematical model of electrophoretic
ion motion was used for examining effect of
ion association on the decreases of peaks areas.
Deviation of calculated association constant (eq.
6) from introduced in model using eqs. (11) and
(12) for magnitude of association constant 1 - 300
were below 1,5 %.
Experimentally the separation of chloride
? and sulfate-ions was studied (see Fig.) using
calcium nitrate as background electrolyte.
According to eq.6 association constant of
calcium with sulfate ions were calculated, mean
ionic activity coefficient was calculated from
second Debye-Huckel approach, ?M - with use
of Debye-Huckel ? Onsager equation. As ?M is
present both in numerator and in denominator S?
value wasn?t changed strongly with variation of
?M. lg Kass (??SO4) were 2,39 ± 0,09 (P = 0,95,
5 parallel measurement). This is agreed to results
yielding with using other techniques in particular
capillary electrophoresis technique from changes
of electrophoretic mobility [3] (see Table 2).
Thus the new method based on decrease
of corrected peak area to measure association
constants using capillary electrophoresis technique
with indirect spectrophotometric detection was
investigated. To examine the equations for peak
area correction and calculation of association
constants was used zone mathematical model of
electrophoretic ion motion. Using this method
experimentally association constant of ??SO4 was
measured. The calculated value of association
constant was agreed to value yielding other
tecniques.
mAU
10
5
2
3
0
-5
-10
1
-15
2
4
6
8
10
12
min
Fig. Electropherogram of chloride ? and sulfate-ions. Background electrolyte: 5 ?? ??(NO3)2, U = -15 kV.
2Peaks: 1 ? EOF marker (benzyl alcohol), 2 ? Cl , 3 ? SO4 , equivalent concentration of ions ? 0.5 mM
# 139 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Viktoriya V. Sursyakova, Sergey N. Kalyakin? Measurement of Ion Association Constants from Decrease of Peak Areas?
Table 1. Calculated using eq. (1) peak areas for anions with differ electrophoretic mobility, internal standard ?
anion with ? = 60·10-9 m2·s-1·V-1. S were calculated from model electropherograms. Equivalent concentration
of ions ? 0.5 mM
?·109, m2·s1
·V-1
40
50
0,028725
S?·103,
Eq. (2)
1,143
1,023
S?·103,
Eq. (3)
1,121
0,011406
0, 740
1,010
1,008
0,731
1,003
60
0,006354
0, 569
1,000
0,566
1,000
70
80
0,004168
0, 475
0,993
0,474
0,998
0,003006
0, 415
0,989
0,415
0,996
S
S?
S?
Table 2. The association constant of ??SO4 measured different techniques, 25° ?
Technique
lg Kass (??SO4)
Reference
CE from changes of S?
2,39 ± 0,09
This study
CE from changes of ?
2,551 ± 0,013
2,31
2,27
2,27
2,57
[3]
[16]
[17]
Solubility
Electromotive force
[17]
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???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 142-150
~~~
??? 544.023
???????? ???????????????? ????????? ???????????
?????????????? ??????????????-?????
???? ?. ???????,*, ?????? ?. ?????????,
????? ?. ????????????, ??????? ?. ?????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
???????? ??????????? ???????? ??????????? ? ????????????? ???????????????
????????????? ??????? ?????????? ? ?????? ?????????, ???????????? ??? ??????????????
??????????????-????? ????????? ?????? ? ?????? ???????? ? ?????????? ?? ???????????
?????????????????????? ???????????. ??? ???????? ????????? S/Au = 0,5 - 1,2 ????????????
??????????? Au, ? ?.?. ???????, ????? ???????????? ?? ???????? ???????????. ? ??????
?????????? ???? ?????????? ??????????, ????????????????? ? ????????, ??????, ??????
?? ??????????? ??????????? ????????????? ?????? ?? ???????????????? ?????????????
????????????? ????????? ?????????????? HAuCl4. ???????? ????????? ????????
????????????? ??????????? Au, ???????? ??????????????? ?????????????? ?????, ? ???
??????? ?????????? ???????? ? ???????? ??????? ??????.
???????? ?????: ??????????? ??????, ????, ????????????? ????????, ?????????????????????
??????????,?????????????????????????????,?????????????????????????????????????????,
??????????? ???????? ???????????.
????????
????????? ?? ?????? ??????????????
?????? ? ???? ?? ???????? ????????? ? ??
?????? ????????? ?????? ??????????????.
????? ?? ???????? ??????? ????????? ?????????? ?????? (???) ???????? ??????????
?????????????? ? ?????? ????????? ?????????? ????????? ?????? (III) ?????????? ????????????????. ????????, ??? ???????, ???????? ????? ????????????-???????? ????????,
????? ?????????????? (???????????? ?????
*
1
? ??.), ??????? ???????? ???????????? ??????????? ?? ????????? ? ????????? [1]. ? ?????????? ??????? ??????????? ????????????
????? ??????? ??????? ?????? ????????? ??????????, ?????? ???????? ??????? ??????????? ???, ???????? ????????? ??????, ??????
?????????? ???????????? [2-3]. ?????????
????????????????, ????????????? ????????
?? ?????? ?????????????? ??? ????????????
????? ?????? ??????, ??????????? ??? ?????? ???????? ?????? ?? ?????? ?????????,
Corresponding author E-mail address: yumikh@icct.ru
© Siberian Federal University. All rights reserved
# 142 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
??? ? ?????????? ?????. ??? ??????? ???????? ??????????, ????????, ??????????????
??????????? ???????? (??. [1, 4-6]), ??? ?????? ?? ?????? ?????????.
?????????????? ????????? ??????????
?????? ? ???????-?????? ??? ???????????????
???????? ? ??????????? ?????, ?????? ??????????????? ???????? ??????????? ????????? ? ??????? ??-???????, ??????? ?????????? ???????????? ??????????????? ?????????
? ??? ?????? ?????????? ?????????? ???????? [7-13]. ??? ???????? ???????????? ???????
??? ?????????????, ?????????????? ? ??????
?????????? ?????, ?? ?? ???????, ?????????
? ???? ?????? ?????????? ?????? ?? ??? ???
?? ????. ???????????????? ??????? ? ???????? ? ?????????????? ????? ????? ?????????
????????? ????????: ???????? ??????????
??????? ?????????? ????? ????????? ??????? [14-16] ? ???????? ????? ??????????????? ????? ? ?????? ???????? ???????, ??
20 ??, ?????????? ??????, ? ????????? ?????????? ?? ??????????? ????????? ????????
[8-9]. ???????? ? ??????? ??????-???? ?????
?????? ???????? ??? ???????? ? ???????????
???????????? ????? ??????????? ???????? ?
????? ? ????????? ??? ??????????? ?????????? ??????, ????????????? ?, ? ???????????,
????????? ???????? ???????? ?? ??? ??? ????
??????? [15-17].
????? ????????? ?????? ???? ????????
?????????? ?? ??????????? ??????????? ????????? ?????????????? Au(III) ????????? ?????? ??? ????????? ????????????? ????????
? ??????? ??????? ????????????? ??????????????? ????????????? (????) ? ????????????? ? ??????????? ?????????? ??????????? (??? ? ???).
????????? ? ????????
?????????????
????????? ?????????? ??? ??????? ????
???????? ???????????????????????? ??????? HAuCl4 ? ???????? ??????, ?????????????? ?? ????????? ???????????? «??» ? «???»
? ????????????. ???????? ???????? ???????
???????? ??????? ??????????? ??????????
?????????? ???????? 0,1 ? ???????? ?????? ?
30 ?? ???????? 3,33?10-4 ? HAuCl4 ? ????????
????????????? ???????? ? ???????, ?? ??????? ????, ???? ????? ??? ????????? ???????????. ??? ????????? ??????? ?????????
S/Au (????????, 0,6) ??????? HAuCl4 ???????????? ? ??????? 5 ????? ??? ???????? ???????? ???-???? 400 ?? ????? ???????????
?????????.
????? ???????????? ???????? ???????
5-10 ??? ???????? ?? ???????????????? ??????????? ???????????, ?????? ?? ?????????
??? ????????? ??????????? ? ????????? ????????? ???????????????? ????? ??? ???????? ???????? ????????; ??????????? ????? ??
?????????? ???????? ? ???? ? ?? ????????
??? ???????????????? ???????????. ???????
??????????? ???????? ??????????? ?????????? ??????????? (???) ? ??????-???????
??????????? (???) ? ?????????????? ????
? ??????? ?????????????? ????????????
????????? ?????????? Solver P-47 (??-???,
??????) ?? ??????? ??? ????????? ???????????. ? ??? ? ?????????? ????????????? ?
???????? ????? ???????????? ???????????
??????????? 90 % Pt ? 10 % Ir ????, ? ???
?????? ?????? ?????????? ?????????? ? ???????? ??????????? ???????? ????? 150 ???.
??? ??????????? ??????????????? ? ?????????????? ???????? ??????? ????? ?????
???????? ?????????? ? ??????????? SPECS
(????????). ??????? ?????????? ??? ??????????? ??????????????????????? ????????-
# 143 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
?? Mg K? ??? ????????????????????? ?????????? Al K? ????? ????????????? ?????? ???
??????? ??????????? ????????????????? 8 ??
(????? ?????). ?????? ? ????????????? ?????? ??? ?? ???? 10-9 ????. ?????????? ???????
???? ??? ?????????? ????, ?????? ?????? ???
? ??????? ??????? ???????, ??? ??????????????
?????, ?????? ?? ??????????? ????-????????
Au2S/Au [7-9] ??? ??????????? ??? [10-12]. ?
??????????? ?????????? ???????? ?????????
S/Au ???? 1,5 ?????? ???????? ????????, ?
????????????? ??????? ?????? ???????????.
??? ??????????? ? ??????? ??????????????
??????????? ???????????, ??????? ??????????, ??? ? ??????????? ?????????? ????????
?????????? ?????????? ????? ????????????
??????????. ?????? ??? ???? ?? ??????????
??????????, ?????? ?? ???????????? ????????????? ?????, ????????? ?? ???????? ???
?????? ????, ????? ??? ??????????? ??????????? ??? ???????? ??? ??????????? ??????. ????? ????, ?? ?????? ?????????? ?????
????????????? ?????????????? ?????? ??????????? ????????? ? ??????? ???? ? ??? ??????????? ???????????? ??????? ?????????? ?
?????????? ????? ???????????? ??????. ???????? ??? ?????????? ????? ???????????? ?
?????? ??????.
?????????? ????????? ?????????? ? ???????
300-1000 ?? ?? ???????????? Shimadzu UV300.
??????????-???????????????? ????????????
??????????? ? ??????? ???????????????
???????????? ?????????? JEM-2010 (JEOL).
?????????? ? ??????????
???????? ??????? ??????????? ????????? ?????????? ? ????????? ???????? ????????????? ??????????? ????????? [1]. ??? ??????????? ????????????? ??? ???????? ?????
2 ?? ? ??????? ?????????? ?????????? ???????? ??? 510-540 ??, ??????? ???????? ??????
?????????????? ??????????? ????????? [18].
?? ???. 1 ???????? ???????? ??????? ?????????? ??????????? ????????? ??? ???????
?????????? S/Au 0,6, 1,8 ? 3,0. ??? ????????????? ???????????? ???? 0,5 ? 1,2 ???????-
??????????, ???. ??.
3
2
1
450
600
750
900
????? ?????, ??
???. 1. ?????????? ??????? ?????????? ????? ? ??? ??????????? ?????????, ?????????? ???
?????????????? HAuCl4 ????????? ?????? ? ????????? ? ??????? ?????????? S/Au 0,6 (1), 1,8 (2), 3,0 (3)
# 144 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
?? ???. 2 ???????? ??? ???????????
??????, ???????????????? ?? ????????????????????? ??????????? ?? ????????? ????
?????. ?? ????????? ? ??????? ???, ???????? ??????????? ????? ??? ????????????.
???????????, ??????? ????? ???????????? ??
???????????, ????? ???? ?? ????? ??-?? ????,
??? ??? ???????????? ??? ????????? ?????.
? ?????? ???????, ????????? ???????????? ??? ?? ????????? ????? ????? ???????
????????????? ???????? ? ??????? ???????
????????. ?????????? ???? ?????????? ???
? ??? ????????? ? ?? ???????????? ????
?????.
??? ?????????? S/Au=0,6-1,2 ??????????? ???????????? ????????? ?????????? ??????, ?????? ????????????? ??? ? ????????
?????? ???????? ??????????? ? ????????????, ??????, ??????? ?????? ???????????. ?????? ??? ????? ??????? ?? ?? ?????? (???
? ???????? ??? ???? ?????????? ??????????? ??????? ?????????? ????? 20-30 ??). ?????????? ????? ??????? ??????? 12-20 ?? ??????????? ? ??????? ??????????? ????????? ?
???. ??????? ??????? ???????? ?????, ???
???, ????????, ????? ???????????? ?? ???????????.
??? ??????? ????????? S/Au=1,5 ?????????? ?????? ?? ??????????? ??????????,
?????? ??????? ? ???????????? ??????? ????????????? ? ??????? ?? ????????? ????????
??????????? ???????? ?????? ???????? 1530 ??, ???????????? ????????? ??????. ??????? ????? ??????? ????????? ?? 100-150 ??
?/??? ???????????? ???????? ??????????.
???????? ?????????? ??????????? ?????????????? Au(III) ??? ??????? ?????????
S/Au=3,0, ??????? ????? ?????? ? ??????????,
????? ??????? 3 ? 6 ??. ??????? ????????
??????????? ???????????, ???????? ???? ??????? ??? ??????. ?????? ????? ????????
????? ?, ? ??????????? ?? ??????? (????????-
????? ???????? ? ?.?.), ??????? ??? ??????? ??????? (??????? ???????? ???????????, ?????? ?? ???????). ???????????? ???????
??? (??????????? ?? ???. 2 ?? ?????????)
????????, ??? ????????????? ?????? ???????,
? ??? ???????? ???????? ?????????????????
??????????? ?? 5 ?? ?????????.
??????????? ????????????? ??????????????? ??????? ?????? ? ???? ???? ?? ???.
3. ??? ???????? ????????? ????-?????? ?
????????, ?????? 0,65, ????? ?????? ????? ?
?? ???????? ?? ????????? ? ???????? ????????????? ???????. ????????????? ????? ????
????? ????, ? ???????? ???????????? ??????
?? ???????.
??? ?????????? ????????? S/Au ???????
????? ????????? Au 4f ??????? ??????????, ?
????? ????? ????????? ?? ??????? ???????
??????? ?????, ??? ????????? ?? ???????????
?????? ?????? ?????? Au-S. ??? ?? ?????, ???
?????? ????????? ?? ???????????, ????????, ?
???? ???????. ?????????, ?? 0,2 ??, ????????
????????? ????????? ????? ???? ?????????
???????? ????????? ????????? ? ??????????? ???????????? ??????? (? ???????????
??????? ?????) ? ?????????? ??????????????
????????????? ? ???????????? ?? ????????
?????? ?????????. ????????, ?? ???????
??????? ????? ????? ?? ?????????? ???????
????????????, ????? ???? ???????? ????? ??????????? ??????.
????? ???? S 2p3/2,1/2 ? ?????????? ?????
??? = 162,9 ?? ????? ?????????, ? ????? ??????, ?? ??? ???????, ??????? ?????? ??????????? ??????????????, ??- ? ??????????????
???????????. ??????????? ????? ????????,
??? ?????????????????? ??????? ??????
?????????? ?? ???????? ? ???????-???? (??????? ????? ????? 161,5 ??), ??-????????, ????????? ?? ??????????? ?????????? ?????? ???
? ??????? ???????? ??????. ??? ???? ?????
????????????? ?????????? Au 4f7/2 ? ????????
# 145 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
?
?
?
???. 2. ??? ??????????? (?????????????? ????) ? ??????? ??????????? ???????????
? ????????????????? ?????????? ??????????? ?????????????? ???????????????, ???????????
??? ??????? ?????????? S/Au 0,6 (?) 1,5 (?), 3,0 (?)
# 146 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
2Sn
S 2p
Au 4f
22-
5
????, ???. ??.
????, ???.??.
5
4
3
S
SO4
4
3
2a
2a
2
2
1
90
88
86
84
172 170 168 166 164 162 160
82
??????? ?????, ??
??????? ?????, ??
???. 3. ????????????? ??????????????? ??????? ???????????????? ?? ??????????? ????????? (1-5) ?
???????????? (2?) ??????????? ?????????????? ??????, ?????????? ??? ??????? ?????????? S/Au 0,65
(1), 1,2 (2, 2?), 1,8 (3), 3,0 (4), 6 (5)
????? ????? 85 ?? ???????????? ???????????
?????????? ?????? (I). ???????????? ?????????? (??????? ????? ???????? 162,6 ??) ???????? ???????? ??????????? ?, ?????? ?????,
???????? ??????????????? ?? ?????? ? ????????? ????? ????? ?????? S ? ????????? ????????? ?????? ?? ?????? [19-20].
???????? ?? ???? ?????????? ?????????
S/Au ? ????????? ???, ????????? ????????? ?
???????? ???? ???????? ??????????, ?????
0,7, ?????? ????????? ?????? ? ??????? ?????????????? ????????????? ???????, ??? ????????? ??????????? ??? ??? ?????? ????????,
??? ? ??? ?????????? ????????? ????????.
????? ????, ?? ???????????????? ????????
??????, ?????????? ??? ??????? ?????????
S/Au =6, ? ???????? ????? ?? ???????, ???? ?
????????????? ???????? ??????? ?????????
?????? ? ??? ????? 85,4 ?? ? ????????????
????? 161,5 ?? (???. 3, 5). ???????? ????????
??????????? ?? ???????? ??? ?????? ?????????, ?? ????????????? ???????????? ??????
??????????? ?????????? (????????? S/Au ??????).
?????????? ?????????? ????????? ????????????, ??? ??????? ???????? ?????????
?????????????? ??????????????? ????????????? ???????? ??????????? ??????, ??
??????????? ??????? ???? ???????? ???????? ??????????????? ????. ????? ???????? ?????? ????? ????????? ?????????????
?????????? ? ???????? ?????? ??? ???????
?????????? ????/?????? ? ????????. ??????
?? ?????? ????????????????????? ???????
??? ?????????? S/Au=3 ? ????? ?????????? ?
???????? ???????? ??????? ??????. ??????
[21] ???????? ??????? ??????? ???? ?????? ? ???? ??? ?????????????? ???????? ?????????????? ?????? ?? ??????????? ?????????
Au(I) ???????-?????? ? ??????? ?? ? ???????????? Au2S. ??? ????????, ??? ????????????
??????????? ???????????? ?????????? ????? ? ???????? ???????? ? ????, ??? ???????
??????????? ????????? ? ?????? ???? ?? ?????? ??????? ? ?????? ??????? ????? Au 4f7/2
# 147 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
? S 2p (83,9 ? 162,6 ??) ?????? ? ??????? ???
??????? ? ???????????? ??????????????. ???
??????? ????? ?????????, ??? ????????????,
?????? ???????????????? ??????? ??????, ???????????? ??? ???????? ????????? S/Au
= 3 ? ????, ?? ??????????? ??????????? ???
????????? ?????????????? ?????????, ? ?????
?????? ????????????? ? ???????????? ?????????????? ?????? ? ????, ??????? ????????
????????????? ? ???????????? ???????.
?????? ??? ? ??? ??????????? ? ???,
??? ??? ?????????? S/Au ????? 2-3 ? ???????? ? ???????? ????????????? ?????????? ?????????????, ???????? ??? ???? ??????
???????????, ??????? ?????? ????????? ?????????? ? ????, ? ???????? ?????, ??????????? ???????? ?? ????????????? ?/??? ?????????? ??????????. ??? ????, ??? ?????????
???????????? ??????????? ????? ???????????,
????????, ?? ???? ????????????? ??????????
????????????? ???????? [22], ????????????,
??? ???????????? ???????? ??????????????
??????? ???? ?? ???????? ??????? ??????????.
?????????? ????????????? ?????? ?????????????? ?????????? ?????????????? ??????
????????????? ??? ???????? ?????????????
????????????, ? ??? ????? ?? ????? ????????
??????????, ??? ??????????.
?????? ????????? ??? ????????? ??????? ??????????????? ??????? ?? ??? 96, ???????
??????? ???? ?? ??-5487.2006.3 ? ??-2149.2008.3 (?.?. ??????).
?????? ??????????
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# 149 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ??????, ?????? ?. ????????? ???????? ???????????????? ????????? ??????????? ???????????????
A Study of the Immobilized Products of Tetrachloraurate
Reduction by Sulphide Ions
Yuri L. Mikhlina, Maxim N. Likhatskia,
Irina A. Yaroslavtsevab and Zinaida V. Borisovab
a
Institute of Chemistry and Chemical Technology SB RAS,
42 K.Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The products of the reduction of chloroauric acid by aqueous sulfide ions immobilized onto highly
oriented pyrographite (HOPG) have been studied by scanning probe microscopy, electron microscopy,
X-ray photoelectron and optical absorption spectroscopy. The gold nanoparticles (Au NPs), including
tabular ones, formed at initial S/Au ratios of 0.5 ? 1.2 have poor adhesion to the inert HOPG surfaces.
With increasing the content of sulfide, the quantity of Au NPs, which nucleate in the solution, decreases,
while nanostructured films more easily deposit on HOPG from liquid or amorphous intermediates of the
gold reduction. The main end products are metallic Au NPs capped with polysulfide-type species and,
at a high sodium sulfide content, amorphous gold sulfide.
Keywords: gold nanoparticles, sulfur, intermediates, HOPG, immobilized nanostructures, X-ray
photoelectron spectroscopy, scanning probe microscopy.
# 150 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 151-165
~~~
??? 634.085:582.632+547.914
????????? ????????? ???????? ?? ??????? ???? ??????
? ???????? ??? ??????????????? ??????????
???????? ?. ??????????,?*, ??????? ?. ??????????,
?????? ?. ?????????, ??????? ?. ???????,
??????? ?. ?????????, ?????? ?. ??????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????????????, ??????????, 660036 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ??????
?
???????? ????????? ?? ???,
?????????????, ??????????, 660036 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
????????? ?????? ????????? ????????? ???????? ?? ??????? ???? ??????, ???????????
?????? ?????????? ???????? ?? ??????? ???????? ???????? ? ??? ????????????. ?????? ??
??????? ???????????????? ????????? ???????? ? ????????????? ????????????? ????????????.
????????? ????????? ???????? ???????????? ? ??????? ???????-????-?????????????,
FTIR ? ???-?????????????. ??????? ??????????????? ?????????? ??????????? ?????????
???????? ? ????????????? in vitro ? in vivo.
???????? ?????: ??????? ???? ??????, ???????? ????????, ?????????, ?????????????,
??????????????? ??????????.
????????
???????? ????????????? ?????????????
??????? ??????? ?????????? ? ???????? ???????????? ???????? ??????? ? ?????????????
??????? [1]. ? ????????? ????? ?????????? ???????? ???????????? ? ???????????? ??????????????, ?????????? ?? ??????????? ? ??????
????????????? ??????????? [2-5]. ???? ??
???????????? ?????????? ????????? ?????????????? ? ??????? ????? ???? ?????? ? ???????. ???? ??????, ????? ?????????????????,
???????? ?? 40 % ???????? [6-8]. ??????? ?
*
1
??? ??????????? ????????? ??????? ??????
????????????? ?????????? (???????????????,
???????????????, ?????????????????, ???????????????????? ? ??????) [2-5, 9-12].
???????????????? ?????????? ??????????? ????????? ???????????? ????????
?????????? ???????? ? ???? ??????? ? ????????? ???????, ??????? ???????? ?????
??????? ???????? ???????? ? ?????? ????????????. ????????, ??? ??????? ???????? ???????? ?? ????????????????? ???????? [13].
????? ???????? ???????? ??????????? ?????????????? ????????, ????? ??? ???????????,
Corresponding author E-mail address: ksa@icct.ru
© Siberian Federal University. All rights reserved
# 151 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
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??????, ??????????? ?????????????????? ?
????-???-??????????. ??????????? ????????
???????????? ?????????????? ?????? ????????? ????????? ????????? ?????, ????????
????????? ? ??????????. ????? ????, ??????
?????????? ????????? ????????????? ???????? ???????????? ????????? ??????? ? ?1,8
???? ? ???????? ??? ????? ????????????????
?????????? [9]. ????????? ?? ???????? ???????? ???????? ??????????????????, ???????-
???? ???????????? ?? ????????? ???????? ??????? ??????? ???????? ????????. ????? ????,
???????? ?? ?????????? ??????????????????
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???????? ?????? ? ??????? ?? ???????? ?????????? ???????? ? ????????? ????.
????? ??????? ???????????? ????? ?????????? ?????? ???????? ??????? ????????? ???-
??????????????, ??????????????? ? ?????????????????? ??????????? [4?12].
???????? ?????????? [3?,28-?????????????-20(29)-??(1)] (???.1) ???????? ?????????????????? ? ??????????? ????????? [2, 3].
????? ????, ???????? ?????????? ?????? ?????? ??? ?????? ???????????? ????????, ?????
??? ????????? ??????????? ???????, ??????????????? ????????, ?????? ???????????????? ????????? ???????? ? ?????? [14, 15].
?????? ???????? ??????????????? ?? ???????
???? ??????, ????????????? ? ?????????????
??? ?????????, ???????? ??? ???????????????
??????????.
CH3
H2C
CH3
CH3
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CH3
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???. 1. ???????? ????????
????????? ??????? ????????? ?????????
???????? ???????? ?? ???????????? ???????? ?????????????? ????????, ??????????????
??????????? ?? ???? ?????? [14, 16-18]. ???
???????, ??? ???????? ??????????????? ?
??????? ??????? ????????????? ????????? ?
????????????? ?????????. ????????, ??? ??????? ??????? ????????? ???????? ?????? ????????????? ???????? ???????? ???????? ???
????????????? ??????????? ??????? ? ????-
????????????????? ?????
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? ???????? ????? ???????????? ???????
???? ?????? Betula pendula Roth., ????????????? ? ?????? ?. ???????????. ?????????? ?????? ??????? ???? ?????? ??????????? ? ????.
1 [19].
?????? ????????? ???????? ?????????
????? ????????? ???????, ???????????? ??
??????? 2 ? 5 ?? ? ?????????? ??? ??????????? 105 o? ?? ????????? ????? 2 %, ??????? ???????? ???????? ??? ??????????? ??
??????? ? ???????????? ?????, ??????????
???????? ?????????????. ????? ??????????
??????? ???????? ??????? ???????? ?? ???????? ?????????? ?? 1/10 ??????, ? ???????
???????? ? ??????????? ?????????? ????. ???????? ?????? ???????????????, ??????????? ????????? ?? ??????? ????????????????
????? ? ?????????? ?? ???????. ?????????????????? ??????????? ???????? ????????? ??
??????? ? ??????????? ??????????????? ????
????? ??-?.
?????? ? ????????????? ??????????
????????? ?? ?????????????????? ? ???????
????????? ???????? ??????????? ?? ???????-
# 152 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
??????? 1. ?????????? ?????? ??????? ???? ??????
??????????,
% ?? ????? ?.?.?.*
0,52
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24,28
????????, ?????????????? ?????
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?????????
3,85
??????
-
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4,80
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???????
34,4
* ?.?.?.- ????????? ????? ???????.
????-???????????? GCD Plus (?Hewlett
Packard?, ???) ? ?????? ????????????? ??????????? ????????????? ???????? ??????.
??????? ??????????????????? ???? ??????????: ??????????? ????? ????? ? 250 °?,
???????? ??????? ??????????? ? 5,00 °?/???,
???????? ?????? ????-???????? ????? ?????
??????? ? 1,0 ??/???; ??????????? ??????????? ????? ? 250oC, ????????? ????? ? 165oC,
????? ???????????? ????? ??? 70 eV, ?????
???????????? ?????????? ? ?? 45 ?? 450 m/z
??? 0,5 ?/???. ????????? ??????????? ??????? HP-5S, ????? ? 30 ?, ??????? ? 0,25
??. ?????????? ??????????? ????????? ??
???????? ?????????????????????? ?????.
???????????? ?????? ?????????, ?????????
??????? ??????????? ? ?????? ????-????????
? ???????????????? ??????? ??????????
????-????????????.
??-??????????????????
????????????
??????????? ???????? ????????? ?? FTIR????? ???????????? Vector 22 (Bruker). ???????? ???????? ?????????? ? ?????????
?????? ? ??????????? ???????. ?????????
???????????? ?????????? ????????? ? ?????????????? ????????? OPUS/Y (??????
2.2). ???-?????????????????? ????????????
??????? ???? ??????????? ?? ????????????
Bruker DPX-200 ??? ??????? 200 MHz = (1?),
???????????? ? ?DCl3.
?????????? ?????? ?????????? ????????? ? ?????????????? ??????????? ???????????
FLASH TM 1112.
???????? ?? ?????????? ???????? ????????????? ????? ? ??????? ??? ?? ?????????? «Silufol», ?????? ? ????????? : ?????? (20:1).
???????? ??????????????? ??????????
??????????????? ?????????? ?????????
???????? ??????? ? ????????????? in vitro ? in
vivo [20-25].
? ????????????? in vivo ??????????????
????????? ??????????? ????????? ???????
(???) ???????????? ?? ????? ???????????
?????? ????? 200 ? 300 ? ? ???????? ????????????? ???????. ??????????????? ?????????? ????????? ?? ?????????? ??????????
??????????? (???) ? ?????????? ?????????
??????????????????? (???) ? ????????.
????????????????? ???????? ??????????? ?? ??? ??????: ???????? (?????????),
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??????? ????? ???????????? ??????????? ? ??????? ??? ????????? ??????????? ??? ??????-
# 153 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
????? ? ???? ? ????. ?????????? ? ???????
?????? ???? ?????????? ?????????? ????????? ? ????????? ? ???????? ? ????? ? ??????? 2
?????? ?????????. ??????? ?????? ???? ?? 30
????? ?? ?????? ?????????? ?????????? ??????? ?????????, ?????????? ???????? ???????? (50 ?? ????????? ???????? ?? 1 ?? ????
???? ?????????).
??????? ?????? ??????????? ??????????????????? ??????? ?? ????????????? ??????? ????????????? ?????????? ? ????????
????? ? ??????????? ??? ?????????? ?????????? ????????????? ?????-?????????, ??????? ???????? ????????? ?????? ?? ??????
?????????. ?? ????????????? ?????????????
?????????? ?????? ?? ????????????? ?????????? ?????????? ??? ????? ????? 347 ??
(??????????????? «??-46»), ??????????????
??????????? ????????? ????????? ? ??????????? ?? ??????? ???????????? ???????????,
???????? ???????? ?????????? ??? 480 ??.
? ???????? ????????? ??? ???????????? ?????????????? ????????? ? ???????????
?? ?????????? ??????. ? ???????? ?????????
50 ??? ??????????? ??????????? ? 450 ???
??????????? ???????????????? ????. ????????????? ??????????? ??????????? ??????????? 250 ??? ????? ??????/?????????
(2:1). ?????????? ????????? ??????????
???????????? ? ???????????????? ??? 8000
??/??? ? ??????? 15 ?????. ??????????? ???????????? ??? ??????????? ?????????? ???.
??????????? ?????????? ??? ? ??????????
?????? ????????? ??????????. ??? ??????? ?????????? ??? ???????????? ?????????? ???????? ?????????? ???????? ? ??????? ????. ?? ???????? ??????? ??????????
??? ??????? 50 %-? ????????????? ???????
????????? ??????????. ??????? ???????????? ????????????? ???????????? ?? ???????
?.?(50%)=(????????)Ч100%/????, ??? ???? ? ???-
?????? ???????? ?????; ??? ? ????????? ??????? ?????.
?????????? ???????? ?????????? ?? ??????????? ??????????? ? ?????? ???? ????????? ?? ??????????? ? ???? ?????????? ???????
???????? ???????? ? ?????????? ??????? ??
??????????????? «???-2». ?????????? ???????? ???????????? ?? ??????? ?=(????+???)/
(V*t*K), ??? ? ? ?????????? ????????, ????/
(???*??); ???? ? ????????? ???????? ?????;
??? ? ????????? ??????? ?????; V ? ?????
????????? ???????, ??; t ? ????? ?????????,
?; ? ? ??????????? ?????????, ?????? 22,2
?-1??-1.
??????????
??????????
??????????? ?????????? ?? ????????????????
«??-46». ??? ?????????????? ??? ?
2-??????????????? ???????? (???) ?????????? ??????????? ????????? ? ??????????
?????????? ??? ????? ????? 532 ??. ??????
???????????? ??? ??????????? ?? ???????
? = ?*f/?, ??? ? ? ???????????? ???, ????/
?? (??? ?? ????? ?????); ? ? ?????????? ????????? ??? ????? ????? 532 ??; f ? ??????????? ??????????; ? ? ??????????? ?????????
???, ?????? 1,56Ч105 ?-1??-1.
? ????????????? in vitro ????????? ??????????? ????????? ??????? ???????? ????????? ????????? ? ???????? ?????? (II) ? ??????????? ?????, ?????????? ?????????? ?
?????? ????? ????. ?? ?????? ??????????????? ?????????? ????? ?????? ?? ??????????
?????????? ??????????? (???) ? ??????????
????????? ???????????????????? (???) ?
????????.
?????????????? ????????? ???????????
????????? ???????? ???????????? ?????????? ? ??????????? ????????? EXCEL. ???
?????? ?????????????? ????????????? ???????? ???????????? ??????? ??????? ???????????? ???????? ?????????.
# 154 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
?????????? ? ??????????
??????????? ??????? ???????
????????? ???????? ?? ??????? ????
??????
??? ??????? ??????? ?????????????? ??????? ???????? ????????, ??????????????
???????????? ????? ????????? ????????, ??????????? ????????????????? ???????? ?????????????? ?? 0,5 ?? 18 ????? ? ???????????
(??????????? ?????? ??????? ? ?????? ???????? ???????) ?? 1 : 20 ?? 1: 50.
?? ???. 2 ???????????? ?????? ????????????? ????????? ?????????????? ???????
??????? ???????? ???????? ? ??????? 0,5
(???. 2?) ? 18 ????? (???. 2 ?).
???????????, ??? ????????? ???????????? ??????????? ?? ??????? ???????? ???????? ??????? ? ???????? ????????. ?????
????, ? ????????? ??????????? ????????????
??????, ?????? ??????? ? ????? ?????? ? ?????????? ????????.
? ??????????? ?? ??????? ????????? ??????? ???????? ???????? ????? ???????????? ???????? ???????????? ?? 28,0 ?? 43,9 % ??
????? ????????? ????? ???????. ???????????,
??? ???????????? ????? ???????? (43,9 %) ?
?????????? ??????????? ????????? ????????
(83,5 %) ??????? ? ????? ??? ??????????? 1:
20 ? ????????????????? ???????? 18 ?.
?????? ????. 2 ???????????? ???????
????????????????? ???????? ????????? ??????? ??????? ???????? ???????? ?? ????? ?
?????? ???????? ???????? ??? ????????? 1:20.
????????????? ??????????? ???????? ???????? ??? ?????? ????????????????? ???????
???? ????????? ? ??????? ???????-?????????????????.
??? ??????? ?? ?????????? ???????????,
? ??????????? ????????????????? ?????????
??????? ???????? ???????? ? 0,5 ?? 18 ?????
????? ???????? ????????? ? 32,6 ?? 43,9 % ??
????? ????????? ????? ???????. ??? ????
?????????? ????????? ???????? ? ????????
?????????? ? 33,1 ?? 83,5 %, ? ????????????
??????????? ?????????? ???????? ? 51,3 ??
3,7 % .
??????????? ???????????? ????????????, ??? ??? ????????? ??????? ???? ??????
???????? ???????? ???????????? ? ??????????? ???????? ? ??????? ???? ??? ????????????. ????? 30 ??? ????? ?????? ??????? ?????????? ???????? ?????????? 51,3 %, ???????
9,2 %, ? ????????? ???????? ? 33,1 %. ??? ????????????????? ??????? ????? 30 ??? ? ????-
??????? 2. ??????? ????????????????? ???????? ????????? ??????? ??????? ???????? ????????
?? ????? ? ?????? ???????? ???????? (?? 1:20)
*
?????? ????????,
% ?? ????? ????????*
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???????
51,3
9,2
4,3
?????????????????, ?
????? ????????,
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32,6
????????
????????
33,1
4
37,5
67,1
22,6
2,7
4,8
2,8
6
38,8
68,8
22,6
1,7
5,0
1,9
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8
39,8
72,8
17,5
2,2
5,5
2,0
10
39,7
77,6
8,7
0,8
7,4
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14
40,8
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6,4
18
43,9
83,5
3,7
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5,5
?????? ???????-????-??????????????????? ???????
# 155 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
1 ? ??????, 2 ? ?????? ???????, 3 ? ???????, 4 ? ???????? ????????
???. 2. ?????? ????????????? ????????? ?????????????? ??????? ???????? ???????? ???
????????????????? ??????? 0,5 ? (?) ? 18 ? (?)
# 156 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
???. 3. ????-??????? ??????? (?), ???????? (?), ????????? ???????? (?)
# 157 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
??? ??????? ???????? ??????? (?? 1 : 20)
??????????? ??????? ???????????? ????????? ? ??????? ??????????? ?????. ??? ????? 4
???? ?? ?????? ??????? ?????????? ???????? ?
???????? ??????????? ?? 22,6 %, ??????????
??????? ? ?? 2,7 %, ? ?? ????? ??? ?????????? ????????? ???????? ?????????? ?? 67,1 %.
????? 10 ????? ????? ?????? ??????? ?????????? ????????? ???????? ? ???????? ??????????
77,6 %, ???????? ? 8,7 %, ? ??????? ??????? ?
7,4 %.
????????????????????? ?? ??????? ???????? ???????? ??????????? ????? ????? ??????????? ????????? 222 - 223 ??, ??? ????????????? ??????????? ????????? ?????????
????????, ??????????? ????????? ????????
?? ????????? ???????? [26].
?? ????????? ?????? ??????????? ??????? ???????, %: (?) 78,06; (?) 10,2; (?) 11,9. ?????????, %: (?) 77,6; (?) 10,3; (?) 12,2.
?????? FTIR, 1H ???-????????????? ?
???????????? ????????????? (???) ?????
?????????????? ?????????? ??????? ???
???????? ???????? (3?,28-??????????-??? 20
(29)-??), ?34?54?4.
??-?????? (?,??-1): 3070,9 (?=?); 2953,56;
2872,73 (???); 1739,93 (?=?); 1458,23;
1391,79; 1368,56 (??? ); 1246,14; 1151,11;
1108,63 (????? ).
?????? 1?-???: 4,72 (1?, ?, =??2); 4,55
(1?, ?, =??2); 4,47 (1?, ?, ?3); 4,26 (1?, ?,
J10.7 ??, ?28); 3,86 (1?, ?, J10.7 ??, ?28); 2,50
(1?, ?, ?19); 2,08 (3?, ?, ??3??); 2,03 (3?, ?,
??3??); 1,65; 1,02; 0,94; 0,82; 0,80 (??? 3?, ?,
??3).
?? ???. 3 ???????????? ????-??????? ????????????????????? ???????, ????????, ????????? ????????.
?? ???. 4 ?????????? ?????? ????????????? ?????????????????????? ????????
?????????????? ??????? ???????? ????????.
????????
??????
???????-????????????????? ???????????, ??? ????????????????????? ?? ????????? ?????? ???????
????????? ??????? ???????? 95,3 % ?????????
???????? ? 4,7 % ??????? ???????.
???. 4. ?????? ????????????? ?????????????????????? ???????? ?????????????? ??????? ????????
????????
# 158 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
???????????? ???????????????
?????????? ????????? ????????
? ???????????? in vivo ? ????????
????????????? ???????
??????????????? ???????? ???????? ??????????????? ???????????? ???????????????
?????????? ??????????? ???????? ???????
?????? ? ??????? ?????????? ????????? ??????????? ????????? ??????? (???). ????????
?????????? ???????? ??? ???????? ??????????????? ?????????? ????? ???? ????????
???????? ?????? ?????? ? ??????????? ????? ? ???????? ?????????????? ???????. ???
??????????? ??????????? ?????????????
????????? ? ?????? ?? ?????????? ?????????? ????? ???????? ??????????? ?????????? ?
???????? ????????? ??????????, ??????? ???
???????????? ?????. ? ??????????? ? ????????????? ????????????? ??????? ??????????
??????? ????????????????? ????? ??????????? ?????????? ??????????? (???) ? ??????? ? 2-??????????????? ???????? (???), ???
???-????? [20-25].
?????????? ????????????? ?? ??????????? ??? ? ?????? ? ??????????? ????? ????????????????? ???? ???????????? ? ????. 3.
??? ????? ?? ??????????? ? ????. 3 ??????, ???????????? ??? ?????????? ??????
???????? ????????? ?????????? ??? ????????? ???????? ?? 21 %, ? ???????????? ???
? ??????????? ?????????? ?????? ??????????
?? 57 %. ??????????? ?????????? ??????????
??? ? ?????? ????, ?????????????? ?????????? (??????), ?? ????????? ? ???????????? ?????????, ??????????? ? ?????????????
??????? [24]. ??????? ????????, ??? ???????????? ??? ? ?????? ? ??????????? ???????
?????? ????, ?????????? ???????? ????????,
????????? ??????????? ?? ???????? ??? ?
?????? ? ??????????? ????????? ???????? ?
?????????? ??? ?????? ??????? ?????? 439
± 10 ?????/? ????? (? ????????? ???????? ?
434 ± 20 ?????/? ?????), ? ??? ? ??????????? ??????? ?????? ???????? ?????????? 8,0
± 0,4 ?????/?? (????????? ?????? ? 7,0 ± 0,3
?????/??).
?????????? ???????????? ??????????
??? ???????????? ?? ???. 5. ? ??????????
?????? ???????? ?????????? ??? ?????????
????, ??? ? ????????, ?? 36 % ? ?????? ? ??
29 % ? ???????????. ??? ????????? ?? ??, ???
? ????????? ???? ?????????? ????????? ??????????? ??? ???????????? ??????-???????.
????????, ???????? ?????????? ??? ?
?????????? ???????? ??????? ??????????
????????? ???????? ??????????? ?????????
? ????????????? ????????? ???, ???????
? ???? ??????? ??????????? ? ????????? ?
?? ???? ??? ????????????? ???, ???? ?????????? ?????????? ???? ????????? ?????????? ??????? ??????? ???. ? ?????? ??????
????????????? ??????????????? ??????????
??????? 3. ?????????? ??? ? ?????? ? ??????????? ????????????????? ????
???????
????????????
????????? ???????? (n=5)
?????????? ?????? (n=5)
??????? ?????? (n=5)
?????????? ???
??????, ?????/? ?????
??????????, ?????/??
434±20
525±10
(?<0,01)*
439±10
(?<0,01)**
7,0±0,3
11,0±0,5
(?<0,001)*
8,0±0,4
(?<0,001)**
??????????: n ? ????? ???????????? ???????????, ? ? ????????????? ???????????.
* ? ????????????? ???????? ?????????? ?????? ?? ????????? ? ?????????? ?????????.
** ? ????????????? ???????? ??????? ?????? ?? ????????? ?? ?????????? ???????.
# 159 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
?????????
??????????
???????
1,6
1,4
1,2
1
0,8
0,6
0,4
0,2
0
??????
??????????
???. 5. ?????????? ??? ? ?????? ? ??????????? ????????????????? ???? (?.?./?? ? ?.?./? ?????
??? ??????)
??????? 4. ?????????? ???????? ? ?????? ? ??????????? ????????
??????? ????????????
????????? ???????? (n=5)
?????????? ?????? (n=5)
??????? ?????? (n=5)
?????????? ????????
??????, ????/(???*? ?????)
??????????, ????/(???*??)
26,6±0,4
22,8±0,7
(?<0,01)*
28,5±1,8
(?<0,05)**
2,50±0,06
2,64±0,02
(?<0,05)*
3,07±0,07
(?<0,01)**
??????????: n ? ????? ???????????? ???????????, ? ? ????????????? ???????????.
* ? ????????????? ???????? ?????????? ?????? ?? ????????? ? ?????????? ?????????.
** ? ????????????? ???????? ??????? ?????? ?? ????????? ?? ?????????? ???????.
???? ?????? ? ????????? ?????? ??? ? ???????? ??? ???????.
?????????? ?????????? ??? ? ????????,
?????????? ???????? ????????, ?????????
???? ??????????? ?????????? ?????? (?? 6 %
? ?????? ? ?? 92 % ? ???????????), ??? ??????????????? ? ?????????????? ???????? ??????????? ? ?????????? ??? ??????? ????????
?? ????????? ? ????????? ?????????? ?????? ? ? ????????? ? ???????????? ???????????????? ??????????????? ???????. ??????
?????????? ??? ??? ? ???????????, ??? ? ?
??????????? ?? ????????? ??????????? ????????.
???????? ?????? ?? ?????????? ???????? ? ?????? ? ??????????? ????????????????? ???? (????. 4).
?????????? ?????????????? ????????
?????????? ?????? ???????? ???????? ?? 6 %
?? ????????? ? ?????????? ?????????. ? ??
????? ??? ?????????? ???????? ????, ?????????? ???????? ????????, ???????? ?? ????????? ? ?????????? ????????? ?? 23 %.
?????????? ?????????? ? ??????? ??????
?????????? ?????? ???? ?? ????????? ? ?????????? ????????? ????????? ?? 17 %, ? ?
??????? ????????, ????????, ???????????
????????? ?????????? ???????? ? ???????
?????? ?? ????????? ?? ?????????? ???????
???? ?? 25 %, ? ?? ????????? ? ??????????
????????? ? ?? 7 %. ???????? ??????????
???????? ? ?????? ????? ????????? ????????? ?????????? ???, ??? ??? ??? ???????????
?2Ї ? ???????????? ?2?2.
??? ??????????? ???????? ?? ????????
???????? ????????? ??????-??????????
?????????, ??????????? ? ??????. ?????
????????????, ??? ??????? ???????? ?? ???-
# 160 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
?????????? ???????? ????? ???? ???????????? ????? ??? ? ??????? ? ?????????? ?????
????????????????? ?????????. ??????????
??????????? ?????? ??????????, ??? ????????????? ???????? ????????? ??????? ?? ?????????? ???, ???????? ? ????????? ???.
????????????? ?????? ???????????????
? ???, ??? ??????????????? ???????? ?????????
???????? ??? ?????????? ???????? ???????? ?
????????? ????????????? ??? ? ?????????
????? ????. ??? ???????? ????? ????????
? ????????????? ???????? ?????? ???????
?????? ???? ?? ????????? ?? ??????????
??????????? ??????????? ??????? ???, ?????????? ?????????? ??? ? ????????. ??????????? ?????? ????? ????????? ??????????????? ??????????? ????????? ????????.
???????????? ???????????????
?????????? ????????? ????????
? ???????????? in vitro ? ????????
????????????? ???????
?? ??????????????? ???????? ????????
????????? ? ???????????? in vitro ?????? ??
??? ??????????? ?????? ?? ?????????? ???, ?
????? ?? ?????????? ??? ? ????????. ? ???????? ???????????? ???????????? ?????????
??????? ????????? ???????? ?????????????
100 ???/? ?????. ?????????? ??????? ? ???????, 30- ? 60-???????? ?????????? ? ???????
???????? ?????????????? ???????. ?????? ??
?????????? ??? ? ??????? ?????? ???????????? ? ????. 5.
?? ?????????? ?????? ?????, ??? ????????????? ?????????????? ??????? in vitro
?????????????? ??????????? ???, ???????? ?????? ??? ??????????? ????? 30 ?????
????? ??????????? ?????????????? ???????.
?????????? ??? ? ?????????? ????? ?? ????????? ? ??????????? ??????????? ?? 127 %.
???????? ? ?????? ??????? ?????? ????????
????????????? ????????? ???????? ???????
?????????? ??? ?? 62 % ?? ????????? ??
?????????? ???????.
????????? ???????????? ??????????
??? ??? ????????????? ??????? ??????????? ????? 30 ????? ????? ????????? ?????????? ?????? ? Fe2+ ? ??????????, ?? ??????
???? ????????? ???????? ??? ?????? ????
??? ???????? ??????? ????????? ???????? ??
??????????????? ???????? ? ?????????? ?????????????????? (???) ? ????????.
???????? ?????????? ??????, ?????????? ???????? ??????? ?????????? ??? ??
17 %, ?? ????????? ? ????????? ????? 30 ????? ????? ?????? ??????????. ??? ???????? ?
??????? ???????? ????????? ???????? ?????????? ??? ??????? ?????? ???????? ?? 77 %
?? ????????? ?? ?????????? ??????? ????.
??????? ????????? ???????? ?? ?????????? ???????? ? ??????? ?????? ????????????
????. 6.
?????????? ?????????? ???????? ???????? ? ?????? ?????????? ?? 8 % ? ??????????
?????? ???????? ?? ????????? ? ???????????, ? ? ?????? ??????? ?????? ???? ?????????? ?? 20 % ?? ????????? ?? ??????????
???????.
?????????? ?????????? ???????? ? ?????? ?????????? ?????? ???? ??????????, ???
?????????? ?????????? ???????? ????????,
? ??? ???????? ? ???????? ?????????? ???.
????????, ??? ?2?2 ???????? ???????????
???. ????????? ??????? ??????????????????? ? ??????????????? ??????? ???????? ?
?????????? ????????????? ????? ?????????,
??????? ????? ????????????????? ? ?????????? ????????, ??? ?????? ?? ????? ??????????? ????? ???????? ?????????????? ????????.
??? ????????, ?????? ????????????? ???????
?????????? ???????? ???, ??? ???? ???????? ?? ?????????? ?????????? ???????????
??? ????????????? ???????.
# 161 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
??????? 5. ?????????? ??? ? ?????? ????
?????????? ???
??????? ????????????
???????? (n=7)
?????? (n=7)
???? (n=7)
0, ???
30, ???
60, ???
346±7
429±7
(?<0,001)*
416±8
(?<0,001)**
453±9
1030±7
(?<0,001)*
635±4
(?<0,001)**
390±4
398±8
(?<0,01)*
394±3
(?<0,001)**
??????????:
* ? ????????????? ???????? ??????? ?? ????????? ? ?????????.
** ? ????????????? ???????? ????? ?? ????????? ? ?????????? ???????.
??????? 6. ?????????? ???????? ? ?????? ????
??????? ????????????
???????? (N=7)
?????????? ???????? ? ??????,
????/??? ? ?????
33,8±0,6
36,6±0,5
(?<0,01)*
43,9±0,4
(?<0,001)**
?????? (N=7)
???? (N=7)
??????????:
* ? ????????????? ???????? ??????? ?? ????????? ? ?????????.
** ? ????????????? ???????? ????? ?? ????????? ? ?????????? ???????.
???????? ? ????????????? ????? ????????? ???????? ??????? ?????????? ?????????? ???????? ? ???????????????????. ??????????, ???????? ???????? ???????? (???
???? ???????? ??? ????????????????) ????????????? ?????? ??????????????? ?????????.
????????????? ?????? ????????? ???????? ?
?????????????????? ??????? ?????? ?????????. ? ? ??? ? ? ?????? ?????? ???????????
???????? ?????????? ?????????? ??????????? ?? 38 % [27].
??????????
?????????? ??????? ????????????? ?????? ??????? ????????? ???????? ?? ???????
???? ??????, ?? ????????? ???????????????? ????????? ???????? ? ????????????? ????????????? ????????????.
??????????? ?????? ?????????? ???????? ?? ??????? ???? ?????? ? ??? ????????????
??????? ???????? ???????? ??????? ????????
??????? ?????????????? ? ??????? ????
43 % ?? ????? ?.?. ???????. ? ??????????????
??????? ??????????? ???????, ????????????
?????????????, ???????-???? ? ?????????????, FTIR ? ??-????????????? ?????? ??????
???????? ????????? ???????, ? ???????? ?????????????? ?????????? ????????.
??????? ??????????????? ????????
????????? ????????, ????????????? ? ???
??????? ?? ?????????? ???, ?? ??????????
????????? ???????? ? ??? ? ?????? ? ??????????? ????? ????, ???????????? ??????????
???????? (in vivo), ? ????? ??????? ???????
????????? ???????? ?? ?????????? ???????? ?
??????????????????? ? ?????????? ?????????? ??????????? ? ?????????? ?????? ? ????????????? in vitro.
?? ????????? ?????????? ?????? ??
??????????????? ?????????? ????????? ???????? ????? ????????????, ??? ??????????
# 162 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
???????????? ???????? ?????????? ?????????
? ???? ??????? ??? ???????? ???? ?????????, ? ????? ???????? ???? ?????????????
?????? ??????????????? ????????? ? ??? ?
????????, ???? ??????????????? ?????? ?? ??
??????????.
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
??????????? ?.?., ?????????? ?.?. ???????????? ? ???????? ???????????. ?. 2. ???.,
1995. ?. 206-216.
????????? ?.?., ??????? ?.?., ????? ?.?., ??????? ?.?., ????????? ?.?. ??????? ? ??? ???????????. ????? ? ????????????? ?????????? // ????? ? ????????? ??????????? ????????.
2005. ? 13. ?. 1 ? 30.
????????? ?.?., ?????????? ?.?., ??????? ?.?. ? ??. ????????????????? ???????? ?????????????? ???? ?????? // ????????. ? ????. ????????. 1993. ?. 56. ? 4. ?. 53?55.
?????? ?? ? 2276980, ??? ? 61 ? 31/56, ? 61 P 9/04. ???????????????????? ????????.
????????? ?.?., ???????? ?.?., ???????? ?.?., ???????? ?.?., ??????? ?.?. ?????? ?
2005105707/15. ???????? 01.03.2005. ???????????? 27.05.2006, ?? ? 15.
?????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ??????? ?.?. ??????????
???? ?????? ? ????????????? ?????????? ? ????????????????? ???????????. ???????????
???? ?????? // ??????????????? ?????. 2006. ?. 32, ? 1. ?. 42-55.
????????, ?. ?. ????????????? ???????? ???????: ?????????, ??????, ????????, ?????????? // ????? ?????????. 1994. ?3. ?. 3 ? 28.
??????? ?.?., ??????? ?.?. ??????????? ????????? ????? ???? Betulla // ????? ????????? ??????????. 1988. ? 3. ?. 325 ? 341.
?????? ?? ? 2264411 ?????????? ?????????, ??? 7 ?07J 53/00,63/00. ?????? ????????? ???????? / ????????? ?.?., ???????? ?.?., ???????? ?.?., ?????????? ?.?.; ?
2004122661/04; ?????. 23.07.2004; ?????. 27.11.2005, ???. ? 33.
??????? ?. ?., ?????????? ?. ?., ??????????? ?. ?., ??????????? ?. ?.. ?????? ? ????????????????? ?????????? ???????????? ???????? // ??????????????? ?????. 2002. ?. 28. ? 6.
?. 543 ? 549.
??????? ?.?., ????????? ?.?., ?????????? ?.?., ??????? ?.?., ????? ?.?., ??????? ?.?.,
????????? ?.?. ?????? ? ????????????????? ?????????? ?????? ????????, ???????????
??????? ? ???????????? // ??????-???????????????? ??????. 2005. ?. 39. ? 8. ?. 9 ? 12.
??????? ?.?., ????????? ?.?., ?????????? ?.?., ??????????? ?.?., ??????? ?.?., ???????
?.?., ????? ?.?., ????????? ?.?. ?????? ? ????????????????????? ?????????? ????? ??????????????? ???????? // ??????-???????????????? ??????. 2005. ?. 39. ? 8. ?. 9 ? 15.
????? ?.?., ???????? ?.?., ?????? ?.?., ?????????? ?.?., ???????? ?.?., ? ??. ?????? ??????????????? ??????????? ??????????? ? ??????????? ?????? ? ?? ?????????????????
?????????? // ??????????????? ?????. 2005.?. 31.?.1. ?. 320 ? 325.
??????? ?.?., ?????? ?.?., ??????????? ?.?., ??????? ?.?., ????????? ?.?., ?????????
?.?., ?????????? ?.?., ???????? ?.?., ??????? ?.?., ?????????? ?.?., ????? ?.?., ???????
?.?., ????????? ?.?. ?????? ? ????????????????? ?????????? ????????????? ??????? ??-
# 163 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
????????? ??????? ? 28-????-???????????? // ??????-???????????????? ??????. ?.38.?
3. 2004. ?. 31-34.
14. Patent US 7041701. Triterpenoid derivatives. 09.04.2006.
15. ??????? ?.?., ?????? ?.?., ????? ?.?., ??????? ?.?. ????????????? ????????? ????????
? ????????? ??????. ???. ????. IV ??????. ????. ????. «????? ? ?????????? ????????????
???????». ?????????. 2006. ?. 453.
16. ???????? ?.?., ???????? ?.?., ??????? ?.?. ?????? ????????? ????????? ????????. ??17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
???? ?? 2150473. 2000.
???????? ?.?., ?????????? ?.?., ?????? ?.?., ????????? ?.?. ????????? ???????? ? ???????? ?? ???? ??????, ?????????????? ? ???????? «????????? ?????????????». ????? ????????????? ?????. 1998. ? 1. ?.5 ? 9.
Krasutsky Pavel A., Carlson Robert M., Nesterenko Vitaliy V. Method for manufacturing betulinic
acid. Patent US 6271405. 2001.
?????? ?.?., ??????? ?.?., ????????? ?.?. ?????????????? ?????????? ?????? ????????????? ?????. ?.: ?????? ??????????????. 1968. 59 ?.
?????????? ?.?., ?????? ?.?., ?????? ?.?., ??????? ?.?., ???????? ?.?., ???????? ?.?.
????????????? ??????. ???????????? ? ?????????????. ?.: ?????. 2006. 556 ?.
?????? ?.?., ?????????? ?. ?. ???????????????? ??????? ???????????? ???????????????????? ????????? ? ??????????????? ??????? ????????? // ??????? ????????????? ??????????? ????????. 1998. ???.4. ?. 49 ? 53.
?????? ?.?., ???????? ?.?., ?????? ?.?. ??????????? ?????????????? ??????? ??? ??????
???????????. ???????????? ????????????. ??????????, 2001. ?.17 .
??????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?. ?????????? ??????????? ????????? ??????? ? ????? ????. ??????? ? ?????????. 1991. ?. 58-62.
Abuja P., Tatzber F. Monitoring oxidative stress and lipid peroxidation. Clinical laboratory Int.
2001. V. 7. P. 18 ? 19.
???????? ?.?., ?????? ?.?., ???????? ?.?. ?????????? ????????? ??????? ? ?????? ??????????? ????????? ???????????????? ? ????????????? ??????. ???. ????. 1984. ? 9. ?. 540
? 546.
?????? ?? ? 2324700, ?????? ????????? ????????? ??????????. ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?.. ?????? ? 2007101115/04(001177).
??? ?07J 53/00 (2006.01.) ???????? 09.01.2007
??????? ?.?., ????????? ?.?., ????? ?.?., ????????? ?.?. ???. ?? 2014841. ???????????????, ?????????????????????, ????????????????????? ? ??????????????? ????????.
1994.
# 164 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ??????? ?. ?????????? ????????? ????????? ???????? ?? ??????? ???? ???????
Obtaining Betulin Diacetate from the Outer Birch Bark
and Studying it?s Antioxidant Activity
Svetlana A. Kuznetsovaa,b, Natalia Yu. Vasil?evab,
Galina S. Kalachevac, Nadezhda M. Titovab,
Evgenia S. Red?kinaa and Galina P. Skvortsovaa
a
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Institute of Biophysics SB RAS
Akademgorodok, Krasnoyarsk, 660036 Russia
The new method of betulin diacetate obtaining from the outer birch bark was suggested. This method
combines stages of the betulin extraction from the bark by acetic acid and it?s following eterification.
The advanced method don?t require preview of getting betulin and use of eterification catalysts.
Antioxidantion activity of betulin diacetate has been studed in the experiments in vivo and in vitro.
?eywords: birch bark, betulin diacetate, obtaining, identification, antioxidant activity.
# 165 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 166-180
~~~
??? 541:661.183
?????????? ?? ?????????????????? ?????
????????????? ????
?????? ?. ?????*, ???? ?. ???????,
????????? ?. ????????
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
??????? ???????????? ? ??????????? ?????????, ??????????? ? ????? ??????????? ??????,
???????? ?????????? ?????????? ?? ?????? ????, ??????? ????????????? ????????? ? ????????
?????????, ???????????? ???????, ???? ??????????? ?????????. ????????? ? ???????????????
?????????? ???????? ? ????????? ??????? ???, ?????????? ?????, ?????????????,
????????????? ???????, ????????????-???????? ????????, ???? ? ????.
???????? ?????: ?????????? ?????????, ????????????, ??????????? ?????????, ??????? ????.
????????
??????????? ??????? ??????? ???????
??? ???????????? ??????????? ???????? ????????????? ?????, ??????? ????????????
??????? ??????? ??????? ???????????? ???????? ??? ?????????? ????????? ???????????
? ??????? ????????????? ????????? ???????. ? ???????? ??????????? ?????????? ?????????? ???? ????? ?????????? ??????????,
?????????? ?? ?????????, ???????? ????????
????????, ????????? ???? ? ??. [1-7]. ??????
??? ?????????? ????? ??????? ????????? ?
?? 40 ?? 70 ???. ???. ?? 1 ????? [8], ??? ???????????? ???????? ?? ??????????. ???????
???????????? ? ??????????, ???????????? ??
????????? ????? ??????????? ??????????
??????????? ?? ???????? ? ?????????? ?????,
???????????? ??????? ??????? ? ???????????? ???????.
*
1
???????? ????????? ?????????? ??????????? ?????? ????????? ? ????????? ?? 200
?? 700 ??/?3, ??????? ???????? ??????? ?? ??
??????? ??????????????? ????? ?????????
?????? ????????. ?????????????, ??????????? ???????????? ??????????? ?????????
????????????? ???????????? ?? ????????????
????????? ????????????, ???????????????
?? ???????????? ????? ? ????????????.
? ????????? ?????? ????????? ?????????? ???????????? ?? ?????????? ???????????
???????????, ?????????? ?????????? ????????? ??????????? ??????????? ?? ???????? ?
?????????? ? ???????????? ???? ?????.
????????????????? ?????
????? ???? ??????-????????? ????????
?????????? ?????? ?????????? (2-10 %) ? ?????? ??????????? ???? (0,2-1,2 %). ?? ??????
Corresponding author E-mail address: shchipko@krsk.info
© Siberian Federal University. All rights reserved
# 166 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
??????? ???????? ???????? ?? ???????? ??????? ????????? ????????, ??? ?????????????
?? ???????????? ?????? ????????????? [9]. ?
?????? ?????? ???????????? ????? ????? ?2,
?????????? ??????????? ???????? ???
«????». ??????? ???????? ???????????
????????????? ??? ????? ????: ????????? (Wtr )
? 32,8 %; ?????????? ???? (Ad) ? 9,4 %; ?????????? ???? (Std) ? 0,3 %; ?????????? ???????
??????? (Vdaf) ? 47,4 %; ?????? ??????? ???????? (Qir) ? 3820 ????/??.
??????? ??? ??????? ?? ?????? ???? ?
???????? ???????? ???? ?? ?????????????
?????????? ????????????-????????? ? ????????? ????? ? ?????????? ?????????? ??
??? [10]: ??????????? ???????? ? 7500?, ???????????? ???????? ???? ? 30 ??. %, ???????????? ????????? ? ??????????? ????? ? 4,5
??. %, ????????????????? ?????????? ??????
???? ? ???????? ? 15 ???. ????? ????????? ???
????????? ??????????? ? ???????? ????????
???? ????????? ?? ???.1. ????????? ????????
????????? ???????. ????? ?????????? ??
??????? ???????? ?? ????????? ????? 10 ??
? ????????? ? ??????-???????? ????????? 10.
??????????????????? ??????????? ????? ????????? ?? ??????????????? 5, ??? ??????????
????? ???????? ? ????????? ??????, ??????????? ????????????? 1 ????? ??????? 2, ??????? ???????, ??????????? ????? ???????? ??
?????????? 7. ?????? ??????? ??????????????
???????????? ????????????? 3. ?????????
????? ??????? ??????? ????????? ???????????? ?????????? ????????? ? ???????????
????? ? ??????? ???????? ??? ????????? ??????? ?????? ???????????????. ??????????
???????? ???? ? ????? ???????????? ??????????????????? ?????????????? 8.
??????????????? ???? ??????? ? ???????? 11 ?????????????? ???????, ???????
????????????????? ??????? ???????????
????. ???????? ???????? ? ???????? ?? ????-
???. 1. ?????????????? ????? ????????? ????????????-????????? ? ??????? ????: 1 - ????????????; 2 - ???????; 3 - ??????????? ???????????; 4 - ????????; 5 - ??????????????; 6 - ??????????; 7 - ????????? ???????
?????????? ???????; 8 - ?????????????; 9 - ???? ???????????????? ??????????; 10 - ??????????? ???????;
11 - ???????; 12 - ????????-????????; 13 - ??????; 14 - ???????? ???????? ?????; 15 - ??????????????
# 167 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
?? ???? ???????????? ?????? ???????????????? ?????????? 9. ?????? ???? (???????????? ?????????, ??????? ????????, ????????)
???????????? ???????????????? 15. ??????
??????????????? ???????? ???????????? ??????????? ??? ????????????? ??????? ? ??????? ????????????? ??????. ??? ??????????
? ???????? ????????????? ?????????????? ?
?????????????????? ?????? ? ???? ??????
?????. ????? ????????? ???????? ?????????????? ??????? ????????? ? ???????? ?
???????? 12. ?????? ??????? ???????? ????????? ? ???? ?????????? ????????? 13 ?
???????? ? ????????? 14.
??????? ??? ??????? ? ???????? ?? ???????????? ????? ? ?????????? ?????? (?????? ??? «?????????-?») [11]: ??????????? ?
??????? ???? ???????? ? 800-900 °?, ? ??????
? 600-800 °?; ?????? ??????? ? 250-350 ?3/(?2
Ч?), ?????? ???????? ???? ? 65-75 ??/(? Ч?),
???????? ?????? ?????? ???? ? 320-390 ??/(?2
Ч?). ????????? ????????? ????????? ? ??????? ?? ??????? ??????????? ????.
? ???????? ????? ??? ?????????? ??????????? ???????????? ????? ????????? ??????????, ?????????? ?? ????????? ???????
????????????? ????????? ? ???????? ????????? (?????, ?????, ?????????), ???????????
?????? ????????????? ?????????????? ??????
? ???? ??????????? ?????????.
????????? ?????-????? ???? ?????????
5,0 %; ????????? ? 1,8 %; Vdaf ? 5,8 %; Cdaf ?
91,3 %; Hdaf ? 2,6 %. ????????? ?????-?????
??? ??????? ?? ????????? ???-5? ? ??????
???? ?????? ????????????? ????. ??? ?????????? ??????????? ????????? ? ???????? ?
??????? ????? [12] ??? ??????????? 850 °?;
????? ????????? ?????????? 0,5 ?, ???????????? ????????? ? ???? ? ??????????? ????? ?
5 ? 35 ??. % ??????????????. ?? ??????????
???????? ????????? ???????? ???? ? ???????
? ???????? ????? 0,1 ??. ??????? ?????????
2
?????????? ????-????? ????????? ?? ??? ???????: ????????? ???-1 (? ???????? ??????
????? 1,0 ??) ? ??????????????? ???-2 (?
???????? ?????? 0,1-1,0 ??). ????? ????????
????????? 80 ? 20 % ??????????????.
??????????? ?????? ????????????? ?????????????? ?????? ???? ????????? ?????????????? ( %): ????????? ? 3,6; ????????? ? 1,6;
Vdaf ? 63,4; Cdaf ? 72,3; Hdaf ? 4,1. ???????????
?????? ?????????? ???????? ? ???????????
??????????? ????????? ? ???????? ?? ???????????? ?????. ??????? ???????? ?? ??????????? ?????, ????? ?????????? ??????? 43
??, ????? 500 ??. ??????? ???????????? ??????? ????????? ? ???? ????? ? ???????? ??????????? ?? 500 °? ? ????????? ? ??????? 1 ?.
??? ???????? ??????????????? ????????????,
????? ??????????? ????????? 36?38 %. ?????????? ??????????? (??? ????????????????
??????????) ?????????? ??????????? ????????? ??? ??????????? 800 °?; ??????? ?????????????? ???????? 0,5 ?; ?????? ????????
???? (50 ??. %, ????????? ? ????) 0,25 ??/??
????? ????????? ?????????-?????? ?????.
???? ??????????? ????????? ????????
?? ?????????? ?????????? ??????? ? ???????????? ??????????? (???????????? ???? ??????????????? ???????? ?? ?????? ?? ????? 1
? ?? ?????), ?????????? ?? ????????-??????
?????????, ??????????, ???????? ????? ????????? ?? 0,5 ?? 5,0 ??. ??????????? ????????? ???? ????????? ? ????????????? ????????. ??????? ???? ??? ? ???? ????? ? ????????
??????????? ?? 650 °? ? ????????? ? ???????
0,5 ?. ????????? ??????????????? ???? ????????? ??? ??????????? 800 °? ? ??????? 0,5
? ??? ?????? ????? ???????? ???? (50 ??. %) ?
????????? (1 ??. %, ????????? ? ????).
??? ??????????? ??????-?????????? ?
????????????? ??????? ?????????? ??????????? ???????????? ????????? ???????? [5,7].
????? ??? ?????????? ? ????????? ????????
# 168 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
?? ??? (?. ???????????) ??????? ?????????
????? ????? ? ????????? ????????????? ????????? ??? ??????????? ??????? ????? (??????
?????? ?? ????????????? ????? ???????? ??????? ????????? ?? ???? [13]).
?????????? ?????????? ??????????
???????? ??? ??????? ?????? ?????????
?? ???? ? ?????, ??????, ??????????????,
????????????-???????? ??????? (????????:
?????????, ???????? ??-12, ????????????????? ??????? ???????? (???); ??????????: ???????? ??) ? ??????? ????????????? ??????
(??????????, ???????? ???????). ??? ?????
???????????? ????????? ?????? ????????
?????? ? ????????????? 50 ??/?, ?????????????? (????? ?????? ????????? ??????) ? 80
??/?, ??????? ????????????? ?????? ? 6,5-100
?????/?, ???? (???????? ????), ????? (????????? ?????), ????????????-???????? ??????? ? 100 ??/? ? ??????? ?? ???????? ????????. ?? 92 % ????????? ???????? ?????????
???????????? ???????????????????? ??????.
???????? ???????? ???????? ??-12 ????????
?? 48 % ????????? ?????????????? ???????
?10-?13 ? 23 % ???????????????? ??????. ???
???????? ?? ????? 50 % ????????????????,
27 % ?????????????? ? 20 % ???????????
?????. ??????? ?? ????????? ? ???????????? ?????????? ?????, ???????? ?????????
???????? ?? 48 %, ????????? ?????? ? 0,6 %,
????? ????????? ?????? ? 1,8 %. ????????????? ?????????????? ? ???????????? ?????????? ???? ??????? ??? ???????? ?????? ???????????????? ?????????? ???????????? ?
????????????-??????? ??????? ???.
??? ?????????? ??????????? ?????????????? ???????? ??????????? ???????????
????? ?????????? ??????????? ? ????????
?????????????? ?????????, ??????? ????????? ? ??????? ????????, ????????? ??????????????? ????????? ?????????? ???????????
1? ??????? ???????? ? ??????????? ?????-
??? ???????????????? ????? ? ?????? ???
105 °?.
??????????????? ????? ?????????? ?????????? ?????????? ??????????? ??? ??????????? 105-110 °? ? ??????? 2 ?, ????? ?????????? ? ?????????? ??? ?????????? ??????????
? ????????? ?? 0,2 ??. ?????, ??? ?????????
?????????? ??????????? ?????? ????, ???????? ? ??????? ? ?????????? ??????? 98-99 %
??? ?????????? ????????? ????????? ??????
??? ??????????? 40 °? [1, 6].
??? ???????? ???????????? ??????????????? ????????? ??????? ??????????? ?????? 0,5 ? ???????? ? ????? ? ??????????
???????? ?? 150 ?? ??????? ???????? ??????????, ??????????? ? ????? ?????????????? ?
??????? 5-300 ???. ?????? ??????? ????????
??????????????????, ?????????? ??????????
?????????? ?????????? ? ???????? ?? ????????? ????????? [14]. ??? ?????????? ???????
????????? ??????? ?????????? ???????????
?????? ?? 0,1 ?? 10 ? ??????????? ? ????? ?????????????? ? ?????? ????????? ??????????
? ??????? 48 ?.
?????????? ? ??????????
???????? ?????????????? ??????????
???????????, ?????????? ?? ?????? ???? ???????????? ????????????? ??????-?????????
???????? ? ???????? ? ??????? ????? (???) ?
???????? ?? ???????????? ????? (???), ????????? ? ????. 1. ? ????. 2 ???? ???????? ?????????????? ???????? ?????????? ???????????,
?????????? ?? ????????? ??????? ????????????? ????????? ? ???????? ????????? ???-1
(?????????), ???-2 (???????????????), ???????????? ??????? ??? (???????????????)
? ???? ??????????? ????????? ???? (???????????????) [15-25]. ??? ?????????????
????????? ????? ???????? ???????? ????????????? ???????????????? ????????? ???? ??
# 169 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
??????? 1. ??????-?????????? ? ????????????? ???????? ???????????? ???????????
?????????? ??????????
??????????
???
???
?????????, ???. %
9,6
3,0
????????? (?d), ???. %
12,3
24,4
0,49
0,51
????????? ????? ??? ?? ????, ??3/?
????? ???????? (?? ???), ?? /?
0,13
0,09
????? ???????, ??3/?
0,33
0,38
???????? ??????????? (?? ???), ?2/?
????????????? ?????????? ??
????, %
???????????? ????????, ??/?
????????? ?? ?????????, %
560
485
46,0
25,0
68,0
48,0
23,0
53,2
3
??????? 2. ???????? ?????????? ???????????, ?????????? ?? ????????? ???????
??????????
?????????, %
?????????? ??????????
???-1
???-2
???
???
????
7,4
0,3
0,5
6,4
7,2
?????????, %
2,6
3,5
17,5
1,7
8,8
???????? ?????????, ??/?3
????? ??? (?? ???), ??3/?
?????????
????????
????????????? ?????????? ??
????, %
???????????? ????????, ??/?
186
279
336
293
110
1,80
0,28
1,94
0,39
1,01
0,20
0,60
0,38
2,60
0,33
63,0
77,0
70,1
101,3
70,0
27,0
68,0
61,9
51,1
40,5
???????????? ??????? ???, ??????????? ??
??????????? ????????????? ??????.
?????? ??????????? ??????????? ??????????, ??? ?????????? ?????????? ?????????? ???????? ???????? ?????? ?????????????
??????????? ?? ???????????? ???????? (? ???????????? ? ???????????? ????????????????
????????? ???????? ????? ?????????? ??????
?????????? ?? ????? 210-225 ??/?). ??????? ??
?????????? ??? ?????????? ????????????
??????? ???, ? ????????? ??? ??????? ??? ??
??????????, ?? ?????????????. ??????????
?????????? ????? ?????????? ??????? ????????????? ?????????? ?? ???? (46-70 %) ?,
??-????????, ????? ???? ???????????? ???
??????? ??????? ??? ?? ?????????????? ? ???????????? ????????.
? ????. 3 ????????? ?????????? ???????????? ???????????? ????????? ?????? ?? ?????? ????????? ?? ?????????? ???????????
[26-28]. ??? ? ????????? ???????, ????? ??????? ???????? ????????? ?????? ? 2,49-2,80
??/(?Ч???) ? ??????????? ??? ????????????????? ???????? ?? 5 ??? ?? ???????????????
?????????? ??????????? ???-2 ? ???. ???
????????????????? ???????? ????? 180 ???
??????????? ?????????????? ?????????? ????????? ??????: ????????? ???????? ????????? ?????????? 0,01-0,02 ??/(?Ч???).
?? ???. 2,3 ????????? ???????? ????????? ??????, ??????????????, ???????????????????? ???????, ??????? ?????????????
??????, ???? ? ????? ?? ?????????? ??????????? [29-39]. ??? ????????????? ????-
# 170 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
??????? 3. ???????? ????????? ?????? ?? ?????????? ???????????
???????? ????????? ?????? (??/(?Ч???)) ?? ???????????
?????????????????
????????, ???.
???
???
???-1
???-2
???
???
5
0,75
0,46
0,48
2,80
2,49
0,45
15
0,38
0,27
0,36
0,96
0,94
0,36
30
0,27
0,23
0,27
0,48
0,48
0,26
60
0,17
0,14
0,16
0,24
0,24
0,19
120
0,10
0,09
0,10
0,12
0,12
0,11
180
0,07
0,07
0,07
0,08
0,08
0,08
240
0,05
0,05
0,05
0,06
0,06
0,06
300
0,04
0,04
0,04
0,05
0,05
0,05
?????? ??????????? ?????????? ????????
????????? II ???? ?? ????????????? ???
[40]. ??? ??????????????? ? ??????? ? ?????????? ??????????? ?????? ? ???????????
????????????? ?????????? ????- ? ????????
?, ?????????????, ? ?????????? ???????????????? ?????????. ?????????? ??????????
??????????????? ?????????? ????????? ??
???????????? ??????? ???; ???????? ????????? ?????? (???. 2) ????? ???? ???????? ?
I ????, ?.?. ???????? ???????????? ?????????
?????????????? ????, ? ????? ???? ???????
??????? ???????????????? ????????? ? ?????????? [30, 33].
??????????? ???????? ??????????? ??????????? ?? ????????? ????????????? ????-
?
60
4
5
40
7
3
20
6
2
1
0
0
10
20
30
?, ??/?
???. 2. ???????? ????????? ?????? ?? ?????????? ???????????: 1 ? ???; 2 ? ???; 3 ? ???-1;
4 ? ???-2; 5 ? ???; 6 ? ???; 7 ? ????; ? ? ????????? (??/?), ? ? ??????????? ????????????
??? ??? ?????????? ??????????? ????????????? ??????????? ???? ?????????? ???????.
?????????? ??? ?? ??????? ??? [36-39]. ???
??????????? ????????????? ?? 40-50 ??/? ??
???????? ????????? ???????? ??? (???. 3)
????? ??????????? ? ????????? ???: ???????? > ??????? ??-12 > ???. ????? ???????????? ??? ? ????????????? ???? ??????? ? ????????????? ?? ??????????? ????????
? ???????. ?????????? ??????????, ? ?????
????????? ?????? ??? ????????? ??????????,
??? ??????????????? ???????? ????? ??????
???????????????? ???????????? ???. ????????? ????????? (92 % ??????????????????? ??????) ??????????? ???? ????????? ???????? ??-12 (23 % ????????????????) ?? ????
????????? ????????????? ??????????? ????????????. ???, ???????? ?? ????? ???????
?????????? ????????????????, ??? ? ???????? ??-12, ?????????? ??????????? ???????
???????? ?????????. ??? ??????? ? ????????
? ??? ??????? ?????????? ???????? ?????????? ??????????? ?????. ?????????? ??????
????????? ????????????? ????????? ? ?????????? ????????? ? ???, ??? ?? ????? ??????
?? ??????????? ????????????? ??????, ??? ??
??????????????? ??????? ???????? [41]. ???
??????? ?? ??????? ?????, ??? ?????? ?????
???????? ????????? ?? ??????????? ? ?????? ????? ????????? ???? ?????. ???????????
# 171 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
? 60
?
?
4
40
?
50
5
2
6
25
3
20
8
1
7
0
0
0
10
20
?
30
?, ??/?
?
1,5
10
1,0
9
0,5
0,0
0
4
8
12
?, ?????/?
??????? ??????????? ???? ?????????? ??? ?????????? ?????????? ?????? ??????? ???????
???.
??????? ?? (????????? ???) ??? ??????????? ????????????? ?? 50 ??/? ???????? ??
????????? ????????????? ????????? ?????
????????? ??-12 ? ???: ???????? > ???????
??-12 > ??????? ?? > ???. ??? ???????????
????????????? ???? 50 ??/? ?????????? ????????? ???????? ?? ? ???? ??? ?? ?????????: ???????? > ??????? ?? > ??????? ??-12
> ???. ????? ????????? ????????? ???????? ?? ? ???? ???, ??-????????, ??????? ?
???????? pH ?????: ?????????? ???????????
???????????? ???????? ?? ? ???????? ?????????? ??? ?????????? ??????????? ???? ??????????. ??? ????????????? ? ?????? ??????
?????????? ????? pH ?????? ??????? ?????
8, ? ?????????? ??????? ???????? ????????
?? ???? ?????????? ?????? ??? ? 40-50 ???.
??????? ?????????? ??????????? ?????????-
0
20
40
60
80
?, ??/?
???. 3 ???????? ????????? ???? (1); ????? (2);
?????? (3); ?????????????? (4); ????????? (5), ???????? ??-12 (6), ??? (7), ???????? ?? (8); ?????????? (9), ???????? (10) ?? ?????????? ??????????
???-1; ? ? ????????? (??/?; ??? ?????????????
?????? ? ?????/?), ? ? ??????????? ????????????
??? ??? (?????????? ??????????? ???? ??????????) ?????????????? ??????? pH ??????
???? ? ??????? ??? ??????? ??????????. ?
?????????? ????? ?????????? ??????? ??????
???????????, ??????????? ????????????? ???????? ??????? ??????????? ?, ??? ?????????,
??????????? ????????????? ???????? ????????? ???????? ??, ???????? ? ????????? ????????? ???????? ?? ? ???? ????????? ???.
?????? ?? ????????? ????????? ???
??????????????? ? ???????????????? ???????? ?? ???????????? ??????????? (?? ???????????? ??? ?????????? ??? ??????????
???????) ????????? ????????????? ????????? ?? ??????? ?? ?????????????? ??? ?????? ? ????????????????? ??????????????
???????????? ?? ????????? ?? ????? ???.
????????? ????????? ?? ??????? ??????
???? ?? ?????? ? ?????????????? ?? ???????????? ??????????? ??? ? ??? ? ???????????? ???????? (??????? ????????? 25 ??,
# 172 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
??????? ???? ?????????? ? 250 ??, ????????
???????? ?????? ????????? ??????????? ? 20
?-1) [34]. ???????????? ?????????? ????? ??????? ???????????? ??????? ??? ?? ??????
(48-90 ??/?), ??? ? ?? ?????????????? (123-256
??/?) ? ??????? ??????? ???????????? ????????? ???????? ? ???????? ?????? ????????: ?????? 50-500 ??/? ? ?????????????? 89,51030 ??/?. ????????? ?????????????? ???? ??
???????? ????????? 60-80 ?. ??? ?????????
???????, ???????? ????? ?????????? ???????? ??????????? ??????????? ? ???????????
???????????? ?????????? ? ???????? ????????. ???, ??? ?????????? ???????????? ?????? ? ???????? ???????? ? 10 ??? (?? 50 ?? 500
??/?) ???????? ??????????? ????? ??????????? ? 2 ????. ??? ??????? ??????? ????????
?????????????? ?????????? ????????? ???????????? ?????? ?????????? ???????? ? ???
?? ????????, ??? ? ??? ???????? ??????: ???
?????????? ???????????? ?????????????? ??
90 ?? 1030 ??/? (? 11,4 ????) ???????? ??????????? ????? ??????????? ? 1,8 ????.
?? ??????? ??????? ??? ???????????
??????? ?????? ?????????? ??????????? ?,
?????????????, ????????????? ??????????
???????? ????????????? ???????. ? ????. 4
????????, ??? ??????? ?????????? ?????? ??
??????? ??????? ?????? ???? ??? ??????? ?????????? ???-1: ?? 6 ?? 20 ??/?3.
?????? ?????????? ??????????? ?????
???? ??????????? ?????? ?? ???? ??????????
??????????? ????????????? ??????? ? ????
???????????? ??????? ??????????????? ????????????? ?????????? (??? ????????? ???????????) ??? ?????????-??????????? (???
??????????????? ???????????).
??? ?????????? ???????? ????????? ?
??? ??????? ???????? ?????? ??????? ???????????? ?????? ?? ?????? ??????? ? 10 ???, ?.?.
?? 50 ?? 5 ??/?, ? ?? ?????? ??????? ?????????
???????, ?????? ???????????? ?????? ?? 5 ??
0,1 ??/? (????. 5). ??? ?????????? ????????
????????? ? ??? ??????? ???????? ?????? ??????? ???????????? ?????? ? ?????? ????????
?? ?????? ??????? ?? 50 ?? 10 ??/?, ?? ??????
? ?? 10 ?? 2 ??/?, ? ?? ??????? ? ?? 2 ?? 0,1 ??/?.
? ?????????? ????????????? ???????????????
????? ??????? ?????? ?????????? ??????????? ??????????? ? 4,9-7,2 ????; ? ??? ??????????????? ????? ?????? ?????????? ??????????? ??????????? ? 1,5-1,8 ?? ?????????
? ??????????????? ?????? ? ? 7,3-12,7 ???? ??
????????? ? ???????????????.
?????????? ???????????????? ?????
??????? ??????? ??? ?? ??? (????. 6). ???
?????????? ????????? ? ??? ??????? ????????
?????? ?? ?????? ??????? ??????? ???????????? ??? ? ?????? ???????? ? 10 ???, ?.?. ??
100 ?? 10 ??/?, ? ?? ?????? ??????? ?????????
???????, ?????? ???????????? ??? ?? 10 ??
1 ??/? (?????????? ???????????? ??? ???
????????????? ????????????? ????). ???
?????????? ???????? ????????? ? ??? ??????? ?? ?????? ??????? ???????????? ??? ?
?????? ???????? ?? ?????? ??????? ?? 100 ??
20 ??/?, ?? ?????? ? ?? 20 ?? 3 ??/?, ?? ???????
? ?? 3 ?? 1 ??/?. ? ?????????? ?????????????
??????????????? ????? ??????? ?????? ??????????? ?????????? ??????????? ?? 36-57 %
?? ????????? ? ???????????????, ? ??? ??????????????? ????? ?????? ??????????? ?????????? ??????????? ?? 16-29 % ?? ????????? ?
??????????????? ? ?? 56-70 % ?? ?????????
? ???????????????. ???????? ?????? ???????
??????? ?? ???????? ????????? ??????? ????????. ? ???????????????? ???????? ???????
(? ?????) ??????? ??????? ??????????????
???????????, ??? ??? ?????????? ??????????
???????? ??????? (?.?. ?????? ????? ?????????? ??? ?????????-???????????) ???????? ?
????? ????????????????? ?????????? ????????? ???????? ??????????.
# 173 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
??????? 4. ??????? ?????? ????????? ?? ???????? ?? ?????????? ?????????? ???-1
?????????
????????
????????????
??????????
??????? ??????? ?????? ????????? ( %)
??? ??????? ???????????
10 ??/?3
20 ??/?3
6 ??/?3
????
100 ??/?
74,9
96,9
99,7
????
100 ??/?
94,0
98,5
99,9
?????
50 ??/?
94,0
98,8
99,4
????????
100 ??/?
74,2
90,1
95,0
??????? ??-12
100 ??/?
64,6
86,0
92,0
???
??????? ??
?????????? ???????
???????? ???????
100 ??/?
33,9
53,0
78,0
100 ??/?
12,5 ?????/?
25 ?????/?
12,5 ?????/?
25 ?????/?
57,5
37,2
22,3
40,5
25,5
73,6
48,6
34,7
58,5
39,4
87,5
69,2
55,1
81,7
66,1
??????? 5. ?????? ??????????? ??? ???????????????? ????? ????????? ??????
?????? ??????????? ?????????? (??/?3) ??? ????? ????????
?????????
1
2
3
???-1
41,58
4,09 + 4,08 =8,17
2,86 + 0,94 + 1,58 = 5,38
???-2
10,85
1,06 + 1,07 = 2,13
0,65 + 0,25 + 0,41 =1,31
???
49,90
5,29 + 4,9 = 10,19
3,48 + 1,45 + 1,9 = 6,83
???
33,27
1,36 + 3,27 = 4,63
1,04 + 0,30 + 1,27 = 2,61
??????? 6. ?????? ??????????? ?????????? ???-1 ??? ????????? ???, ?????????????? 99 %-???
??????? ???????
???
?????? ?????????? (??/?3) ??? ????? ???????? ???????
1
2
3
????????
33,00
11,25 + 3,00 = 14,25
6,76 + 4,25 + 0,67 = 11,68
??????? ??-12
45,00
15,00 + 4,09 = 19,09
8,25 + 4,48 + 0,91 = 13,64
???
82,50
45,00 + 7,50 = 52,50
22,86 + 12,14 + 1,67=36,67
??????? ??
49,5
20,00 + 4,50 = 24,50
11,76 + 5,31 + 1,00 = 18,07
# 174 #
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???????? ?? ?????????? ???????????, ?????????? ?? ?????? ????, ????????? ???????
????????????? ????????? ? ???????? ?????????, ???????????? ???????, ???? ???????????
????????? [35-39]. ?????? ????? ????????
????????? ??????: 1) ????????? ???????
??????? ??? ?? ?????????? ??????? ? ?????????? ?????????? ????????????? ????????;
2) ?????????? ?????? ????????????? ??????? ?? ????????, ????????? ?? ??????? ??????????????? ?????????? ?????????? ???
????????????? ?????????? ?????????? ???
?????????-??????????? ??? ????????????? ???????????????? ??????????; 3) ?????? ????????? (??? ????????????? ????????????????
??????????) ? ?????????? ????????????? ??????????. ?? ???? ????????? ?????????????
??????? ??????????? ?????????? ? ??????
????????? (????????-??????????) ??? ??????????, ????????? ????? ??????? ???????????
?????????? ? ???????? ? ???????? ?????????
??????? ? ??????????????? ????? ????????????? ???????. ????? ??????? ??????????
??????????????? ?????????, ??????????????
????????????? ???????????? ? ????? ????
????????? ?? ???????????? ??????????, ???????????????, ???????????????????? ?
?????? ???????? ??????????????.
????? ?? ????????? ??????????? ???????????, ?????????? ?? ????? ????? ? ?????????? ?????, ???????? ?? ?????? ????????????
????????? ? ???????????? ? ?????????. ??????????????? ? ?????? ?????? ??????????
?????????? ????? ?? ?????????? ????????
???????????? ???????????????? (?????????
?? ????????? ? 55-68 %). ??????????? ????? ??????????? ??? ??? ???? ???????? ???????????????, ??? ??? ????????? ???????????
?? ????????? ????? ?????? ????? ???????????
?? ????????? 40-45 %. ?????? ????????? ????????? ???????? ??????????? ???????, ??? ??
???? ??????? ?? ??????? ???????? (Qir) ? «???????????? ?????????» ?????????? ?? 5800 ??
7200 ????/??, ?? ???? ??????????? ????, ??? ?
???????? ?????? ????. ????? ???????, ??????
?????????? ?????????? ???????? ????????????? ????? ???????? ? ??????? ?????????????? ??????????, ?????????? ?? ??????????
???????.
? ???????????? ???????? ????????????
?????????? ??? ? ??? ???? ???????? ???
??????? ????????????????? ??????????????? ??????? ??? ???????????? «??????»
[34, 42]. ??? ?????????? ??????? ??????? 9095 % (???. 4) ?????? ??????????? ???????? 2540 ??/?3 ??? ???????? ???????????? ??????
? ?????? 1,07 ?/? ? 70-90 ??/?3 ??? ????????
???????????? ?????? 5,64 ?/?. ???????? ???????????? ?????? [6], ??? ??????? ??????????????????????? ??????? ??? ????????????
??????????? ?????? ??????????, ???????????
?? ??????????????????? ?????????? ?????,
????? ?????????? 90-100 ??/?3. ??? ???????,
????? ??????????????????????? ?????? ???????, ??????? ?????? ??????????? ?? ??????
????????????.
???????????? ?????????? ???? ???????? ??? ??????? ????????? ???? ????????????
????????? ??????? [20]. ???????? ???? ?????
????????? ?????? (??/?): ???????? ? 0,012;
?????? ? 0,05; ?????? ? 6,86; ???? ? 0,16; ????
? 0,086; ???? ? 0,007; ????????????? ? 1,36;
??????? ?????? ? 0,01. ????? ?????????????
??????? ? ???????? ????????? ????????? ???
???????? ???????? 6-8 ?-1 ?????????? ???????? ????????? (??/?): ?????? ? 0,05; ??????
? 0,005; ???? ? 0,001; ????????, ????, ????,
?????????????, ?????? ?? ??????????. ????????? ?????????? ???????? ? ?????????
???? ??????????? ???? ????????? ?????????? ????????.
# 175 #
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?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
?
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?
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D
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0,8
60
0,6
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0
4
3
2
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100
80
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????
????
???. 4. ??????? ??????? ?????????? ??? (????, ?/?) ?? ?????????? (???????????) ???????????? ???????
(??, ?/?) ? ????????? ????? ? ??????? ??????? ??? (?, %) ??? ???????? ???????????? ??????? ? ???????
?????: ? ? 5,64 ?/?, ? ? 1,07 ?/?
?? ???????????? ?????????? ??? ????
????????? ??????? ??????? ??????? ??? ????????? ??????????? ????????? ???? ? ???????? ????????? ????????? ??? ???????? ???????? 15-20 ?-1; ??? ???? ???????? ??????????
?????????? 20 ?? [29]. ???????? ??????? ????
(???????? ????? ??????? ??????????) ?????
????????? ?????? (??/?): ?????? ???????
(????????) ? 49,7; ? ??? ????? ????? ? 19,9;
?-?????? ? 6,1; ?-?????? ? 4,8; ?-?????? ? 7,3;
????????? ? 11,6; ????????? ?????? ? 1,6.
????? ?????????? ????? ???? ?????????????
?????????? ? ?????? ????????? ??????????
????????? ?????????? ??????????? ??????????? ? ???????? ????????? ????????: ????? ? 1,5 ??/?; ??????? ? 2,4 ??/?; ?????????
? ????????? ?????? ?? ??????????. ?????
?????????? ????? ???? ?????????? ?? ??????
????????? ?????????? ?????? ? ???????? ?
????????? ??????? ????? ?? ?????????
0,003-0,005 ??/?.
??????????????? ?????????? ?????????
???-2 ??? ??????????? ??? ??????? ???? ???????????? ??????????????? ??????? ???
???????????????? ??????????? [33]. ??????-
??? ????? ????????? ?????????????? (??/?):
?????????? ???????? ? 760; ????? ??????? ?
186; ?????????? ? 97; ??????? ? 17,2; ???????? ? 139; ??????? ?????? ? 310; ?????????
?????? ? 2,6; ??? ? 1400 ?? ?/?. ???????
???? ????? ?????? ???????????????? ????????? ?????????? ??????? ? ?????????????
???????, ????????????? ??????? ? ??????? ??
???? ?????????-???????????, ????????? ????????????? ?????????? ????????? ? ???? (??/?):
?????????? ???????? ? 82; ?????????? ? 10;
??????? ?????? ? 0,008; ????????? ??????
???????????; ??? ? 45 ?? ?/?. ??? ?????????
???????????? ????? ????? ????????? ???? ?
??????? ????????? ???????????.
????????? ??????? ??????? ??? ???????????????? ?????????, ? ????? ???????????
?? ?????????? ?????? ? ???????? ??????
[39]. ??????? ??????? ??? ???? ?????????
?? ?????????? ?????????? ???-1 ? ????????
????????? ????????? (???????? ????????? 40
??, ?????? 450 ??) ??? ???????? ????????
8-10 ?-1. ???????? ??????? ???? ????? ????????? ??????: ???????? ??? ? 52-130 ??/?;
?????? ? 0,1-5 ??/?; ??? ? 1020-1200 ?? ?/?.
# 176 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
????? ?????????? ????? ???? ??????????? ?????????? ?????????? ????????? ???????? ??????????? ????????? ? ?????????: ????????
??? ? 0,5-2,0 ??/?; ?????? ? 0-0,01 ??/?; ???
? 510-560 ?? ?/?. ???????????? ???????????? ??????? ? ????????? ????? ???? ????????????? ?????????? ??? ?????? ? ????????
???????, ?? ?????? ????????????? ?????????? ??? ?????? ??????? ??? ????????? ??????????? ? ??????? ????????? ??????????? ???
??????????? ?????????.
??????
??????? ??????????? ?????????? ??????????, ?????????? ?? ?????? ???? ? ???????
??????????? ?????????, ? ????????? ???????
?????? ???? ?? ?????? ???? ??????????????
(????, ????) ? ???????????? (?????, ?????????????, ????????, ??????? ??-12, ???????????????? ?????? ???????, ??????? ??, ?????????? ? ???????? ???????) ????????.
????????? ????????, ??? ??? ????????????? ??????????? ??????? ??????? ??????????? ??????????? ?????????? ????? ???????
??????????? ?? ???????????? ??????????,
??????????????? ? ????????????????????
??????????????.
???????????? ?????????? ??????????
????????????? ????????????? ????? ???????? ? ?????????????? ?????????? ? ????????
??????????????? ???????.
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
??????? ?.?. ??????????? ??????? ????. ?.: ?????,1982. 168 ?.
????????? ?.?., ???????? ?.?. ???????? ??????? ????????????? ???????????, ?????????? ?? ?????????? ?????. ????? ???????? ???????. 1997. ?3. ?.56.
?????? ?.?., ???????? ?.?. ???????? ?????? ????? ? ?? ???????????? ?????????????:
??????????. ?.: ?????, 1994. 254 ?.
????????? ?.?. ????????? ?????????? ??????????? ? ????????? ????????????? ?? ?????
????????? ?????? ????????????. ????? ???????? ???????. 1997. ? 3. ?.39-46.
????? ?., ????? ?. ???????? ???? ? ?? ???????????? ??????????. ?.: ?????, 1984. 216
?.
????????? ?.?., ???????? ?.?., ??????? ?.?. ??????? ??????? ??? ????????????????????? ???????. ?.: ?????, 1985. 256 ?.
???????? ?.?. ???????? ????: ??????????. ?.: ?????, 1985. 56 ?.
?????-???? ??? «???????????» ?? 16.08.2005.
??????? ?.?. ?????? ? ???????? ??????????? ????????????? ????? ????? ??????????????? ????????. ????? ? ????????? ??????????? ????????. 1996. ?.IV. ?6. ?. 459-465.
????? ?.?., ??????? ?.?., ???????? ?.?. ?????? ????????? ??????????????? ????. ??
?????? 2051096, 1995.
??????? ?.?., ???????? ?.?., ??????? ?.?., ?????? ?.?. ?????? ????????? ??????????. ??
?????? 2014882, 1994.
??????? ?.?., ????? ?.?., ???????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?., ?????????? ?.?. ????????? ????????? ????? ? ????????? ???????? ????. ????? ? ?????????
??????????? ????????. 1996. ?.4. ?3. ?.193-199.
????????? ?.?. ???????? ???????. ???????????, 1995. 518 ?.
????? ?.?. ????????????? ????? ???????????? ??????? ???. ?.: ?????, 1984. 448 ?.
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
15. ??????? ?.?., ??????? ?.?., ???????? ?.?., ????? ?.?., ???????? ?.?., ???? ?.? ????????????? ?????????? ????????? ??????????? ??????????? ????? ?????. ????? ????????
???????. 1994. ?4-5. ?.142-147.
16. ??????? ?.?., ????? ?.?., ?????????? ?.?., ???????? ?.?., ??????? ?.?. VII ??????????? ?? ????? ? ?????????? ???????? ???????: ??. ??????? ????????. ?., 1996. ?.211.
17. ??????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?. ?????????? ??????????. ????????????? ???????: ?????? ????????. ????????, 1997. ?.18.
18. ??????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?. ???????? ??????? ??????? ??????????: ????????, ?????????? ?????? ? ???????????, ??????????: ????? I ????.-?????. ????.
?? ?????????? ??????????? ??????? ????????? «???????? ??????? ?????????? ? ???????????? ????». ??????????, 1997. ?.244.
19. ???????? ?.?., ??????? ?.?., ???????? ?.?., ???? ?.?. ??????????? ????????? ??????? ?
???????? ? ????????????? ?????. ????? ????????????? ?????. 1999. ?2. ?.53-59.
20. ????? ?.?., ???????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?., ?????????? ?.?.
??. ????. ?????? ????????? ????? ? ?????????? ?????????? ?? ???. ??????????, 2001.
?.212.
21. ???????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?., ?????????? ?.?. ?????????
?????????? ??????????? ?? ????????? ?????????????? ??????????? ???? ??????????? ??22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
???????. ????? ????????????? ?????. 2002. ?2. ?.57-61.
???????? ?.?., ??????? ?.?., ?????????? ?.?., ????? ?.?. ??????? ??? ?????. ??????? ??????. ??? ???. ????. ?.?.?????????. ??????????, 2002. ?.121.
???????? ?.?., ??????? ?.?., ?????????? ?.?., ????? ?.?., ???????? ?.?. ????????? ?
?????????? ??????? ?????????? ?????????. ????? ????????????. 2003. ?1. ?.24-25.
??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?., ???????? ?.?., ??????? ?.?.
?????????? ?????????? ?? ?????? ???? ??????-????????? ????????. ?????????? 2004. ??????? ??????????? ? ????????????? ????????. ????????? ???????????. ???????????
?????????? ??????????. 2004. ?2. ?. 55.
??????? ?.?., ???????? ?.?., ??????? ?.?., ?????????? ?.?. ????????? ? ????????????
??????: ??????. ????. ?????? ????????. ?????????, 1998. ?.166.
??????? ?.?., ??????? ?.?., ???????? ?.?. ??????????????? ? ?????????????? ???????
??????????? ??????????? ???????????? ?????: ????????????? ????.-?????. ????. ???.
????. ???????, 1998. ?.167.
??????? ?.?., ???????? ?.?., ????? ?.?., ????????? ?.?. ????????? ?????? ?? ??????
????????? ??????????? ????????????. ?????? ?????????? ?????. 2000. ?.73. ???.2.
?.254-257.
??????? ?.?., ???????? ?.?., ????? ?.?., ???????? ?.?., ??????? ?.?. ????? ?? ??????
???????????: ????????????? ??????? ????. ? ?????-??????? ??????. ??.??????. ?.:
???-?? ???, 2000. ?.202.
Eremina A.O., Golovina V.V., Shchipko M.L. Proc. Fourth Intern. Symp. ?Catalytic and
Thermochemical Conversions of Natural Organic Polymers?. Krasnoyarsk, Russia, 2000. P.333.
Shchipko M.L., Golovin Yu.G., Golovina V.V., Eremina A.O., Rudkovsky A.V. Ibid. P. 158.
Eremina A.O., Golovin Yu.G., Golovina V.V., Shchipko M.L. Ibid. P. 166.
# 178 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
32. Kuznetsov B.N., Shchipko M.L., Golovin Yu.G., Golovina V.V., Eremina A.O., Rudkovsky A.V.
EUROCARBON 2000: Book of absracts of 1st world Conf. on Carbon. Berlin, 2000. P.517-518.
33. ??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?. ?????????? ?????????? ?? ????????? ??????? ? ???????? ??????? ??????????????? ???. ????? ????????????? ?????.
2004. ?2. ?.67-71.
34. ??????? ?.?., ???????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?. ????????? ??????
? ?????????????? ?? ??????????? ?????????? ?? ?????? ????. ????? ???????? ???????.
35.
36.
37.
38.
39.
40.
41.
42.
2004. ? 4. ?.32-39.
??????? ?.?., ???????? ?.?., ???? ?.?., ???????? ?.?., ??????? ?.?. ????????????? ?????????, ??????????, ???????????, ?????????: ????????? ??????. ????.-????. ????. ??.
????. ??. ??? ????? ???. ?.?.???????. ??????????: ??????, 2004. ???.10. ?.1. ?.35.
??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?., ???????? ?.?., ??????? ?.?.
????????? ???????? ????????????-???????? ??????? ?? ?????? ????????? ?? ??????????
???????????. ????? ???????? ???????. 2004. ? 3. ?.60-66.
??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?. ????? ?????????? ? ????? ?
?????????? ?????????? ????????????? ?????: ????????? II ????????????? ???????????.
????? 2. ???????: ???-?? ?????????? ??-??, 2005. ?. 694.
??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?. ?????????? ?????????? ?? ??????? ??????????? ????????? ??? ??????? ??????? ???. ?????????? 2005: ??????? ??????????? ? ????????????? ????????. ??????? (??????). ?????? ???????????? ??????????????. ??????? ?????????. 2005. ? 8. ?.29.
??????? ?.?., ???????? ?.?., ???? ?.?., ?????????? ?.?. ???????? ???? ?? ??????? ??????????? ????????? ??? ??????? ??????? ??? ?? ????????????-???????? ???????. ??????
?????????? ?????. 2004. ?.7. ???.5. ?.779-782.
??????? ?.?. ?????? ????????????? ???????. ?.: ?????, 1984. 592 ?.
??????????? ?.?., ???????? ?.?., ???????? ?.?., ???? ?.?. ????????? ???????????? ??????? ?? ????. ?.: ?????, 1990. 256 ?.
??????? ?.?., ????????? ?.?., ??????? ?.?., ???????? ?.?., ???? ?.?. ?????????? ???????????? ???????????, ?????????? ? ??????? ???? ??? ??????? ??????????????? ???.
????? ???????? ???????. 1998. ? 6. ?.34-39.
# 179 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????, ???? ?. ???????, ????????? ?. ????????. ?????????? ?? ?????????????????? ??????
Adsorbents from Carbonaceous Raw Materials
of Krasnoyarsk Territory
Maxim L. Shchipko, Anna O. Eremina
and Valentina V. Golovina
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
Carbon adsorbents from brown coal and wood wastes (mixed wastes of birch and aspen wood lumbering,
hydrolytic lignin, larix sibirica bark) have been produced by pyrolysis and air-steam activation. Grained
and powder like carbon adsorbents were tested at the phenol, oil-products, aliphatic acids, surfaceactive substances, copper, chromium-contained waters treatment. Results of kinetic and isothermal
investigations of these substances adsorption are presented.
Keywords: carbon adsorbent, pyrolysis, air-steam activation, water treatment.
# 180 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 181-189
~~~
??? 631.0.861.16
??????????? ???????? ?????????????? ????????? ?????
???????? ???????? ? ??????????? ????????? ????????
? ?????-?????????? ????????????
???????? ?. ?????????a,*, ???????? ?. ????????,
????? ?. ?????????, ??????? ?. ??????????,
??????? ?. ?????????????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ??????
?
???????? ????? ? ?????????? ?????????? ?? ???,
?????????????, ??????????, 660036 ??????
?
???????? ????????? ? ??????????? ?????????????
???????????? ?? ???, ???????????? ?????,
?????????????, ??????????, 660036 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
??????????? ???????? ?????????????? ???????? ?????????????? ????????? ????? ? ?????
«???????? ??????? ? ???????? ???????? ? ?????-????????? ???????????». ???????????
?????? ??????????? ??????? ???????? (???????????, ?????????????????, ???????????,
?????? ??????????? ?????), ?????????????? ??????? ????? ???????????? ???????? ? ??????
??????????? ??????????? ???????.
???????? ?????: ????????? ?????, ??????????????, ???????? ???????, ???????? ????????,
?????-????????? ???????????, ??????????? ???????, ?????, ??????.
????????
???????????? ????????? ???????? ???????? ??????????????? ????????? ??????????
??????????? ?????????? ?????. ??????????
??????????? ???????????? ? ???? ??????? ??????? ? ??????????? ????? ????????? ?????????????? ?????????, ?????????????? ????????? ?????? ? ???????? ?????????, ? ?????
????????????? ???????????? ?? ????????????.
????????????? ?????, ?????????? ??? ?????????? ????? ???????? ????????? ???????*
1
???? ????????? ???????? ?? ??????? ??????????????, ???????????? ???????????? ??????
???????? ? ???????????? ????????, ????,
???????? ????????, ???????????? ? ????????????????? ????? [1-3]. ??? ?????????? ??
???????????? ?????????? ??????????????
????? ???????????: ??????????? ????????????? ?????????????? ???????? ?????????,
?????? ???????????? ??????, ??????????
???????? ?????????? ?????????. ?????????
???? ??????????? ????????? ?????? ???????
Corresponding author E-mail address: ksa@icct.ru
© Siberian Federal University. All rights reserved
# 181 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
??????????? ????????? ???????? ??????????????? ??????????.
??? ?????????????? ???????????? ??????????? ???????? ?????????????? ?????????
?????? ???????? ??????? ? ????????? ???????? ?????????? ???????????? ????????? ???????????? [4-6].
????????, ??? ?? ?????????? ????? ???????? ???????? ??????? ????????????? ?
??????????-???????? ?????????????? ??????? ????????? ?????.
????? ????????? ?????? ???? ????? ??????????? ??????? ?????????????? ?????????
????? ? ????? «???????? ??????? ? ????????
???????? ? ?????-????????? ???????????»,
?????????????? ??????? ????? ????????????? ???????????? ???????? ? ?????? ??????????? ??????????? ???????.
???????? ????????????
? ???????? ????????? ????? ???????????? ???????????? ????????? ?????
???????????? (Populus tremula L) (??????? 5Ч2Ч0,5 ??), ?????? ?? ??????? ????????? ?????. ??? ????????????? ???????????? ? ??????????? ???? ????? (???????
20Ч15Ч0,5 ??). ?????????? ???????? ??????????? ? ??????????? ????????? ?????
(% ???.): ????????? ? 46,3, ?????? ? 21,8, ????????????? ? ???????? ??????? ? 24,3, ????????????? ???????? ? 7,6.
??? ????????????? ?????????????????
????????? ???????????? ???????? ???????
????? «??» ?? ???? 61-75, ???????? ???????? ?? ???? 177-88, ???????????????? ????
?? ???? 6709-72, ?????? ??????? ?? ????
4204-77.
?????????????? ?????????? ??? ??????????? 103±2 °? ??????? ????????? (10 ?)
???????? ? ??????? ?????????????? ?? ??????????? ????? ??????? 200 ??3, ???? ?????
????????? ????? ???????? ???????, ???????-
?? ????????, ???? ? ?????? ???????. ?????
?????????????????? ???????? ??????????
????? ???????, ????? ?????????? ??????????? 10. ? ????????????? ?? ??????????????
????????????? ????????? ?????????: ??????????? ?? 120 ?? 140 °?, ???????????? (%
???.) ?????-?????????? ???????????? ?? 1,0 ??
2,5, ????????? ???????? ?? 1,5 ?? 8,2, ???????? ??????? ?? 21,8 ?? 28,5, ????????????????? ???????? ?? 2 ?? 3 ?????.
????????????? ????? ???????? ????????????? ????????????? ?SNOL 67/350? ? ????????? ??????????? ??????????? ±2 °?. ????? ??????????? ????????????? ????????? ??
??????????? ???????? ??? ??????????? 10
? ???????????? ?2?2 4,2 % ???. ????? ?????????????? ?????????? ??????????? ???????
???????? ?? ??????, ????????? ???????????????? ??????? ????? ?? ????????? ???????
?? ??????????? ????? ? ?????????? ??? ??????????? 103±2 °? ?? ?????????? ?????.
?????? ???????????? ???????? ????????? ?? ??????????? ????????? [7]. ?????????
????????? ?????????? ??????? ???????????,
?????????? ????????? ???????? ????????,
??????? ? ?????-????????? ??????? ? ??????????? ????????.
??? ???????????? ???????????? ? ?????????????? ????????? ??????????? ???????????
?????? ?????? ???????????? ???????????? ?
?????????????? ???????. ??? ?????????? ??????????? ????????????? ???????????? ????? Multifactor ANOVA ? Experimental design
?? ?????? ?????????? ???????? Statgraphics
Plus [8].
??? ????????????? ????? «???????? ??????? ? ???????? ???????? ? ????» ??????????? ????????????? ?????????????? ????????? ????? [4] ? ??????????? [5] ????????
?????? ???????. ? ????????? ?????? ????????? ??????????????? ???????????? ?? ??????? ??????? ?????????????? ?????????,
# 182 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
?????????????? ????????? ? ????????????
??????? ???????????? ???????? ???????? ????????.
?????????? ? ??????????
???? ??????? ??????? ???????????, ??????? ????????????????? ?????, ??????????? ? ????????????????? ????????? ?? ?????????? ???????? ?????????????? ?????????
?????. ??????????? ???????? ????????????? ?
????????? 120-150 °?, ????????????????? ??
2 ?? 5 ?????, ???????????? ?2?2 ?? 1,5 ?? 8,2
% ???., ??3???? ?? 19,9 ?? 28, 5 % ???. ?????????? ????????????????? ?????????? ???????????? ? ????. 1-3.
??? ??????? ?? ??????????? ? ????. 1 ??????, ??? ????????? ??????? 5Ч2Ч0,5 ?? ???
??????????? 10 ? ???????????? ?2?2 4,2 %
???. ???????????? ?????????? ????????? ?
??????????? ???????? ??????????? ??? ??????????? ?????????????? 130 °? ? ??????? 3 ?????. ??? ???? ????? ???????? ?????????? 48,8
% ???., ?????????? ? ??? ????????? ? 79,3 %
???. ? ??????? ? 0,8 % ???. ??? ???????????
15, ??????????? ?????????????? 120 °?, ????????????????? 2 ????, ???????????? ?2?2 6,4
% ???. ????? ???????????? ???????? ?????????? 49,9 % ???., ?????????? ? ??? ?????????
? 79,4 % ???. ? ??????? ? 0,3 % ???.
??? ?????????????? ???? ?????????
????? (??????? 20Ч15 Ч0,5 ??) ???????? ??????????? ???????? ? ????? ???????, ??? ???
??????? 5Ч2 Ч0,5 ??, ??????????? ???????
(????. 2).
??? ??????? ?? ?????????? ???????????,
??????????? ?????????? ?????-??????????
???????????? ? ???????? ?????????? 2 % ??
????? ?.?.?. ??? ????? ???????????? H2SO4 ?
?????? ?????? ??????? ????????? ??????????? ?????????? ??????? ????? ????????????
???????? ? ??????? ??????????? ?????????
(????. 1). ?????? ??? ?????????????? ?????
??????? ??????? ????????? ????? ?????????? ??????????? ??????? ?????????? ?? ?????
7,2 % (????. 2).
? ????. 3 ????????? ?????? ? ???????
?????????? ????????? ???????? ? ????????????????? ???????? ?? ????? ? ?????? ???????????? ???????? ????????? ????? ???????
5 ? 2 ? 0,5 ??) ? ??????????? H2SO4
(2 % ???.).
???????????, ??? ??? ????????? ???????????? ????????, ??????????? ????? 80 %
????????? ? 0,8-1,2 % ??????????? ???????,
????????????? ???????????? ????????????????? ???????? ? ????????? ?????????????
?2?2 4,2-6,4 % ???.
??? ??????? ??????????? ??????? ?????????????? ????????? ????? ?????? ??????????? ????????? ? ??????????? ????????
??????????????? ?????????? ???????? ??????????????, ?????????????? ?????????
???????????? ???????? ? ??????????? ??????????? ??????? ??? ??????? ?????????
??????????? ? ???????? ??????????: ?????
???????????? ???????? ?????? ???? ? 42% ??
????? ???????? ?????????; ?????????? ????????? ? ???????? ?????? ???? ? 75%.
? ???????? ??????????? ?????????? ??????? ????????? ?????????: ?1 ? ?????????
???????????? ?2?2 ? ??????????? ????????,
%; ?2 ? ??????????? ???????? ??????????????, °?. ????????? ???????: ??????????? 10,
????????????????? ?????????????? 3 ????,
????????? ???????????? H2SO4 2 % ?? ?????
?.?.?.
?????????? ??????? ??????????? ? ???????????? ?? ?????? ??????? ??????????
???????????? ??? ?????????????? ?????????????? ??????? ? ????? ???????? ? ?????
????????????? ???????????? ? ??????. ?
???????? ???????? ?????????? ???????: Y1
? ????? ???????????? ????????, % ?? ?????
???????? ?????????; Y2 ? ?????????? ?????-
# 183 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
??????? 1. ??????? ??????????? ? ????????????????? ???????? ?????????????? ????????? ?????
(??????? 5Ч2Ч0,5 ??) ??? ??????????? 10, ?????????? ?2?2 4,2 % ???., ??3???? 25,8 % ???.,
?????-?????????? ???????????? 2 % ???. ?? ????? ? ?????? ??????????? ?????????
???????????,
°?
120
130
140
?????? ????????, %**
?????,
?
????? ???????????? ????????, %*
?????????
??????
2
63,4
64,7
6,1
3
50,3
74,6
4,4
2
51,5
75,6
1,2
3
48,8
79,3
0,8
2
50,8
78,8
1,6
3
46,4
78,1
1,7
* ?? ????? ????????? ????? ????????? (?.?.?.).
** ?? ????? ????????? ?????? ???????????? ???????? (?.?.?.?.).
??????? 2. ??????? ???????????? ?????-?????????? ???????????? ?? ????? ? ?????? ????????????
????????, ??????????? ??????????????? ???? ????????? ????? (??????? 20Ч15 Ч0,5 ??) ???
??????????? 130 °?, ??????????? 10, ?????????? ?2?2 4,2 % ???., ??3???? 25,8 % ???.,
????????????????? 3 ?
???????????? H2SO4, % ???.
????? ???????????? ????????, % *
0,0
1,0
?????? ????????, %**
?????????
??????
59,6
65,7
23,9
58,0
69,8
19,8
1,5
56,8
72,2
9,9
2,0
46,9
86,4
7,2
2,5
46,0
84,3
8,5
* ?? ????? ?.?.?., ** ?? ????? ?.?.?.?.
??????? 3. ??????? ???????????? ?2?2 ? ????????????????? ???????? ?? ????? ? ?????? ????????????
????????, ??????????? ?? ?????? ????????? ????? (??????? 5Ч2Ч0,5 ??) ? ??????????? 2 % ???. H2SO4
??? ??????????? 130 °?, ??????????? 10 ? ????????????????? ???????? 3 ????
?????? ????????, %**
???????????? ?2?2,
% ???.
????? ???????????? ????????,
%*
?????????
??????
1,5
54,6
71,7
7,0
4,2
48,8
79,3
0,8
6,4
41,1
80,8
1,2
8,2
36,6
83,1
5,8
* ?? ????? ?.?.?., ** ?? ????? ?.?.?.?.
# 184 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
???? ? ??????????? ????????, %; Y3 - ?????????? ??????????? ???????, %.
???????? ?????? ??? ????????????
???????????? ? ????. 4.
?????????? ?????????? ??????? ???????????? ???????????? ????????? ? ????. 5.
?????????? ?????????????? ??????? ?????????????? ????????? ????? ????????? ?
????. 6.
???????????, ??? ???????????? ????????
?1 ? ?2 ?????? ???????????? ????? ? ????????? ????????? ???????? ??????????.
?? ???????? ?????? ??????????? ??????? ????????? ????????? Y3 ??? ?????????
?????????? ???????? ?1 ? ?2 ??????????????
???. 1.
??????????? ?????????? ?1 ? ?2 ?????????? ?? ?????????
?i Xi
?i
?
(0)
,
??? ?i(0) - ???????? ???????, ?i ? ??? ????????????.
??????? (?????????????) ? ???????????
????????? (?i) ?????????? ?? ?????????
?i = (?i0) + ?i??i.
??? ?????????? ????????? ???????????
? ???????? ?????????? ? ??????????? ???????? ??????????? ????????? ??????????
???????? ??????????? W?, ????????? ?????
Multifactor ANOVA ? Experimental design ??
?????? ?????????? ???????? Statgrafics Plus
[9]:
p
¦ ?idi
i 1
P
W?
,
¦ ?i
i 1
??????? 4. ???????? ??????? ? ?????? ?? ????????????
?????????? ???????
?????????????? ?????
?????????
???????????? ?2?2 ? ???????? (?1), %
??????????? ???????? (?2), °?
???????? ???????, ??? (0)
4,2
130
??? ????????????, ??
2,2
10
??????? ???????, ?? (+1)
6,4
140
?????? ???????, ??- (-1)
2,0
120
+
??????? 5. ??????? ???????????? ???????????? ?? ?????????????? ????????? ????? ? ???????????
2% ???. H2SO4 ? ?????????? ??????????
?????? ????????
?
?????
?????????
????????????
?2?2, % (?1)
???????????
????????,
°? (?2)
?????
????????????
????????, % (Y1)
?????????, %
(Y2)
??????????
??????, % (Y3)
1
2,0
120
53,6
76,9
7,8
2
6,4
120
49,9
79,1
3,8
3
2,0
140
46,4
79,0
3,6
4
6,4
140
41,4
76,2
1,8
5
2,0
120
53,0
71,0
7,6
6
6,4
120
49,8
79,8
3,6
7
2,0
140
46,5
78,1
3,4
8
6,4
140
41,2
76,4
1,7
# 185 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
??????? 6. ?????????? ?????????????? ??????? ???????? ???????? ?????????????? ????????? ?????
??? ???????????? ???? ????????*
????????
?????????
?????
???????
???????
?????????
???????
????????
????? ???????????? ???????? (Y1)
F?????????
???????
??????????
?????? ?1
25,92
1
25,92
60,63
0,0015
?????? ?2
39,61
1
39,61
92,64
0,0007
55,68
0,0017
?1??2
23,805
1
23,805
???????
1,71
4
0,4275
????? (???????.)
91,04
7
?????????? ????????? (Y2)
?????? ?1
15,68
1
15,68
32,16
0,0048
?????? ?2
10,58
1
10,58
21,70
0,0096
?1??2
6,125
1
6,125
12,56
0,0239
0,4875
???????
1,95
4
????? (???????.)
34,335
7
?????? ?1
41,8613
1
41,8613
360,10
0,0000
?????? ?2
4,96125
1
4,96125
42,68
0,0028
?1??2
1,36125
1
1,36125
11,71
0,0267
0,11625
?????? ? ????????? (Y3)
???????
0,465
4
????? (???????.)
48,6488
7
* ?1 ???????????? ?2?2 ? ??????????? ????????, % ? ?2 ? ??????????? ???????? ??????????????, °?.
???. 1. ??????????? ??????? ????????? ????????? ? ?????????? ??????????? ??????? ? ???????????
???????? (Y3) ??? ????????? ????????? ???????????? ?2?2 (?1) ? ???????? ? ????????? ???????????
?????????????? (?2) ????????? ????? ? ??????????? H2SO4
# 186 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
??? ?i ? ???? ???????? ?????????? (?????? ??
???????? ????????? ? ????????? 0 ? ?i ? 1); di
? ??????? ??????? ??????????, ??????? ?????
???? ?????????? ?? ?????????.
di
M 0 (X) Yi ( )
Yi
()
Yi
()
,
??? ?0(?) ? ?????? ????????? ????????? Yi ?
????? ?; Yi(+) ? Yi(-) ? ?????????????? ?????? ?
?????? ???????? ????????? ????????? ? ???????? ????????? ???????.
??????? ???????????? ? ??????????
???????? ??????????? ????????? ? ????. 7.
??????????? ??????????? ???????????
????????? ??????????? ???????? ?????????????? ????????? ????? ???????????? ??
???. 2.
?????????? ???????? ??????????? ???????? ?????????????? ????????? ?????, ???????? ?????? ????. 7, ?????????? W?=0,926.
??? ????????????? ?????? ??????????????:
??????????? 130 °?, ???????????? ?2?2 ? ???????? 4,2 % ???., ??????????? 10, ????????????????? 3 ????.
????????? ?????? ????????? ? ??????? ???????????? ? ??????????????????
?????????????? ???????? ??????????????
????????? ????? ? ????? «???????? ???????
? ???????? ???????? ? ????» ? ???????????
?????-?????????? ????????????.
??? ????????????? ??????????? ??????? ?????????????? ??????? ????????????
??????????? ??????? ? ??????? 48,8 % ???.
??????? 7. ??????? ???????????? ? ????????? ??????????? ?? ?????????? (Y1, Y2, Y3) ? ??????????
???????? ???????????
?/?
?1
?2
Y1
Y2
Y3
Wa
1
-1
-1
53,6
71,0
6,8
0,385
2
0
-1
52,0
74,2
4,4
0,433
3
+1
-1
49,4
79,8
3,8
0,702
4
-1
0
51,0
75,0
4,4
0,464
5
0
0
48,3
79,3
0,9
0,926
6
+1
0
43,9
75,8
1,2
0,699
7
-1
+1
46,5
78,1
1,8
0,783
8
0
+1
46,2
78,8
1,7
0,823
9
+1
+1
41,4
76,4
1,4
0,605
Wa 0,98
0,88
0,78
0,68
0,58
0,48
0,38
-1-0,6
1
0,2 0,6
-0,20,2
-0,2
0,6 1 -1 -0,6
x2
x1
???. 2. ??????????? ??????? ??????????? ????????? ??????????? W? ???????? ??????????????
????????? ?????
# 187 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
?? ?.?.?., ??????? ???????? 79,3 % ?????????
???????? ? 0,8 % ??????????? ???????.
??????????
???????? ???????? ?? ???????? ??????????????? ???????? ?????????????? ????????? ????? ? ????? «???????? ??????? ? ????????
???????? ? ?????-????????? ???????????».
???????????, ??? ??????????? ???????????? ???????????? ? ?????????????????
????? ????? ???????? 2 % ?? ????? ????????? ????? ????????? (?.?.?.). ??? ?????? ?????????? ????????????, ??????????? 130 °?
? ????????????????? ???????? 3 ? ????? ???????????? ???????? ?? ????????? ????? ?????????? ????? 50 %, ? ?????????? ? ??? ????????? 79,3 % ???.
?????????? ???????????? ??????? ???????????? ????????? ???????? ? ????? ?? ??-
??? ? ?????? ???????????? ????????. ??? ????????? ????????, ??????????? ????? 80 %
????????? ? 1 % ??????????? ???????, ????????? ???????????? ????????????????? ???????? ? ????????? ????????????? ?2?2 4,2-4,6
% ???.
????????? ??????????? ???????? ?????????????? ?????????????? ????????? ????? ??? ???????????? ???????? ??????????,
?????????????? ??????? ????? ?????????
? ?????? ??????????? ??????????? ???????.
?????????????????? ? ?????????? ????????
???????????, ??? ??? ??????????? ??????????
??????????? ??? ??????????? 130 °?, ??????????? 10, ??????? ??????????? ????? (% ???.
?? ?.?.?.): ??3???? -25,8 , ?2?2 ? 4,2, H2SO4 ?
2,0, ????????????????? ???????? 3 ????.
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
Poppulius-Levlin K., Mustonen R., Muovila T., Sunquist J. Milox pulping with acetic acid ?
peroxyacetic acid // Pap. ja. Pun. 1991. V. 73. N 2. P. 154-158.
?????????? ?.?., ??? ?.?., ??? ?.?. ?????????????????? ?????????????? ?????????. 5.
??????????? ??????????? ????? // ????? ????????????? ?????. 1999. ?2. ?. 45-47.
Kuznetsov B.N., Kuznetsova S.A., Danilov V.G., Kozlov I.A., Taraban?ko V.E., Ivanchenko N.M.,
Alexandrova N.B. New catalytic processes for a sustainable chemistry of cellulose production
from wood biomass // Catalysis Today. 2002. V.75. P. 211-217.
Kuznetsova S.A., Danilov V.G., Kuznetsov B.N., Yatsenkova O.V., Alexandrova N.B., Shambasov
V.K. and Pavlenko N.I. Environmentally friendly catalytic production of cellulose by abies wood
delignification in ?acetic a?id ? hydrogen peroxide ? water? media // Chemistry for Sustainable
Development. 2003. V. 11. P.141-147.
????????? ?.?., ???????? ?.?., ??????? ?.?., ???????? ?.?. ????????????? ?????????????? ????????? ??????????? ? ????? ???????? ??????? ? ???????? ???????? ? ???? ? ??????????? ???????????? H2M??4 // ????? ????????????? ?????. 2005. ?4. C. 35-39.
????????? ?.?., ??????? ?.?., ???????? ?.?., ????????? ?.?. ???????????? ??????????
??????? ????????? ????????? ?? ????????? ?????? // ?????? ?????????? ????????????
????????????. 2008. ? 1. ?. 80-87.
?????????? ?.?., ????????? ?.?., ???????? ?.?. ???????????? ?????? ?? ????? ????????? ? ?????????. ?.: ????????, 1991. 320 ?.
??? ?.?. ???????????? ???????????? ? Statgraphics. ??????????: ??????-???????????,
2003. 246 ?.
# 188 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ?????????, ???????? ?. ???????? ??????????? ???????? ?????????????? ????????? ??????
Regulation of Aspen-Wood Delignification by Acetic Acid
in the Presence of Hydrogen Peroxide and Sulfuric Acid Catalyst
Svetlana A. Kuznetsovaa, Vladimir G. Danilovb,
Olga V. Yatsenkovab, Natalia M. Ivanchenkob
and Natalia B. Alexandrovac
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
c
Krasnoyarsk Department of Institute Economics
and Industrial Engineering SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
Main regularities of aspen-wood delignification in the medium ?acetic acid ?hydrogen peroxide
? sulfuric acid catalyst? have been established. The optimal conditions of delignification process
(temperature, time, liquid to solid ratio, reaction mixture composition) were selected. They supply the
high yield of cellulosic product with low content of the residual lignin.
Keywords: aspen-wood, delignification, acetic acid, hydrogen peroxide, sulfuric acid catalyst, cellulosic
product, yield, composition.
# 189 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
Journal of Siberian Federal University. Chemistry 2 (2008 1) 190-199
~~~
??? 539.19
???????? ??????????? ??????? ??????????? ????? (I)
?? ??????? ??????? DFT
???????? ?. ????????a, ??????? ?. ???a,
????? ?. ???a, ???????? ?. ????????a,?,
???????? ?. ???????a,?
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ?????????? 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ?????????? 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
????????? ???????????? ??????????? ??????? ??????????? ????? (I) ?? ?????????? ????????
???????? ??????????????? ??????? ????????? (????? ??????????? ?????????) ?
???????????? ???????. ???????? ???????? ????? ???????? ????????? ??? ???????????
??????????? ???????????????? ??????? ??????????? ??????? Rh(CO)2+. ????????? ???????
????????? ?? ????? ? ???????? ?? ????? ? ??????????? ?????????? ??????????? ????? (I).
???????? ?????: ????? ??????????? ?????????, ?????????? ????? (I), ???????????, ???????,
?????? ??????????? ????????.
????????
????????? ?????, ???????????? ?? ????????? ???????? ?????????, ???????? ?????????????? ?????? ?????? ???????, ????? ???
???????????? ?? [1, 2] ? ???????????? ????????????? [3, 4], ???????????????? ???????? [5,
6] ? ??. ?????? ???????????? ??????????????
?????? ?????? - ???????????? ??????????????
??????????? ?????????? ?????? ?????????
?????? ? ???????????? ???????? ????????.
??????????? ??????? ??????????? ????? (I) ??
????????, ??????????, ???????? ?????? ?????
????????????.
????????????????? (?? ? EXAFS) ? ????????????? ???????????? ??????????? ?????
*
1
(I), ??????????? ? ??????? ????????????????????? (Si/Al=100) ??????? Y, ????????, ???
??????????? ?????? Rh(CO)2+ ??????????
?????????????? ?? ??????????? ???????, ????????? ? ??????? ????????, ? ????????????
???????????????? ????????? ???????????????? ????? [7, 8]. ? ?? ?? ????? ??????????
?????? ?? ?????, ??? ?? ????????? ?????????? ?????????? ??????????????? ??????
??????????? ????? (I), ? ????????????? ???????
????? ?? ?????? ????????? ???????? [7, 9].
????? ????????? ?????? ???????? ?????? ??????? ?????????? ????????? ?? ???????????, ????????? ? ?????????????? ?????????????? ????????????????? ?? ???????
Corresponding author E-mail address: shkulepo@rambler.ru
© Siberian Federal University. All rights reserved
# 190 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
????????? Rh(CO)2+, ? ????? ????? ??????
??????????? ??????????? ???????????????
?????????? ? ??????? ????????????? ?????????????? ?????????? ??????, ? ???????
????????-???????????? (??) ??????? ?????????? ? ???????? ????????? ?????????, ??????????? ?? ?????? ???????????? ????????
(??).
????????? ??/?? ???????????
??????????? ???????? CovEPE
??????? ??????????? ???????? ???? ????????? ? ??????? EPE ?????? ???????????
????????????? ????????? (Elastic Polarizable
Environment, EPE), ?????????????? ??? ???????? ???????? ??????????? ??????? (????????, ???????) - covEPE [10]. ? ?????? ??????
EPE ??????????? ??????? ??????????? ?? ???
????: ??????? I ? ??-???????; ??????? II ? ???
???????????-???????????? ?????????.
? ?????? EPE ?????????? ???????? ??????????? ??-???????? ? ??? ??-?????????.
????????? ?????? ?? ??-??????? ????? ????
????????? ? ?????????????????? ????. ????????? ???????? ?????????????? ?????
????????? I ? II ????? ??????? ????, ? ?????
????, ??????????? ?? ??/MM-???????, ??????????? ??????? ????????? ?? ??????? ?????????? ? ???????????? ????????? (?????????, ? ??????? ??????????? ???????????????
???????, ??????? ??? ???? ???????). ???????????? ??? ????????????????? ??????? ?
??-???????? ???????????? ?????????? ??????? ???????.
?????? ? ?????? CovEPE ??????? ?? ????????? ??????: (1) ??-??????????? ????????? ????????? (regular - reg) ?????????????
???????; (2) ??????????? ??-???????? (cl),
???????????? ??????? I ??? ????????????
(reference - ref) ???????, ?????????? ? «????????????» ?????????; (3) ??????????? ??????? ???????????? ??????? ? ???????? (??????-
???????? ??????, ????????, ??????? ? ?.?.);
(4) ?????????? ??????? II ? ?????? ?? ?????????????? (???????????? ? ???????????????????) ? ???????? I. ????????? ???? ???????,
??????? ?? ? ???????????? ???????, ???????????? ??????????? ???????????? ??????
??????? ?? ??????? 3 ? 4. ??? ?????????? ???????????? ???????????? ????????? ???????
II ?????????? ?????? ????? MM-??????? ??
??-???????? ???????????? ???????? ? ????????? ????????? ? ? ????? ???????????????.
?????? ???????? ??????????? ??? ????????
????? ????? ????????? ?????????? ? ??????????????????? ?????? ????????? ??- ?
???????????? ??-???????? ?????????????
??????? ? ??????? I, ??????????? ?? ??????????????? ??????? 1 ? 2 ??????????????:
corr
Eint
U
tot, MM
cl
R
R
Ulat Rlat V short
reg
cl
, Rppreg Ucltot, QM Uclref, Rclref, Rppref ||
reg
cl
ref
ref
, R reg
pp / R lat V short R cl , R pp / R
,
lat
??? Rcl, Rpp, Rlat - ??????? ?????? ? ????????,
?? ??????? ? ? ?????????? ???????, ??????????????, ?????????? (reg) ? ????????????
(ref) ????????. ??????? ????? ?????????? ???????????? ??????????? ?????????????? ?????
????? ?????????? ???????????. ?????????
EPE ????? ??????? ?????? ??????? ???????
????????? ????????? ????????? ????????????? ?????? ? ?????? ???? ???????? ???????
??? ??-, ??? ? MM-????????.
????????????? ?????? covEPE ??????
???????? ????????????? ????????? ???????????? ??? ???????? ?????????????? ?????
??????? ???????-?????????. ?????????? ????? ??-???????? ?????????? ??????????????
???????????????????? ??????? ?* (p?), ???????????? ??????????? ?????? ??????????????? ???????. ????????? ???? ?????????
?????? ????????? ????? ???????, ????? ?????????????? ????????? ???????? ?????? ?????????, ? ????? ?????????????? ??????????
??????????????????? ???? ?? ??????? ????????.
# 191 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
????? ???????? ????????????? ??????????????? ????????, ????????????? ??????????????? ????? ?????????????? ?????????
???????? Si ??-??????? ? ????????????
???????? ?? ??????? ??-???????, ?????????
? ??-???????? ??-????? ??????? ????? ???????? ???????????? ???????????????????? ???????? Si* [10d].
??-??????? II ??????????? ? ??????? ???????? ???? ?????????? ?????????????????? ???
????????? ? ??????????????. ??? ???????????
???????? ?????????????????? ???????? ????????? ???????? ???? ???????? ?? ???????????????????????? ??-??????? ? ????????? ??????????? ??????? ???????. ????? ????????
????? covEPE ?????? ? ??????? [10 a, b], ???????? ?????????????? ???????? ???????? ?
[10 d].
?????? ????????
??? ?????????? CovEPE ???????? ????
??????????? ????? ???????? ParaGauss [11,
12], ??????????????? ? ?????? ?????????????? ????? LCGTO-FF-DF (Linear Combination
of Gaussian-Type Orbitals Fitting-Functions
Density Functional) [13]. ??-????? ???????
??????????? ? ??????????? ????????????
???????-??????????????? ??????????? BP86
[14 ?, b]. ???????????????? ??????? ???? ????????? ??? ????? ?????????????? ????????.
??? ???????? ????????? ????????? ????
???????????? ???????? ?????? ??????????????? ????????? ??????? ??? ?????? O ?
C (9s5p1d/5s4p1d), Al ? Si (12s9p2d/6s4p2d)
[15] ? Rh (19s15p10d/8s6d4d). ???????? ?????
??? ????? Rh ??? ??????? ??????????? ?????? (17s12p8d) [16] ????? s- (? ????????????
0,01303, 0,2253), ????? p- (0,03666, 0,09165,
0,2291) ? ????? d-????????? (0,04588, 0,1147)
[17, 18]. ??????????????????? ?????? O* (pp)
??????????? ???????????????? ????????
??????? (5s5p1d/4s3p1d) [10d]. ??????? ???-
?????? ???? ???????? ???????? ??????????? ???????? ????????? ?????? ???????????
?????? ??????? ??/??-???????. ??? ??????? ?????? ????????? ????????????? ????
????????? Rh(??)2+.
??? ??????? ?????????? ??????? ????????????? ?????????? ? ???????????? ???????
Rh(CO)2+ ??????????? ??? ?????-???? ??????????? ?? ????????? ? ???????????? ?? ?????
????????, ?????????? ??????????? ????????? ????????? ??????????? ??????? ? ??? ???????????????? ??????????? ???????????? d8.
??????? ?????????????? Rh(CO)2+ ? ????????? ???????? ???????????? ? ?????? ???????? ?? ???????????? ???????? ???????.
?????? ??????????? ????????
? ????? ???????????? ??-????????,
???????????? ?????? ??????????? ???????
??????????? ????? (I), ???????????? ?????
???????????? ?????????? (-1 ?.?.) ?????????
??????? ??????? ????????, ? ??????? ??????????? ???? ??????? ??? ??????? ?? ????
????????. ??? ???? EPE ????????? (???????
II) ?????????? ???????????????. ???????????
????? ??????? ?????? ????????????? ??????-
???. 1. ???????? ??????? ???????? ? 5?
?????????, ?????????????? ? ????????. ????????
???????????????????? ???? ?????? ?????????
# 192 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
??? ??????? ? ???????????? ?????? ??????????? ???????? (Si/Al=?).
? ??????? ???????? ??????? ??????
??????????????????? ????????? ???? ??????
????????? [19], ?????? ???????? ??? ?????????????? ? Rh(CO)2+ ?????? ?? ?? ???, ???
??? ???????? ???? ???????????? ??? ????
??-?????????: ????? ? ???????????. ??????
???, ????????? ?? ?????? ????????, ????????
???? ?????? (Si, Al), ?????????????? ? ??????????????? (T) ???????? (5? ???????). ????? ??????? ????? ???????? Al(OSiO*3)4, ???
??????? ? ???????????? ???????: ?1, ?2 ? ?4
(???. 1).
?? ??????????? ??????????? ??????????? ????? ?? ???? ????? ?????? ?????????,
????????????? ?????? ????? ????????: (A)
O1 ? O4 ? ????????????????? ?????? ???????? (???. 2a), (?) O1 ? O2 ? ??????????????
?????? ?????????????? ?????? (???. 2?), (?)
O2 ? O4 ? ???????????? ?????? ???????????
?????? (???. 2?). ????????????? ?????????
??????? ??????????? ????? (I) ?? ???. 2 ????????????? ??????? 12R (twelve-ring), 4R (fourring) ? 6R (six-ring).
???? ???????? ??????? ???????? OSiO*3?
????????, ?????????? ??? ??? ????????? ??????????????? ????????? Rh(CO)2+ (???. 2?,
2? ? 2?, ??????? ???).
??? ?????? ??????????? ???????????,
?????????????? ? ????????? ????????????? ??
???????? ??-???????? ? ???????? ?????????
?????? (O*, Si*) ???? ???????????? ??? ??????????? ??-????????, ?????????? ?? ????????? 5? ???????? ????? ????????? ? ???? ?????????????? SiO4 ??????????, ??????????
??/??-??????? ?? ????????? ?????? AlO4 ?
???? ????????? ????????????. ????? ???????, ???? ???????? ??-???????? ?????????
???. 2. ??????????? ??????????? ????? Rh(CO)2+ (A) ? ????????????????? ?????? ???????????? (??????
12R), (?) ? ?????????????? ?????? ?????????????? ?????? (?????? 4R), ? (?) ? ???????????? ??????
??????????? ?????? (?????? 6R). ? ??????? ???? ???????? ????? 5? ??????, ? ?????? ???? ?
??????????? ?????? 7? ? 8?
# 193 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
7? (??? ??????? 12R ? 4R) ? 8T (??? ??????
6R). ??????????? ?????????? ?????? 4R ? 6R
????????? ????????? ???????? ? ??-???????
???????- ? ???????????? ?????? ?????????????? ?????? ? ??????????? ?????? ?????????????? (???. 2? ? 2?, ?????? ???).
???????? ????????? ?????? ?????????? ???????? ??-????????? ????? ?????? ??
?? ??????????? ? ?????????????? ??????????????. ??????????????? ????? ? ??????????? ?????? ?????? ?? ??????????? ?????????? ? ???????? ? ???????? 1 ?? ??? ????
?????????? ??????, 1є - ??? ????????? ?????,
1-5 ???/???? - ??? ??????? ??????????????
Rh(CO)2+ ? ????????. ?????????? ??????????
????? ?????? ????????? ?????? ? ??????? ????????? ??????? Rh ? O, ??????? ??? ?????????? ??????? ?????????? ?? 1-2 ?? (????. 1).
?????????? ??????????
???????????
???????????? ??????????? ? ?????????????? ????????? ?????????? Rh(CO)2+,
???????????????? ?? ???????, ?????????
? ????. 1. ???????? ???????? ???????? ????????????? ???????? ???????? ?????? 12R,
??????????????? ??????????? Rh(CO)2+ ?
????????????????? ??????, ? ???????? ?????????????? ?642 ???/???? (????. 1). ???????
?? ???????? ??????? ?????????????? ??????????? ????? (I) ? ???????? ??????? ?????
(?654 ???/????) ???? ???????? ? ? ??????
[7]. ? ?? ?? ????? ????? ????????, ??? ? ?????? ?????? ???????? ?????? Rh(CO)2+ ?????????????? ?? ?????????? ???????????????
?????? ?????????????? ??????. ????? ??? ??
????? ??????, ????? ?????? (4R) ??????????????? ?????????? ???????? ??????????????
(?594 ч ?600 ???/????) ????? ?????????????. ??? ???????? ??????????? ???????????
????? (I) ? ???????????? ?????? ??????????? ??????, ?? ? ?????? [7] ?? ???? ????????
?????????? ????????? ??? ?????? ???????.
??? ????? ?? ??????? ????????????? ? ????? ????????, ??????????????? ????????????? ?? ??????? ???????????? ?????? 6R
(?620 ч ?625 ???/????). ?????? ??????????? ?? ????? ???? ????????? ?? ??? ????,
??? ???????? ?? ??-???????? ??????????? ?
?????????????????? ???????? ???????????-
??????? 1. ????????? ????????????????? ? ????????????? ??????? ????????? ??????????? ?????
?? ??????? (????? ?????? ? ??, ???? ? ????, ??????? ? ???/????)
???????
EA ?)
?E?)
Rh-O (N) ?)
Rh-Al
Rh-C
Rh(CO)2 /NaY[7]
210?215±2
????. ??????
215-216 (2)
273-274 (1)
186 (2)
213, 215, 347
214, 216, 350
214, 220, 316, 342
214, 222, 308, 325
215, 217, 322, 334
215, 219, 328, 345
219, 223, 333
297
297
280
279
290
288
280
188
188
188
188, 189
188
188
187, 188
188
+
?)
C-Rh-C
??????
Rh(CO)2+
12R (5T)
12R (7T)
4R (5T)
4R (8T)
6R (5T)
6R (8T)
Rh(CO)2+/Zeo [7]
-642
-641
-600
-594
-620
-625
-654
0
0
-42
-47
-22
-16
86,7
87,7
86,7
90,2
89,5
88,1
88,0
90,4
??????? ?????????????? ??????????? ????? (I) ? ???????? E A E ¬Є Rh(CO )2 / Zeo јє E > Zeo@ E ¬Є Rh(CO )2 јє; ?) ????????????? ??????? ??????????????; ?) ? ??????? ????????? ????? ?????? ??????? ????; ?) ???????? Rh(CO)2+, ???????????????? ?? ??????? Y, EXAFS ??????: N ± 10 %; R ± 2 ??.
?)
# 194 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
????? ????????? ???????, ??????? ????????????? ??? ???????? ? ?????? [7].
???????? ???????? ???????? Rh(CO)2+ ?????????????? ?? ???? ?????? ????????? ????????, ??????? ????? Rh?O ?????? 213-222 ??.
?????? ?????????? Rh?O ????????? 300 ??, ?
?????????? Rh?Al ????????? ? ????????? 279297 ??. ??? ?????? ?????? ??????????? ?
???????????? 209-216 (Rh-O), 270-280 (Rh-Al)
? 320-340 (Rh-O) ??, ?????????? ? ???????
?????? EXAFS [7]. ?? ???? ???? ??????? ????????? ???????????????? ?????????? ??????????? ????? (I) ?????? ? ????????????????, ???
?? ??? ? ???????? ?????????????? ? ??????????????????? ?????????? [20]. ??????????
?? 90є ???? C?Rh?C ?????????? ?? ????? 3,3є, ?
?? ????? ??? ???? O?Rh?O ????? 73-74є.
??????????? ?????????? ????????????
???????????????? ?????????? ? ?????? ????? Rh?O ? ?????? C?Rh?C: ??? ?????? ?????
? ?????? ????????? ???? C?Rh?C ?? ????????? ?? ????????? ???????? Rh(CO)2+, ???
???? ??????? (?? ??????????? ????????) ???
?????????????? ? ????????? ?????????. ???,
????????, ???????? ?????????? ?????? 12R
???????? ?????? ????????? ?? ????????????? ??????? ??????? Rh?O (214 ? 216 ??) ?
???????????? ????? ??????? ???????????
Rh?Al (297 ??). ??????????? Rh(CO)2+ ? ?????????????? ?????? ??????????? ??????
???????? (?????? 4R) ???????? ???????. ???
??????????????? ?????? ???????? ???????
Rh?O (214 ? 222 ??) ? ????? ????? ????????
?????????? Rh?Al (279 ??) ????? ????????????? ??????????. ??????????? ???????????
????? (I) ? ???????????? ?????? (?????? 6R)
??????? ???????? ????????????? ????? ????? ??????????? ?? ??????? ??????????????
????????? ? ????????. ? ?????? ?????? ?????????? ??????????? ???? ?????? Rh?O ?????? 215 ? 219 ??, ? ?????????? Rh?Al ?????????? 288 ??.
? ????. 2 ????????? ????????? ?????????????? ?????????? ? ????????????????? ??
???????? ?????????? Rh(CO)2+. ????????????
??????? ????????? ?? ????????? ?? 30-40 ??-1
????, ??? ???????????????? ??????????? ????????. ? ?????????? ??????????? ??????????? ????? (I) ?? ??????? ?????????? ?????????
?????? ????????????? ? ?????????????????
??????? 2. ???????? ?? ? ????????? ? ???????????????? ?? ??????? Rh(CO)2+ ?????????? (????? ?????? ? ??, ????? ?? ?????? ? ?.?., ??????? ? ??-1)
???????
d(C-O)
qa)
?(CO), as/s
?? ?)
???? ?)
66
-26/-92
60
58
-34/-94
???????????
CO [7]
2143
Rh(CO)2+/NaY ?) [7]
2117/2051
??????
????????? CO
114,1
2112
Rh(CO)2
114,6
+1,00
2144/2096
12R (7T)
115,7 115,8
+0,43
2078/2018
6R (8T)
115,7 115,8
+0,37
2076/2018
4R (8T)
115,6
+0,33
2082/2026
56
-30/-86
Rh(CO)2 /Zeo [7]
115,6
2082/2028
54
-30/-84
+
+
-36/-94
????????? ????? ?? Rh(CO)2+ ?? ?????????; ?) ???????? ??????????? ????? ???????????????? ? ????????????
????? ????????? ???????????? ?????, ?? = ??as ? ??s; ?) ???????? ???????????? ??????? ?? ????????? ? ???????? CO;
?)
???????? Rh(CO)2+, ???????????????? ?? ??????? Y.
?)
# 195 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
CO ????????? ?? 30 ? 34 ??-1 ? 86 ? 94 ??-1 ?????????????? ?? ????????? ? ???????? ?????????
?????????? ??, ??? ????????? ? ????? ???????
???????? ? ??????? ??-????????????? [7]. ?
?? ?? ?????, ????????? ?????? ??????????????, ?????????? ??????? ??????????? ????? ?
??????????????? ??????? Rh(CO)2+, ??????????? ? ????????????. ??????????????????
???????? ????? ??????????????????? ? ?????????? ??????? ??????????? ? ??? ???????? ?? (???????? ????? ???????????????? ?
???????????? ?? ???????????). ????? ????,
???? ??????? ????????????? ????? ??????????? ?? ?? ???? ????????????????? ??????,
? ???????? ??????? ???????? ? ?????????????
??????????? ??? ????????? ??????????? ????? (I), ??????????????? ? ???????? ???????
????? (?????? 12R).
???? ??????? ?????????? ?????? ?????????? ??????????? ? ??????????????????
?????????? ?? ????? ????????? Rh(CO)2+,
????????????????? ? ?????????????? ??????
(?????? 4R), ? ??????????? ????????? ??????
[7], ???????????? ??? ????? ???????? ????????? (????. 2). ?????? ???????, ??? ??????? ???????????????? ????????? ???????, ?????? ???
??????????? ??????? ??????? ??????????????
? ????????, ?? ??????????? ?? ?????????? ??
?????, ???????, ?????? ?????, ??????? ?? ????????? ???????????????? ??????, ?. ?. ???????
????????. ????????? ?? ????? ? ??????????
???????? ?????? ???????????, ???????????
?????? ?? ??????????? ???????? ??????????
[20]. ???? ??????? ??????????, ??? ? ?????????? ?????????????? Rh(CO)2+ ? ?????????
????????? ?????????? ??????? ???????????
????????? ?? ??????? ?? ???????? ?????. ???
????? ? ????????? ??????? ?????? ?????????
?? +0,33 ч +0,43 ?.?. (? ????????? ??????????)
?? ????????? ? ??????? +1,0 ?.?. ? ?????????
?????????. ??????????? Rh(CO)2+ ?? ???????
?????????????? ?????????? ????????? ??????
?? ????????? (?? ?62 ч ?66 ??-1 ? ?70 ч ?78 ??-1
??? ???????????????? ? ???????????? ???
??????????????) ? ??????????? ? ??????????
??????? ?????? ?????????. ??????????? ? ???????? ???????? ?????? ?? ?????????, ? ????? ????????? ??????? ?????? ????????? ? ?????? ???????? ? ??????? ??-????????????? ?
????????????? ???????? ????????????? ?????????? Rh(CO)2 ? ????????? ??????? ????????? ????? Rh (+1, 0, ?1) [21]. ??? ?????? ??????????????? ? ????????? ??????? ?????????
Rh ? ?????????? ?????????????? ???????????
????? (I) ? ????????? ?????????.
??????????
??????? ????????? ??????? ??????????? ????? (I) ? ????? ?????????????????????
???????? ? ??????? ???????????? ????????? ??/??-??????, ??????????? ???????
????????? ?? ???????? ???????????????
?????. ????????, ??? ? ???????? ??????? ????? Rh(CO)2+ ?????????????? ?? ???????????
??????? ?????????????????? ?????? ???????????? ???????. ??????? ?????????????
???????? ????? ???????? ???????????????
??????? ??????? ??? ??????????? ??????????? ???????? ???????????????? ???????
??????????? ??????????? ????? (I). ? ?? ??
????? ????????, ??? ??????????? ? ?????????
?????????????? ?? ????? ??????? ? ????????
?? ???????? ???????? ???????, ?. ?. ????????? ????????? ??????. ? ?????????? ??????????? ??????????? ????? (I) ?? ???????? ?????????? ????????? ????????? ??????????????
????????? ????? Rh.
# 196 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
?????? ?????????? ????????? ????????????????? ????? ?? ??? ?? ??????????? ?????????? ????????, ? ????? ?? ??? (?????????????? ?????? ?79) ?? ?????????? ?????????.
?.?. ???????? ???????? ???????????? ??????????????? ????????????? ???????? ????? ?????
?? ??????????????? ????? (?G17068). ?.?. ??? ?????????? ???? ?????????? ?????????????
????? ?? ?????????????? ?????????? ????????? ? 2008 ?.
?????? ??????????
1.
2.
3.
4.
5.
Rhodium carbonyl clusters in NaY zeolite made basic by treatment with sodium azide:
characterization by infrared spectroscopy. L. Basini, R. Patrini and A. Aragno, B. C. Gates, J. Mol.
Catal. 70 (1991) 29.
Rhodium in basic zeolite Y: a stable, selective catalyst for CO hydrogenation. T.J. Lee, B.C. Gates,
J. Mol. Catal. 71 (1992) 335.
Rhodium supported on faujasites: effects of cluster size and CO ligands on catalytic activity for
toluene hydrogenation. W. A. Weber, B. C. Gates, J. Catal. 180 (1998) 207.
NaY zeolite-supported rhodium and iridium cluster catalysts: characterization by X-ray absorption
spectroscopy during propene hydrogenation catalysis. W.A. Weber, A. Zhao, B.C. Gates, J. Catal.
182 (1999) 13.
On the mechanism of carbonylation in acetic acid and higher acid synthesis from methanol and
syngas mixtures on supported rhodium catalysts. L. Chateau, J. Hindermann, A. Kiennenman,
E. Tempesti, J. Mol. Catal. A 107 (1996) 367.
6. Heterogeneous carbonylation of methanol on rhodium introduced into faujasite-type zeolites.
H.-E.Maneck, D. Gutschick, I. Burkhardt, B. Luecke, H. Miessner, U. Wolf, Catal. Today 3 (1988)
421.
7. Structure and bonding of a site-isolated transition metal complex: rhodium dicarbonyl in highly
dealuminated zeolite Y. J. Goellner, B. C. Gates, G. N. Vayssilov, N. Rцsch, J. Am. Chem. Soc.
122 (2000) 8056.
8. The formation of a well defined rhodium dicarbonyl in highly dealuminated rhodium-exchanged
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and G. Spoto, J. Chem. Soc., Faraday Trans. 1, 85 (1989) 2113.
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D. A. Johnson, G. Blyholder, J. Phys. Chem. B 102 (1998) 10112.
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U. Birkenheuer, N. Rцsch, J. Phys. Chem. B 107 (2003) 2228; (b) Effects of the aluminum content
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by an accurate embedded-cluster method. R.C. Deka, V.A. Nasluzov, E.A. Ivanova Shor, A.M. Shor,
G.N. Vayssilov, N. Rцsch, J. Phys. Chem. B. 109 (2005) 24304; (d) First hybrid embedding scheme
for polar covalent materials using an extended border region to minimize boundary sffects on the
# 197 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
quantum region. A.M. Shor, E.A. Ivanova Shor, V.A. Nasluzov, G.N. Vayssilov, N. Rцsch, J. Chem.
Theory Comput. 3 (2008) 2290.
T. Belling, T. Grauschopf, S. Krьger, F. Nцrtemann, M. Staufer, M. Mayer, V. A. Nasluzov,
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T. Kerdcharoen, A. Woiterski, A. B. Gordienko, S. Majumder, N. Rцsch, PARAGAUSS version 3.0,
Technische Universitдt Mьnchen, 2004.
T. Belling, T. Grauschopf, S. Krьger, M. Mayer, F. Nцrtemann, M. Staufer, C. Zenger, N. Rцsch in:
High Performance Scientific and Engineering Computing; ed. H.-J. Bungartz, F. Durst, C. Zenger,
Lecture Notes in Computational Science and Engineering, Vol. 8, Springer, Heidelberg, 1999, p.
439.
The Gaussian-type orbitals density-functional approach to finite systems. B. I. Dunlap; N. Rцsch,
Adv. Quantum. Chem. 21 (1990) 317.
(a) Density-functional exchange-energy approximation with correct asymptotic behavior.
A.D. Becke, Phys. Rev. A 38 (1988) 3098; (b) Density ? Functional approximation for the correlation
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(a) Gaussian Basis Sets for Molecular Calculations, ed. S. Huzinaga, Elsevier, Amsterdam, 1984; (b)
Gaussian basis set for molecular wavefunctions containing second-row atoms. A. Veillard, Theor. Chim.
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O.J. Gropen, Comput. Chem. 8 (1987) 982.
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surface. I. V. Yudanov, G. Pacchioni, K. Neyman, N. Rцsch, J. Phys. Chem. B 101 (1997) 2786.
Adsorption of d-metal atoms on the regular MgO(001) surface: Density functional study of cluster
models embedded in an elastic polarizable environment. K.M. Neyman, C. Inntam, V. A. Nasluzov,
R. Kosarev, N. Rцsch, Appl. Phys. A 78 (2004) 823.
On the cation and water positions in faujasite. W. H. Baur, Am. Mineral. 49 (1964) 697.
??????????? ????????? ? ???????????? ????????????? ???????? ?????????????? ??????????
????? (I) ? ?? ???????????? ????????. ?. ?. ???, ?.?. ???, ?.?. ????????, ?.?. ???????,
????. ????????. ????? 46 (2005) 228.
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catalyst systems. M. Zhou, L. Andrews, J. Am. Chem. Soc. 121 (1999) 9171.
# 198 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
The Study of Rhodium (I) Dicarbonyl Coordination in Faujasite
Cavities by DFT-method
Svetlana S. Laletinaa, Alexey M. Shora, Elena A. Shora,
Vladimir A. Nasluzova,b and Anatoliy I. Rubayloa,b
a
Institute of Chemistry and Chemical Technology SB RAS,
42 K.Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The study of rhodium (I) dicarbonyl coordination in faujasite cavities by hybrid method of quantum
(Density functional theory) and molecular mechanics has been carried out. The importance of taking
into account environmental effects to determine correctly preferable Rh(CO)2+ cation coordination
centers has been demonstrated. The vibrational frequencies of CO groups have been calculated and
theirs connection with rhodium dicarbonyl (I) electron state has been shown.
Keywords: Density functional theory, rhodium (I) dicarbonyl, coordination, faujasite, embedding
cluster models.
# 199 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????. ?????? ??????? ?????? ????????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 200-205
~~~
??? 547.902.659.4
?????? ??????? ?????? ????????
?????? ?. ?????*
????????? ??????????? ???????????,
??. ?????????,79, ??????????, 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
????????????? ????? ??????? ????? ????????: 28-?-1-????????? ????????, 28-?????????????? ???????? ? 3,28-?????????? ???????? ???????? ?????????????? ?????
????????? ? ?????????????? ??????????????? ???????. ???????? ?????????? ??????????
??????????? ?? ????????? ??-, 1?-???-????????????? ? ??????????? ??????????? ???????.
???????? ?????: ??????? ????? ???????? ? 28-?-(1-?????????) ????????, 28-?????????????? ????????, 3, 28-??????????, ??????, ???????, ????????????? ??????????
??????, ????????, ??-, 1?-???-?????????????.
????????
????????????? ????????? ?? ?????? ????????????? ????? ?? ????????? ? ?????????????? ????????? ????? ??? ???????????.
?????? ???????? ?? ???????, ??? ????????
????? ????????????, ??????? ??????? ??
?????? ???????? ? ???????????? ?????????????? ???????? ?? ????????, ????? ???????,
??? ???????? ??????? ?? ??? ? ???????????.
????? ????, ????????? ????????????? ?????????????, ?????????? ??????? ??????????????? ????????, ??? ???????, ???? ????????
? ????? ????????? ???????? ????????. ????????????, ??????????? ??????????? ? ??????
????????????? ???????????, ????? ????? ??????????????. ????????? ??? ??????????? ????
????????? ????????? ??????? ?? ???????? ?
??????? ???? ???????? ?????????? ?? ??????
?????????????? ?????????? ????. ? ?????????????? ?????????? ???? ????????? ??????? ?
*
1
??? ???????????. ??????? ?????? ????????????? ? ????? ?????????? ??????????? ? ?????
?????????? ?? ??????? ??????, ? ??????? ???
????? ???? ?? 35 %.
????????
???????????
???????? ????????? ?????????? ????-?????????????????????, ???????????????, ?????????????????????, ??????????????? ?
?????????????????? ??????????. ???, 3,28?-??????????? ???????? ????????? ?????????????????? ? ????-???-??????????. ???????????, ??? 3,28-?-??????????????? ????????
????????? ??????? ????-???-??????????, ?????? ??????????????????? ??????????? ???????? ????????? ????? ?????????, ??? ?3 ???
?28 ????????? [1]. ???????? ???????????
???????? ???????? ???????????????????
??????????. ????????, ??? ??? ???????? ???????? ??????????? ?????????????????? ???????? ???????? ? ????????, ?????????????
Corresponding author E-mail address: kogay@lan.krasu.ru
© Siberian Federal University. All rights reserved
# 200 #
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??????? ? ?????????? ?????????? ???????????? ? ????????? ?????????????? ???????
??????????? [2]. ??????????????? ??????
?????????????? ? ???????????? ???????? ?????????? ?????????? ?????????? «??????» ?
«????» ? ????? 12 ? 20 ??/??. ????? ????????
???? ??????? ????????, ??, ?????? ? ???, ??????????? ????? ?????? ??????????? ????????
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?????? ??????????????.
? ???????? ??????????? ????????? ????
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??????????, 3-??????????????? (?????????????), ????????? (??????????) ??????,
??????????????? ?? ???????? [4] ?? ?????? ?
?????????????? ???????. ??? ??????? ????
??????? ??????, ??? ??? ???? ??? ?? ??????????? ???????? ????????????? ???????????
[5,6]. ??????? ????? ???????? ????????????? ?? ???????? ? ??????????????? ??????????????:
? ????????????? ? ????????? ????????? ????????? ????????????? ???????? [3].
?????? ???????????? ?????? ???????,
??? ?????? ???????? ??????????? ????????
???????? ????????????? ??????????? ????CH3-C=CH2
CH3-C=CH2
O
R
C
Cl
CH2OH
HO
CH2O
O
I
II ( a,b,d)
a - R* = H, R = 1- ?????????
b - R* = H, R = Ph-?CH2 ?CH2
d - R* = R = C7H15
????????????????? ?????
???????? ???? ??????? ????????????
??????? ??? ?? ?????????? «Silyfol» ? ?????????????? ????????????? ????????? ? ??????? - ?????????? ??????? ? ???????????
100:2:0,5. ??-??????? ?????????? ?? ???????
?Vektor?-22 ? KBr, ??????? 1?-??? ? ?? ??????? ?Avance 200? (BRUKER) ? ??????? ???????? 200 ??? ? CDCl3. ???????????? ???????
? ?????? ?? ??????????? ?????????.
???????????? ???????? ?????????????? 1-??????????????????? ???????. ?
?????????? ?????, ?????????? ????????,
???????? ????????????? ? ????????? ????????, ????????? 2 ? ???????? ? 10 ?? ??????
????????. ???????????? ?????????-1 ?????????? ??????? ? ?????????? 1,2 ? ?????????? ?
10 ?? ?????? ??????? ? ??????????? ? ???????
20 ??? ??? 0 0?, ????? ???? ??????????? ?????????? ???????? ?? ????????? ? ?????????
?? 8 ????? ??? 20 0?, ?????????? 2 ?? ????,
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???????????? ? ??????? 30 ???. ????????????
???????? ??? ???????? ????????????? ??????.
??????? ?????????????? ????????????, ????????? 1 ?. ??????? ????????, ??????????
????????? ??????????? ?????? ? ????? ?? ??????????? ?????, ?????? ??? ????????? ????????? ??????. ???????????? ????????. ???????
????????? ?? ?????????????? ?????????? ???
?????? ????????????? ???????????? ????????????? ?? ??????????. ? ???????? ???????
???????????? ????? ????????? ? ??????????
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??- ? ???-?????????????, ????????????
??????? ??????????? ???????.
28-?-(1-?????????) ???????? (IIa)
????? 45, 2%; ??-??????, ?, ??-1: 3629,0;
3419,8; 2913,5; 2851,9; 1716,6; 1454,0; 1232,1;
1078,5; ?????? 1? -???, (?, ?.?.): 0,87; 0,90;
0,95; 1,04 (15?, 5?., 5??3); 1,10 ? 2,00 (41?, ?.,
??2, C?); 1,94 (3?, ?., 3??, ????.); 2,43 ? 2,56
(3?. ?., ?13, ?16); 3,06 ? 3,18 (1?, ?., ?19);
3,21 (1?, ?., ?3); 3,77 (1?, ?., ?: ?? ??? ?3);
4,32; 4,26; 3,86; 3,81 (2?, ??., J=12, ?28); 4,62
(1?, ?., ?29?); 4,71 (1?, ?., ?29??). ??????? %:
? 81,23; ? 10,29. C41?64?3. ????????? %: ?
81,46; ? 10,60.
???????????? ???????? ?????????????? ????????????? ???????. ? ??????????
?????, ?????????? ????????, ???????? ????????????? ? ????????? ????????, ???????? 3,36 ? ????????, 10 ?? ??????????? ????????, ????????? ?? 0 0?. ????? ?? ??????
? ??????? 10 ??? ????????? ??????? 2,35 ?
????????????? ????????????? ??????? ? 10
?? ??????????? ???????, ???????????? ? ??????? 30 ???, ????? ???? ??????????? ?????????? ???????? ?? ????????? ? ????????? ??
8 ????? ??? 20 0?. ????? ? ??????????? ?????
?????????? 2 ?? ???? ? ???????????? ? ??????? 30 ???. ?????????? ????????? ???????
? ?????? ??????????? ?????????? ?????????,
??? ? ?????????? ???????.
28-?-????????????? ???????? (IIb)
????? 56,4 %; ??-??????, ?, ??-1: 3629,0;
3028,2; 2918,9; 2849,7; 1728,4; 1605,0; 1500,0;
1460,0; 1454,1; 1180,0; 745,2; 698,8; ?????? 1?
-???, (?, ?.?.): 0,87; 0,90; 0,95; 1,04 (15?, 5?.,
5??3); 1,10 ? 2,00 (29?, ?., ??2, C?); 2,43 ?
2,56 (3?. ?., ?13, ?16); 2,66 (2?, ??., J=7,6;
??2: ?-?????); 2,95 (2?, ??., J=3,6; ?-?????)
3,06 ? 3,18 (1?, ?., ?19); 3,21 (1?, ?., ?3); 3,77
(1?, ?., ?: ?? ??? ?3); 4,32; 4,26; 3,86; 3,81 (2?
??., J=12, ?28); 4,62 (1?, ?., ?29?); 4,71 (1?, ?.,
?29??); 7,23 ? 7,42 (5?, ?., ????????.).
??????? %: ? 80,94; ? 10,35. ?39?58?3 ????????? %: ? 81,53; ? 10,10.
???????????? ???????? ?????????????? ?????????? ???????
? ?????????? ?????, ?????????? ????????, ????????????? ? ????????? ????????,
????????? 3,4 ? ???????? ? 10 ?? ??????????? ????????, ????????????. ????????????
?????????? ??????? ? ?????????? 2,47 ?, ???????????? ? 10 ?? ??????????? ???????, ??????????? ? ??????? 20 ??? ??? 0-5 0?, ???????????? 30 ???, ????? ???? ???????????
?????????? ???????? ?? ????????? ? ????????? ?? 8 ????? ??? 20 0?. ????? ????????? 2
?? ???? ? ???????????? ? ??????? 30 ???.
?????????? ????????? ??????? ? ?????? ??????????? ?????????? ?????????, ??? ? ?????? ???????.
3, 28-?-?????????? ???????? (IId)
????? 79,6 %; ??-??????, ?, ??-1: 2956,0;
2858,1; 1745,2; 1642,3; 1439,4; 1371,5; 1247,8;
1047,6; 844; ?????? 1? -???, (?, ?.?.): 0,87;
0,90; 0,95; 1,04 (15?, 5?., 5??3); 1,10 ? 2,00
(48?, ?., ??2, C?); 2,43 ? 2,56 (3?. ?., ?13,
?16); 3,06 ? 3,18 (1?, ?., ?19); 4,32; 4,26; 3,86;
3,81 (2?, ??., J=12, ?28); 4,50 (1?, ?., ?3); 4,62
(1?, ?., ?29?); 4,71 (1?, ?., ?29??); ??????? %:
# 202 #
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?????? ?. ?????. ?????? ??????? ?????? ????????
? 79,09; ? 11,55. ?46?80?4. ????????? %: ?
79,54; ? 11,23.
?????????? ? ??????????
?????????? ????????? ??????? ????????? ????????????? ??????????? ????????. ?
???????? ??????????? ?????????, ??? ???????, ????????? ????????? ??? ?????????????
?????????? ?????? ? ??????????? ????????
??? ????????? ??????. ? ???????? ??????????? ????????? ???? ???? ???????????? ????????????? 1-???????????????????, ????????????? ? ?????????? ??????. ????????????
???????? ????????? ? ????? ???????. ??????????? ???????? ? ???????????? ????????
?????????? 1: 2 ?? ???? ??????.
? ??-??????? ???????? ???????????? ???????? ?????????????? 1-????????? ?????????? ??????? ???????????? ?????? ??????????
??? 1716,6 ??-1, ??????????????? ?????????
?????????? ???????????? ?????? ???????
??????. ?????? ?????? ?????????? ??????????? ? ??-??????? ????????. ?????? ??????????
??? 1232,1 ??-1, ????????????? ????????? ?????????? ????? ??? ????????????? ??????.
? ???????? ???????????? ??????????? ??????
?????????? ??? 1788 ??-1 ???????????????
????????? ?????????? ???????????? ?????? ????????????? 1-???????????????????
???????, ??????????? ????? ?????? ?????????? ??? 1693,5 ??-1, ??????????????? ????????? ?????????? ???????????? ??????
1-??????????????????? ???????. ????? ???????, ?? ????????? ?????? ??-?????????????
????? ??????? ????? ? ??????? ????????????? ????? ? ?????????? ???????? ???????.
???? ????? ???????????? ?????? 1?-????????????????. ? ???-??????? ?????????????? ?????????? ??????????? ????? ????????
??????????? ???????? ??? ?28 ? ???????
????? ??????? ???? (4,32 ?.?.; 4,26 ?.?.; 3,86
?.?.; 3,81 ?.?.) ?? ????????? ? ????????? ????
???????? ? ???????? (3,78 ?.?.; 3,83 ?.?.; 3,31
?.?.; 3,37 ?.?.). ????? ???????? ???????????
???????? ? ????? ?????? ???? ???????????????
? ????????? ????? ? ???? ????? ???????? ???????????????? ???????????, ??? ??-??????,
??? ????? ???? ????????? ???????? ?-??
=? ?????? ??? ?28 ????????. ?????? ?????????? ??????????? ???????? ????? ???????, ??? ?? ???????? ?????????? ???????? ?
1-??????????????????? ???????. ??????????????? ????? ?????? ?????????? ????????????? ?????? ??????? ??? ?3 ?? ????????? ?
???????? ????? ??????? ? ???????? (3,21 ?.?.)
? ??????? ? ??-??????? ????? ?????????? ??????? ?????? ?????????? ? ??????? 3629 ??-1
(????????? ????????? ????? ?-?), ??? ?????????? ??? ????????????? ????????????? ????????? ????????????? ??????. ?????? ??- ?
?-???-????????????? ???????????? ??????? ??????????? ???????. ????? ???????, ? ?????????? ???????????? ???????? ?????????????? 1-??????????????????? ??????? ???????
???????? ? 28-?-(1-?????????) ????????.
???????????? ???????? ??????????????
????????????? ??????? ??????? ? ??????????? ????????? ????????, ??? ??????? ?? ??????? ?????? ??- ? 1?-???-????????????? ?
?????? ??????????? ???????. ? ??-???????
??????????? ?????????? ?????????? ??????
??? 1728,4 ??-1, ??????????????? ?????????
?????????? ???????????? ?????? ????????
?????, ? ????? ??????? ?????? ??? 1180 ??-1-,
??????????????? ????????? ?????????? ???
????????????? ?????. ??? ?????? ?????????? ??????? ????????????? ??? 745 ??-1 ?
698,8 (?????????????? ????????? ?-? ?????
? ?????????????? ?????????????? ????????? ?-? ????? ??????????? ??????) ????????????? ?????????????? ??????????? ???????.
? ???-?????? ???????? ?????????????? ???????? ? ????????????? ????????????? ??????? ??????????? ????? ???????? ????????
1
# 203 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????. ?????? ??????? ?????? ????????
??????????? ?????? ??? ?28 ? ??????? ??????? ???? (4,32 ?.?.; 4,26 ?.?.; 3,86 ?.?.; 3,81
?.?.) ?? ????????? ? ???????? ???? ????????
? ????????. ?????? ???-??????? ???????????
???????? ??????? ?????, ??? ?? ???????? ?????????? ???????? ? ????????????? ???????:
??????????? ????? ???????? ???????? ??? ?3
?? ????????? ? ????????? ???? ???????? ? ????????. ?????????? ???????? ?????? ??? ?3
?????????????? ??????? ??-?????????????:
?????? ?????????? ? ??????? 3629 ??-1 ??????????????? ? ??????? ????????? ????????????? ??????, ????????? ? ???????????????
????????. ??????????? ????????? ???????? ?
????????????? ??????? ???????????? ??????? ??????????? ???????.
????? ???????, ?? ????????? ?????? ??? ???-????????????? ? ?????? ???????????
??????? ??????? ??????????, ??? ???????????
?????????? ???????????? 28-?-?????????????
????????.
???????? ???????????????????, ??? ?
????????? ???????, ???????? ????????????
?????????? ???????. ???-?????? ???????????? ???????? ??????? ??????????? ??????
?????????? ????????? ????????. ? ??-???????
?????????? ??????? ????????????? ???????????? ????????????? ?????????? ??????????? ?????? ?????????? ??? 1745,5 ??-1 ?
??? 1247 ??-1, ??? ????????????? ?????????
?????????? ?????? ????? ?=? ? ??? ???????
??????. ? ???-??????? ????? ?????????? ??????????? ????? ???????? ???????? ????????-
??? ?????? ??? ?28 (4,32 ?.?.; 4,26 ?.?.; 3,86
?.?.; 3,81 ?.?.) ? ??????? ??? ?3 (4,50 ?.?.) ?
??????? ??????? ???? ?? ????????? ? ????????? ????? ??????? ? ???????? (3,21 ?.?.). ?????
??????? ??????? ??? ?3 ??????? ? ??????? ????? ???????????????? ???????????, ??? ????????, ??? ????? ???? ????????? ?????????
???????? ?????? ? ??? ?????????. ???? ?????
?????????????? ??????????? ? ??-??????? ?????? ?????????? ? ??????? ????????? ????????? ????? ?-?. ????? ???????, ?? ?????????
???????????? ?????????? ? ?????? ??????????? ??????? ????? ??????? ????? ? ???, ???
?????????? ?????????? ???????????? ??????
?????????? ??????? ? ???????? ? 3,28-??????????? ????????.
??????????
???????? ???????????? ???????? ??????????????? 1-???????????????????, ????????????? ? ?????????? ?????? ? ????? ???????
? ??????????? ?????????? ???????? ??? 0 є?
???????? ????? ??????? ????- ? ???????
????????. ???????? ?????????? ??????????
??????????? ?? ????????? ?????? ??- ? 1????-????????????? ? ??????????? ??????????? ???????.
????????, ??? ??? ??????? ????????? ???????? ? ????????????? ???????, ?????? 1:2,
?????????? ?????????: 28-?-(1-?????????)
???????? ? 28-?-????????????? ????????.
???????????? ?????????? ??????? ????????
?????? ? 3,28-?-?????????? ????????.
?????? ??????????
1.
2.
3.
?????????, ?.?., ???????, ?.?., ??????? ?.?., ??????? ? ??? ??????????? // ????? ? ????????? ??????????? ????????. 2005. ?.13. ?6. ?. 1-30.
??????, ?.?. ?????? ??????????? ?????. ?.: ?????? ?????, 2001. 248 ?.
???????, ?.?., ????????? ?.?., ?????????? ?.?., ??????? ?.?., ????????? ?.?. ?????? ?
????????????????? ?????????? ?????? ????????, ??????????? ??????? ? ????????????//
??????-????. ????. 2005. ?.39. ?8. ?. 9-12.
# 204 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????. ?????? ??????? ?????? ????????
4.
5.
6.
???????-?????????. ?????? ???????????? ? ???????????? ?????. ?.: ?????, 1969. ?. 232.
?????????, ?.?., ?????, ?.?. ??????????????? ?????. ?.: ????????, 1991. 358 ?.
??????, ?.?. ????????????? ??????????????????? ?????? ??? ??????????? ????????????? ??????? ? ???????????? ???????? ??????????// ??????-????. ??????. 1987. ?.21. ?.
931-940.
Synthesis of Ester of Betulin
Tamara I. Kogay
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Novel ester of betulin ? betulin-28-O-(1-adamantat), betulin-28-O-hydrocinnamat, betulin-3, 28-Odikaprilat were produced from betulin and appropriate chlorangidrids of carbon acid in absolute
benzene at 0 єC. The IR-, 1H-NMR- and elementary analysis evidence support this structure of these
esters of betulin.
Keywords: esters of betulin ? betulin-28-O-(1-adamantat), betulin-28-O-hydrocinnamat,, betulin-3,28O-dikaprilat, synthesis, betulin, chlorangidrids of carbon acids, structure, IR-, 1H-NMR-spectroscopy.
# 205 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 206-211
~~~
??? 542.182.024:546.98
?????? ???????? ??????????? ???????? ???????? ???????
??????????? ?????????????????
???? ?. ?????????,?, ????? ?. ????????,
???????? ?. ?????????, ???? ?. ?????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
??????? ??????????? ????????????????? ??????????? ??????? ???????? ? ??????-??????
?????????. ???????? ?????, ??????????? ???????? ???????? ???? ?? ???-?????? ?
?????????????? ? ???????? ???????? ????????? ???????? ???????? ? ????????? ????????
????????????. ?? ??????? ???????? ????? ???? ?????????? ???????? ??????? ???????????
??????????? ????????, ???????? ??????? ?????? ??????????? ? ???????????? ?? ???????
?????????.
???????? ?????: ??????? ????????, ??????????? ?????????????????.
????????
???? ?? ?????????? ??????? ????????????????? ??????? ? ??????????? ????????????????? (???) ? ??????? ???????????? ???????? ?????, ????????? ????????? ????????
????????? ????????????????? ??????????
? ???????? ? ????????????? ?????? ?????????? ??????. ????????????? ?????? ??? ???????? ? ?? ??????????? ?????? ???????? ?
?????? [1].
??? ???????, ? ?????? ??? ?????????
???????? ????????, ?? ??????? ???????????
?? ??? ???? ????????????-?????????????????
???????. ??? ???????????? ??? ?????, ????? ?? ??????????? ???????? ??????????
?????????. ?? ???? ??????? ???????? ?????*
1
?????? ???????? ?????????? ???????, ?????????? ????????? ????????? ??????????
??????? ?????, ??? ???????, ? ???????, ??? ??
?????????? ???????? ???????.
???????????????? ??????? ??????????
??????, ? ????????? ????????, ??????? ??????? ?????????? ?? ?????? ???????? ????????? ?????????? ?????????, ????????? ??
??????????? ????????????? ?????????? ??????????, ??? ??????????? ??????? ???????????? ???????????????????, ??????????????????????????, ????????????? ? ??????
??????. ?????? ?????? ????? ??????? ?????????? ??????????????, ?? ?????? ?????????? ???????????? ? ? ???? ??????? ??????? ??????? ????????? ????????????????? ??????.
Corresponding author E-mail address: ov_bel@icct.ru
© Siberian Federal University. All rights reserved
# 206 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
??????? ?????????? ?????????????? ???????,
? ????????? ?????????????????, ?????????????? ?????????? ?????????????.
????? ???? ???????? [2], ??? ???????????????? ????????? PdCl42-/Pd0 ??????? ?? ???????????? ?????????????? ????????. ??????????? ?????????? ?? ??????? ?????? ??????
??????????? ?????????? ???????.
? ??????? ??????????? ????? ???? ??
???-?????? ?? ???????????? ???????? ??????? ? ?????? ????????? ??????. ?????? [3],
???????? ????????????????? ???????? ?? ???????????? ??????????? ????????? ? ?????????????????? ???????????? ???????? ???????
???, ??????????, ??? ???????? ????????? ??
??????????? ???????? ?? ??????? ????. ??????? ????????????????? ?????????? ???????? ?????? ??????? ? ??? ????? ??????? ?????????????? ? ???????????? ??? ???????????.
? ?????? [4] ????????, ??? ?????????????????
???????? ????? ???????? ??????????? ?? 0,3
?? 5 ?2/? ? ??????????? ?? ??????????????
???????????? ? ??????????? ?????????. ???????????, ??? ?????????? ??????????? ???????? ? ???? ??????? ????????? ??????????
??????????? ? ??????? ? ??????? ???????? ????????????.
?? ?????? ??????, ??????? ???????
??????? ??????????? ????????????? ????????
????????? ?? ????? ???-??????, ? ?????????
?? ????????? ????????? ? ??????? ????????? ????.
????? ???????, ????? ????????? ??????
???????? ???????????? ??????????? ?????????? ????????????? ??????????? ?????????????????????? ?????? ??? ?????? ???????? ??????????? ???????? ???????? (0).
????????????????? ?????
????????, ?????????????? ? ??????, ?????
???????????? ?? ???? ?.?. ???????? H2PdCl4
???????? ???????????? ???????????????? ??-
???????? PdCl2 ? ???????? ??????? ???????.
??????? ???????? ???????? ????? ???????????
?????????? ?????? ????????? ???????? H2PdCl4
? 1 ? HCl. ???????????? ???????? (II) ? ???????? ?????????? ??????-????????????? ?
?????????????????????? ????????. ???????
???????? ? ??????????? ???????? ???????????? (???????? ????? ?? ??????????????
??????????? ?????? ???????????????? ???????????? [2]) ??????? ??????? ???????????????? ???????? ? ????????? ?????? ???
1000?. ??????????? ????? ????????????? ??
?????????, ????????? ? ?????? [5].
??????????? ??????? ????????? ????? ???
??????????? ???????? ???????? ???? ????????? ? ??????? ??????????? ASAP-2420
(Micromeritics, USA) ??? 77?. ?????? ???????? ??????????? ???????? ?????????? ? ?????????????? ?????? BET [6]. ?? ?????????
????????? ????????? ? ????????? ????????
????????????? ????? ?????? ????????? ???
????????? 353 ?, ????????????????? ??????
? 10-12 ?. ????????????? ???????? ??? ??????????? ??????? ???????? ? ????????? ?? 0,01
?? 0,99 P/P0.
????????????????? ???????????? ????????? ? ????????????? ???? ???????????,
???????????????? ??????????????? ??????
??????? 35 ??3 ??? ??????????? 333 ?. ???
?????????????????????? ????????? ????????????? ???????????? ??-50-1-1 ? ?????????????? ??-8 ? ???????????????? ?????????????? ???????? ???1. ????? ???????????,
??? ???? ???????? ????? [2], ????? ????????????? ?????????????? ???????????? ??????????, ? ?????? ? ???????????? ?????????
??????????? ????????????? ????????????
????????. ? ???????? ???????? ? ????????????????? ????????? ????????????? ????????, ?????????? ? ?????????? ???????????
????????. ???????? ???????????? ????????
(???????) ? ???? ?????????????, ?? ??????
# 207 #
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???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
??? ????-?????????????, ?? ???????????. ?
???????? ???????????????? ?? ???? ?????????? ???????????? ?????????? ??????????
????????, ???????? ??????????? ???? ??????????? ???????. ?????????? ?????????
?? ???? ??????? ?????? ???????? ?????????????? ????????. ? ???? ???? ?????????????
????? ??????? ?????????? ?????.
?????????? ? ??????????
????????????? ?????????? ????????????????? ?????? ????????? ?? ?????????? ?????? ????????????? ????????? ??????????
??????? ??????????? ??????????. ??????????? ???????? ??? ??????????? ???-??????
???? ????????? ??????????? ????????? ????
??? ????????? ???????? ????????, ????????????? ?? ?????? ?? ?????, ?? ? ?? ???????
????????????.
????????????? ??? ?????? ???????????
??????? ??????????? ???-?????? ?????????? ???? ?????????? ??????? ? ?????? ??????? ????????? ??????????, ? ????? ???????????? ? ??????? ?????????? ????????. ? ????????
?????????? ???????? ???? ??????? ?????? 1?
HCl. ???? ????????, ??? ??? ?????????????
????????? H2PdCl4 ? ????????? ????????????
10-4 ? 10-2 ????/? ???????? ????? ?? ???????????. ???????????????? ??????????????
???????????, ??? ???????? ? ???? ???????????? ?????????? ??????????? ? 1? c??????
???????, ??????? ? ?????????? Pd(II) ? ???????? ? ????????? 10-6?10-5 ????/?, ? ??????????? ?? ???? ????????? ? ??? ?????. ??? ??????
???????? ????????? ?????????? ??????????,
????? ?????????? ????????????? ? ??????????? ? ???? ????? ???????? ???? ?????????,
???????? ??? ??? ??????????? ???????, ?
????? ?? ??????????? ??????????? ?????????? ??????????? ?????????. ?????? ????????
? ??????????????? ????????????? ?????????
???????????? ???????? ?????????: ??????
?????? ???????? 200 ??, ??????? ? 400 ??, ???????????? ??????????????? ????????? ?????????.
???????????????? ????????, ??? ??? ????????????? ??????? ?????? ? 1? HCl ???????? ???? ????? ????????????? ??? ????????
? ??????? ????????? ????????????.
? ????????? ?????? ??????? ??? ?????????: 1 ? ??? ??????????? ??????????? ?????????? ???????? ??????????????; 2 ? ????????
??????????? ??????????? ????????? ????? ??
?????????????? ???????????.
??? ??????? ???????? ????????? ??? ?????????? ???????? ?? 5 ??/? ?? 200 ??/?. ????????? ?????? ?? ?????????? ????????? 10,
20 ? 50 ??/? ??? 20,2 ?? ?????????????????
???????? ? 1M HCl ????????? ?? ???. 1. ???????????, ??? ???????? ????????? ???????????
?????? ?? ????????? ????????? ?????????
????, ? ?????? ?? ???? ?? ?????????? ???????? ?????????? ? ??????? ???????? ???????? ??????????. ???????? ????? ??????????
???. 1. ???-?????? ??? ?????????????????
???????? ??? ????????? ????????? ?????????
(20,2 ??): 1 ? 50 ??/?; 2 ? 20 ??/?; 3 ? 10 ??/?
# 208 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
???? ?? ???-?????? ??????????? ??? ???????? 20 ??/? ? ??????????? ??????????? ???
???? ???????????? ??????????? ??????????.
?? ???? ??????? ??? ??????????? ?????????
??????????? ? ?????? ????????? ?????????.
?? ???. 2 ???????? ???-?????? ??? 100
?? ??????????? ????????. ????? ?? ???????????? ????? ? ?????? ?????? ?????????? ?
??????? 20-25 ??????, ??? ??????????? ?????
???????? ??????????? ??????????? ?????????. ???????????, ??? ??????????? ??????????
??????????? ????????, ??????????? ??? ??????????? ???? ?? ???-??????, ?????????? 20
??.
? ??????? ?? ??????????? ?????? ?????
?? ???????????? ????? ??? ?????????????
????????????????? ???????? ??????????????
?? 1-2 ?????. ??????????? ?????????? ????????????????? ????????, ??? ???????? ??? ???????????? ?????????? ??? ?? ???-??????,
????????? 4 ??. ?? ???. 3 ????????? ????????? ?????????? ??????? ????????????????? ????????. ??? ????? ?? ???????, ???????? ???? ? ??????????? ??????? ?????????? ?
??????? ????? ?????? ???????????, ??? ????
??????? ????????? ???? ?????????????.
???????? ????????????????? ?????????
? ???????? ??????????? ????????? c ???????? 8 ??2 ????????, ??? ???????? ???????? ?
??????? ??????? ??????????? ??????????? ??
????????? ? ???????????????? ???????????.
???????????? ????????? ????? ???????? ???????? ? ??????????? ????????? (???????). ??????? 1 ? 2 ???????? ???????????????
??????????????? Pd(II) ?????????? ???????????? ? ????????? ?????? ??????????????.
??????????? ????????? 1 ? ????????? ?? ????? ????????????? ???????? [5] ? ?????????
1? HCl ??? 453 ? ? ??????? 2 ? 8 ????? ???????? ??????? 3 ? 4. ???????? 5 ???????
??????? ??????????? ?????.
???. 2. ???-?????? ??????????? ????????
(100 ??): 1 ? ???? ?1; 2 ? ???? ?20
???. 3. ??????????? ????? ???-?????? ?? ?????
??????? ????????????????? ????????: 1 ? 8,3 ??;
2 ? 15,6 ??; 3 ? 21,9 ??
# 209 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
?????? ??????? ????????? ???? (? ???????? ????????) ?????????????? ?? ??? ??????
??????????. ??????????? ??????????? ??????? ????????? ???? ?? ?????????? ???????????? ???????? ? ??? ???????????? (????????
??????? ???????????), ??????? ????????????
?? ???. 4.
??????????? ??????????????? ???????
??????????? ????????? ? ???????? ?? ???? (?
???????? ????????) ???? ?????????? ?????-
??? ??????????? ??????????? ????????
????????. ????????????? ???? ??????????? ?
??????? ?????? ????????? ??????????? ????????? ? ???????. ???????, ??? ??? ???????
??????????? ??????? ? ????? ???????????
?????, ?????????? ??????? ??????, ???????
???????? ??? ??????????? ???????? 2,2 ???,
? ??? ????????????????? ? 40 ??.
????????????? ?????? ???????? ??????????? ???????? ???????? ????????? ???????
???. 4. ??????????? ??????? ???????? ????? ?? ????? ??????? ??? ???????? ?
????????? ???????? ????????????
???. 4. ??????????? ??????? ???????? ????? ?? ????? ??????? ??? ???????? ? ????????? ????????
????????????
???????. ????????? ???????? ??????? ??????????? ???????? ???????? ???
? ??????? ????????? (??) ?????
????????
???????? ???????????, ?2/?
???
??
1
11,4
12,5
2
3,5
3,6
3
1,8
1,6
4
0,9
5
0,2
0,6
# 210 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
????????????, ?? ?????? ??? ????????? ?
??????? ?????????, ??????????? ? ???????,
?????????? ??????? ????????????.
????? ???????, ?? ??????????? ????????? ?????? ???? ??????????? ???????????
?????????? ??????????? ? ????????????????? ?????? ???????? ??????????? ????????
???????? ? ??????? ????????? ???????? ??????.
?????? ??????????
1.
2.
3.
4.
5.
6.
????? ?. ???????????????????? ??????. ?.: ?????. 2006. 326?.
???????? ?.?., ???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?. ???????????
?????????? ????????? PdCl42?/Pd0 ?? ???????????? ?????????????? ????????. ?????? ???.
?????. 2008.?.82.?4. ?.1067-1073.
???????? ?., ?????? ?., ????????? ?. ???????????? ???????? ??????????? ???????? ?
?????? ??????? ??????? ????????????????? ????????? ????????????????. ????????????.
2003. ?.39.?9. ?.1067-1073.
???????? ?.?., ?????? ?.?. ? ??????????? ????????? ???????????? ????
???????????????? ????????? ? ??????????? ?????????????? ???? ???????? ??? ????????
??????? ????????? ??????????. ????????????. 2007. ?.43. ?13. ?.1493-1498.
???????? ?.?., ???????? ?.?., ?????? ?.?., ???????? ?.?. ????????? ???????? ??????
???????????????? ??????????? ????? ? ???????????? ????????? ??? ??????????
????????????. ?????? ???. ?????. 2007. ?.81. ?8. ?.1479-1482.
Brunauer S., Emmet P.H., Teller E. Adsorption of gases in multimolecular layers. J. Am. Chem.
Soc. 1938. V. 60.P.309.
Palladium Powders Specific Surface Estimation by Method
of Cyclic Voltammetry
Oleg V. Belousova,b, Roman V. Borisovb,
Vladimir A. Parfenova and Yuri V. Saltykova
a
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Palladium powders in muriatic solutions were investigated by a method of cyclic voltamperometry. A
regime to obtain cathode peaks in cyclic voltamperometry curves with using varied dispersity palladium
powders as main electrode was selected. Specific surfaces of palladium powders were estimated from
cathode peaks areas. Obtained results are in well accordance with nitrogen adsorption data.
Key words: Palladium powders, cyclic voltamperometry.
# 211 #
????
??????????? ??? ????????? ??????????? ????? (I), ??????????????? ? ???????? ???????
????? (?????? 12R).
???? ??????? ?????????? ?????? ?????????? ??????????? ? ??????????????????
?????????? ?? ????? ????????? Rh(CO)2+,
????????????????? ? ?????????????? ??????
(?????? 4R), ? ??????????? ????????? ??????
[7], ???????????? ??? ????? ???????? ????????? (????. 2). ?????? ???????, ??? ??????? ???????????????? ????????? ???????, ?????? ???
??????????? ??????? ??????? ??????????????
? ????????, ?? ??????????? ?? ?????????? ??
?????, ???????, ?????? ?????, ??????? ?? ????????? ???????????????? ??????, ?. ?. ???????
????????. ????????? ?? ????? ? ??????????
???????? ?????? ???????????, ???????????
?????? ?? ??????????? ???????? ??????????
[20]. ???? ??????? ??????????, ??? ? ?????????? ?????????????? Rh(CO)2+ ? ?????????
????????? ?????????? ??????? ???????????
????????? ?? ??????? ?? ???????? ?????. ???
????? ? ????????? ??????? ?????? ?????????
?? +0,33 ч +0,43 ?.?. (? ????????? ??????????)
?? ????????? ? ??????? +1,0 ?.?. ? ?????????
?????????. ??????????? Rh(CO)2+ ?? ???????
?????????????? ?????????? ????????? ??????
?? ????????? (?? ?62 ч ?66 ??-1 ? ?70 ч ?78 ??-1
??? ???????????????? ? ???????????? ???
??????????????) ? ??????????? ? ??????????
??????? ?????? ?????????. ??????????? ? ???????? ???????? ?????? ?? ?????????, ? ????? ????????? ??????? ?????? ????????? ? ?????? ???????? ? ??????? ??-????????????? ?
????????????? ???????? ????????????? ?????????? Rh(CO)2 ? ????????? ??????? ????????? ????? Rh (+1, 0, ?1) [21]. ??? ?????? ??????????????? ? ????????? ??????? ?????????
Rh ? ?????????? ?????????????? ???????????
????? (I) ? ????????? ?????????.
??????????
??????? ????????? ??????? ??????????? ????? (I) ? ????? ?????????????????????
???????? ? ??????? ???????????? ????????? ??/??-??????, ??????????? ???????
????????? ?? ???????? ???????????????
?????. ????????, ??? ? ???????? ??????? ????? Rh(CO)2+ ?????????????? ?? ???????????
??????? ?????????????????? ?????? ???????????? ???????. ??????? ?????????????
???????? ????? ???????? ???????????????
??????? ??????? ??? ??????????? ??????????? ???????? ???????????????? ???????
??????????? ??????????? ????? (I). ? ?? ??
????? ????????, ??? ??????????? ? ?????????
?????????????? ?? ????? ??????? ? ????????
?? ???????? ???????? ???????, ?. ?. ????????? ????????? ??????. ? ?????????? ??????????? ??????????? ????? (I) ?? ???????? ?????????? ????????? ????????? ??????????????
????????? ????? Rh.
# 196 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
?????? ?????????? ????????? ????????????????? ????? ?? ??? ?? ??????????? ?????????? ????????, ? ????? ?? ??? (?????????????? ?????? ?79) ?? ?????????? ?????????.
?.?. ???????? ???????? ???????????? ??????????????? ????????????? ???????? ????? ?????
?? ??????????????? ????? (?G17068). ?.?. ??? ?????????? ???? ?????????? ?????????????
????? ?? ?????????????? ?????????? ????????? ? 2008 ?.
?????? ??????????
1.
2.
3.
4.
5.
Rhodium carbonyl clusters in NaY zeolite made basic by treatment with sodium azide:
characterization by infrared spectroscopy. L. Basini, R. Patrini and A. Aragno, B. C. Gates, J. Mol.
Catal. 70 (1991) 29.
Rhodium in basic zeolite Y: a stable, selective catalyst for CO hydrogenation. T.J. Lee, B.C. Gates,
J. Mol. Catal. 71 (1992) 335.
Rhodium supported on faujasites: effects of cluster size and CO ligands on catalytic activity for
toluene hydrogenation. W. A. Weber, B. C. Gates, J. Catal. 180 (1998) 207.
NaY zeolite-supported rhodium and iridium cluster catalysts: characterization by X-ray absorption
spectroscopy during propene hydrogenation catalysis. W.A. Weber, A. Zhao, B.C. Gates, J. Catal.
182 (1999) 13.
On the mechanism of carbonylation in acetic acid and higher acid synthesis from methanol and
syngas mixtures on supported rhodium catalysts. L. Chateau, J. Hindermann, A. Kiennenman,
E. Tempesti, J. Mol. Catal. A 107 (1996) 367.
6. Heterogeneous carbonylation of methanol on rhodium introduced into faujasite-type zeolites.
H.-E.Maneck, D. Gutschick, I. Burkhardt, B. Luecke, H. Miessner, U. Wolf, Catal. Today 3 (1988)
421.
7. Structure and bonding of a site-isolated transition metal complex: rhodium dicarbonyl in highly
dealuminated zeolite Y. J. Goellner, B. C. Gates, G. N. Vayssilov, N. Rцsch, J. Am. Chem. Soc.
122 (2000) 8056.
8. The formation of a well defined rhodium dicarbonyl in highly dealuminated rhodium-exchanged
zeolite Y by interaction with CO. H. Miessner, I. Burkhardt, D. Gutschick, A. Zecchina, C. Morterra
and G. Spoto, J. Chem. Soc., Faraday Trans. 1, 85 (1989) 2113.
9. (?) Metal-support interaction: a theoretical approach. G. Blyholder, J. Mol. Catal. A 119 (1997) 11;
(b) Mobility and clustering of Rh and Ru in zeolite. Experiment and theory. L.Conners, T. Hollis,
D. A. Johnson, G. Blyholder, J. Phys. Chem. B 102 (1998) 10112.
10. (a) Elastic polarizable environment cluster embedding approach for covalent oxides and zeolites
based on a density functional method. V.A. Nasluzov, E.A. Ivanova, A.M. Shor, G.N. Vayssilov,
U. Birkenheuer, N. Rцsch, J. Phys. Chem. B 107 (2003) 2228; (b) Effects of the aluminum content
of a zeolite framework: a DFT/MM hybrid approach based on cluster models embedded in an elastic
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J. Chem. Theory Comp. 1 (2005) 459; (c) Comparison of all sites for Ti substitution in zeolite TS-1
by an accurate embedded-cluster method. R.C. Deka, V.A. Nasluzov, E.A. Ivanova Shor, A.M. Shor,
G.N. Vayssilov, N. Rцsch, J. Phys. Chem. B. 109 (2005) 24304; (d) First hybrid embedding scheme
for polar covalent materials using an extended border region to minimize boundary sffects on the
# 197 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
quantum region. A.M. Shor, E.A. Ivanova Shor, V.A. Nasluzov, G.N. Vayssilov, N. Rцsch, J. Chem.
Theory Comput. 3 (2008) 2290.
T. Belling, T. Grauschopf, S. Krьger, F. Nцrtemann, M. Staufer, M. Mayer, V. A. Nasluzov,
U. Birkenheuer, A. Hu, A. V. Matveev, A. M. Shor, M. S. K. Fuchs-Rohr, K. M. Neyman, D. I. Ganyushin,
T. Kerdcharoen, A. Woiterski, A. B. Gordienko, S. Majumder, N. Rцsch, PARAGAUSS version 3.0,
Technische Universitдt Mьnchen, 2004.
T. Belling, T. Grauschopf, S. Krьger, M. Mayer, F. Nцrtemann, M. Staufer, C. Zenger, N. Rцsch in:
High Performance Scientific and Engineering Computing; ed. H.-J. Bungartz, F. Durst, C. Zenger,
Lecture Notes in Computational Science and Engineering, Vol. 8, Springer, Heidelberg, 1999, p.
439.
The Gaussian-type orbitals density-functional approach to finite systems. B. I. Dunlap; N. Rцsch,
Adv. Quantum. Chem. 21 (1990) 317.
(a) Density-functional exchange-energy approximation with correct asymptotic behavior.
A.D. Becke, Phys. Rev. A 38 (1988) 3098; (b) Density ? Functional approximation for the correlation
energy of the inhomogeneous gas. J. P. Perdew, Phys. Rev. B 33 (1986) 8822; 34 (1986) 7406.
(a) Gaussian Basis Sets for Molecular Calculations, ed. S. Huzinaga, Elsevier, Amsterdam, 1984; (b)
Gaussian basis set for molecular wavefunctions containing second-row atoms. A. Veillard, Theor. Chim.
Acta. 12 (1968) 405; (c) Ab initio calculations of the structure and properties of disiloxane. The effect of
electron correlation and basis set extension. M.R. Bдr, J. Sauer, Chem. Phys. Lett. 226 (1994) 405.
Gaussian basis sets for the fifth row elements, Mo-Cd, and the sixth row elements W-Rn.
O.J. Gropen, Comput. Chem. 8 (1987) 982.
Systematic density functional study of the adsorption of transition metal atoms on the MgO(001)
surface. I. V. Yudanov, G. Pacchioni, K. Neyman, N. Rцsch, J. Phys. Chem. B 101 (1997) 2786.
Adsorption of d-metal atoms on the regular MgO(001) surface: Density functional study of cluster
models embedded in an elastic polarizable environment. K.M. Neyman, C. Inntam, V. A. Nasluzov,
R. Kosarev, N. Rцsch, Appl. Phys. A 78 (2004) 823.
On the cation and water positions in faujasite. W. H. Baur, Am. Mineral. 49 (1964) 697.
??????????? ????????? ? ???????????? ????????????? ???????? ?????????????? ??????????
????? (I) ? ?? ???????????? ????????. ?. ?. ???, ?.?. ???, ?.?. ????????, ?.?. ???????,
????. ????????. ????? 46 (2005) 228.
Infrared spectra of RhCO+, RhCO, and RhCO- in solid neon: a scale for charge in supported Rh(CO)
catalyst systems. M. Zhou, L. Andrews, J. Am. Chem. Soc. 121 (1999) 9171.
# 198 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ????????, ??????? ?. ???? ???????? ??????????? ??????? ??????????? ????? (I) ?
The Study of Rhodium (I) Dicarbonyl Coordination in Faujasite
Cavities by DFT-method
Svetlana S. Laletinaa, Alexey M. Shora, Elena A. Shora,
Vladimir A. Nasluzova,b and Anatoliy I. Rubayloa,b
a
Institute of Chemistry and Chemical Technology SB RAS,
42 K.Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The study of rhodium (I) dicarbonyl coordination in faujasite cavities by hybrid method of quantum
(Density functional theory) and molecular mechanics has been carried out. The importance of taking
into account environmental effects to determine correctly preferable Rh(CO)2+ cation coordination
centers has been demonstrated. The vibrational frequencies of CO groups have been calculated and
theirs connection with rhodium dicarbonyl (I) electron state has been shown.
Keywords: Density functional theory, rhodium (I) dicarbonyl, coordination, faujasite, embedding
cluster models.
# 199 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ?????. ?????? ??????? ?????? ????????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 200-205
~~~
??? 547.902.659.4
?????? ??????? ?????? ????????
?????? ?. ?????*
????????? ??????????? ???????????,
??. ?????????,79, ??????????, 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
????????????? ????? ??????? ????? ????????: 28-?-1-????????? ????????, 28-?????????????? ???????? ? 3,28-?????????? ???????? ???????? ?????????????? ?????
????????? ? ?????????????? ??????????????? ???????. ???????? ?????????? ??????????
??????????? ?? ????????? ??-, 1?-???-????????????? ? ??????????? ??????????? ???????.
???????? ?????: ??????? ????? ???????? ? 28-?-(1-?????????) ????????, 28-?????????????? ????????, 3, 28-??????????, ??????, ???????, ????????????? ??????????
??????, ????????, ??-, 1?-???-?????????????.
????????
????????????? ????????? ?? ?????? ????????????? ????? ?? ????????? ? ?????????????? ????????? ????? ??? ???????????.
?????? ???????? ?? ???????, ??? ????????
????? ????????????, ??????? ??????? ??
?????? ???????? ? ???????????? ?????????????? ???????? ?? ????????, ????? ???????,
??? ???????? ??????? ?? ??? ? ???????????.
????? ????, ????????? ????????????? ?????????????, ?????????? ??????? ??????????????? ????????, ??? ???????, ???? ????????
? ????? ????????? ???????? ????????. ????????????, ??????????? ??????????? ? ??????
????????????? ???????????, ????? ????? ??????????????. ????????? ??? ??????????? ????
????????? ????????? ??????? ?? ???????? ?
??????? ???? ???????? ?????????? ?? ??????
?????????????? ?????????? ????. ? ?????????????? ?????????? ???? ????????? ??????? ?
*
1
??? ???????????. ??????? ?????? ????????????? ? ????? ?????????? ??????????? ? ?????
?????????? ?? ??????? ??????, ? ??????? ???
????? ???? ?? 35 %.
????????
???????????
???????? ????????? ?????????? ????-?????????????????????, ???????????????, ?????????????????????, ??????????????? ?
?????????????????? ??????????. ???, 3,28?-??????????? ???????? ????????? ?????????????????? ? ????-???-??????????. ???????????, ??? 3,28-?-??????????????? ????????
????????? ??????? ????-???-??????????, ?????? ??????????????????? ??????????? ???????? ????????? ????? ?????????, ??? ?3 ???
?28 ????????? [1]. ???????? ???????????
???????? ???????? ???????????????????
??????????. ????????, ??? ??? ???????? ???????? ??????????? ?????????????????? ???????? ???????? ? ????????, ?????????????
Corresponding author E-mail address: kogay@lan.krasu.ru
© Siberian Federal University. All rights reserved
# 200 #
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??????? ? ?????????? ?????????? ???????????? ? ????????? ?????????????? ???????
??????????? [2]. ??????????????? ??????
?????????????? ? ???????????? ???????? ?????????? ?????????? ?????????? «??????» ?
«????» ? ????? 12 ? 20 ??/??. ????? ????????
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??????????????? ?? ???????? [4] ?? ?????? ?
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[5,6]. ??????? ????? ???????? ????????????? ?? ???????? ? ??????????????? ??????????????:
? ????????????? ? ????????? ????????? ????????? ????????????? ???????? [3].
?????? ???????????? ?????? ???????,
??? ?????? ???????? ??????????? ????????
???????? ????????????? ??????????? ????CH3-C=CH2
CH3-C=CH2
O
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HO
CH2O
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I
II ( a,b,d)
a - R* = H, R = 1- ?????????
b - R* = H, R = Ph-?CH2 ?CH2
d - R* = R = C7H15
????????????????? ?????
???????? ???? ??????? ????????????
??????? ??? ?? ?????????? «Silyfol» ? ?????????????? ????????????? ????????? ? ??????? - ?????????? ??????? ? ???????????
100:2:0,5. ??-??????? ?????????? ?? ???????
?Vektor?-22 ? KBr, ??????? 1?-??? ? ?? ??????? ?Avance 200? (BRUKER) ? ??????? ???????? 200 ??? ? CDCl3. ???????????? ???????
? ?????? ?? ??????????? ?????????.
???????????? ???????? ?????????????? 1-??????????????????? ???????. ?
?????????? ?????, ?????????? ????????,
???????? ????????????? ? ????????? ????????, ????????? 2 ? ???????? ? 10 ?? ??????
????????. ???????????? ?????????-1 ?????????? ??????? ? ?????????? 1,2 ? ?????????? ?
10 ?? ?????? ??????? ? ??????????? ? ???????
20 ??? ??? 0 0?, ????? ???? ??????????? ?????????? ???????? ?? ????????? ? ?????????
?? 8 ????? ??? 20 0?, ?????????? 2 ?? ????,
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??????? ?????????????? ????????????, ????????? 1 ?. ??????? ????????, ??????????
????????? ??????????? ?????? ? ????? ?? ??????????? ?????, ?????? ??? ????????? ????????? ??????. ???????????? ????????. ???????
????????? ?? ?????????????? ?????????? ???
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???????????? ????? ????????? ? ??????????
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??- ? ???-?????????????, ????????????
??????? ??????????? ???????.
28-?-(1-?????????) ???????? (IIa)
????? 45, 2%; ??-??????, ?, ??-1: 3629,0;
3419,8; 2913,5; 2851,9; 1716,6; 1454,0; 1232,1;
1078,5; ?????? 1? -???, (?, ?.?.): 0,87; 0,90;
0,95; 1,04 (15?, 5?., 5??3); 1,10 ? 2,00 (41?, ?.,
??2, C?); 1,94 (3?, ?., 3??, ????.); 2,43 ? 2,56
(3?. ?., ?13, ?16); 3,06 ? 3,18 (1?, ?., ?19);
3,21 (1?, ?., ?3); 3,77 (1?, ?., ?: ?? ??? ?3);
4,32; 4,26; 3,86; 3,81 (2?, ??., J=12, ?28); 4,62
(1?, ?., ?29?); 4,71 (1?, ?., ?29??). ??????? %:
? 81,23; ? 10,29. C41?64?3. ????????? %: ?
81,46; ? 10,60.
???????????? ???????? ?????????????? ????????????? ???????. ? ??????????
?????, ?????????? ????????, ???????? ????????????? ? ????????? ????????, ???????? 3,36 ? ????????, 10 ?? ??????????? ????????, ????????? ?? 0 0?. ????? ?? ??????
? ??????? 10 ??? ????????? ??????? 2,35 ?
????????????? ????????????? ??????? ? 10
?? ??????????? ???????, ???????????? ? ??????? 30 ???, ????? ???? ??????????? ?????????? ???????? ?? ????????? ? ????????? ??
8 ????? ??? 20 0?. ????? ? ??????????? ?????
?????????? 2 ?? ???? ? ???????????? ? ??????? 30 ???. ?????????? ????????? ???????
? ?????? ??????????? ?????????? ?????????,
??? ? ?????????? ???????.
28-?-????????????? ???????? (IIb)
????? 56,4 %; ??-??????, ?, ??-1: 3629,0;
3028,2; 2918,9; 2849,7; 1728,4; 1605,0; 1500,0;
1460,0; 1454,1; 1180,0; 745,2; 698,8; ?????? 1?
-???, (?, ?.?.): 0,87; 0,90; 0,95; 1,04 (15?, 5?.,
5??3); 1,10 ? 2,00 (29?, ?., ??2, C?); 2,43 ?
2,56 (3?. ?., ?13, ?16); 2,66 (2?, ??., J=7,6;
??2: ?-?????); 2,95 (2?, ??., J=3,6; ?-?????)
3,06 ? 3,18 (1?, ?., ?19); 3,21 (1?, ?., ?3); 3,77
(1?, ?., ?: ?? ??? ?3); 4,32; 4,26; 3,86; 3,81 (2?
??., J=12, ?28); 4,62 (1?, ?., ?29?); 4,71 (1?, ?.,
?29??); 7,23 ? 7,42 (5?, ?., ????????.).
??????? %: ? 80,94; ? 10,35. ?39?58?3 ????????? %: ? 81,53; ? 10,10.
???????????? ???????? ?????????????? ?????????? ???????
? ?????????? ?????, ?????????? ????????, ????????????? ? ????????? ????????,
????????? 3,4 ? ???????? ? 10 ?? ??????????? ????????, ????????????. ????????????
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?????????? ???????? ?? ????????? ? ????????? ?? 8 ????? ??? 20 0?. ????? ????????? 2
?? ???? ? ???????????? ? ??????? 30 ???.
?????????? ????????? ??????? ? ?????? ??????????? ?????????? ?????????, ??? ? ?????? ???????.
3, 28-?-?????????? ???????? (IId)
????? 79,6 %; ??-??????, ?, ??-1: 2956,0;
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1047,6; 844; ?????? 1? -???, (?, ?.?.): 0,87;
0,90; 0,95; 1,04 (15?, 5?., 5??3); 1,10 ? 2,00
(48?, ?., ??2, C?); 2,43 ? 2,56 (3?. ?., ?13,
?16); 3,06 ? 3,18 (1?, ?., ?19); 4,32; 4,26; 3,86;
3,81 (2?, ??., J=12, ?28); 4,50 (1?, ?., ?3); 4,62
(1?, ?., ?29?); 4,71 (1?, ?., ?29??); ??????? %:
# 202 #
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?????? ?. ?????. ?????? ??????? ?????? ????????
? 79,09; ? 11,55. ?46?80?4. ????????? %: ?
79,54; ? 11,23.
?????????? ? ??????????
?????????? ????????? ??????? ????????? ????????????? ??????????? ????????. ?
???????? ??????????? ?????????, ??? ???????, ????????? ????????? ??? ?????????????
?????????? ?????? ? ??????????? ????????
??? ????????? ??????. ? ???????? ??????????? ????????? ???? ???? ???????????? ????????????? 1-???????????????????, ????????????? ? ?????????? ??????. ????????????
???????? ????????? ? ????? ???????. ??????????? ???????? ? ???????????? ????????
?????????? 1: 2 ?? ???? ??????.
? ??-??????? ???????? ???????????? ???????? ?????????????? 1-????????? ?????????? ??????? ???????????? ?????? ??????????
??? 1716,6 ??-1, ??????????????? ?????????
?????????? ???????????? ?????? ???????
??????. ?????? ?????? ?????????? ??????????? ? ??-??????? ????????. ?????? ??????????
??? 1232,1 ??-1, ????????????? ????????? ?????????? ????? ??? ????????????? ??????.
? ???????? ???????????? ??????????? ??????
?????????? ??? 1788 ??-1 ???????????????
????????? ?????????? ???????????? ?????? ????????????? 1-???????????????????
???????, ??????????? ????? ?????? ?????????? ??? 1693,5 ??-1, ??????????????? ????????? ?????????? ???????????? ??????
1-??????????????????? ???????. ????? ???????, ?? ????????? ?????? ??-?????????????
????? ??????? ????? ? ??????? ????????????? ????? ? ?????????? ???????? ???????.
???? ????? ???????????? ?????? 1?-????????????????. ? ???-??????? ?????????????? ?????????? ??????????? ????? ????????
??????????? ???????? ??? ?28 ? ???????
????? ??????? ???? (4,32 ?.?.; 4,26 ?.?.; 3,86
?.?.; 3,81 ?.?.) ?? ????????? ? ????????? ????
???????? ? ???????? (3,78 ?.?.; 3,83 ?.?.; 3,31
?.?.; 3,37 ?.?.). ????? ???????? ???????????
???????? ? ????? ?????? ???? ???????????????
? ????????? ????? ? ???? ????? ???????? ???????????????? ???????????, ??? ??-??????,
??? ????? ???? ????????? ???????? ?-??
=? ?????? ??? ?28 ????????. ?????? ?????????? ??????????? ???????? ????? ???????, ??? ?? ???????? ?????????? ???????? ?
1-??????????????????? ???????. ??????????????? ????? ?????? ?????????? ????????????? ?????? ??????? ??? ?3 ?? ????????? ?
???????? ????? ??????? ? ???????? (3,21 ?.?.)
? ??????? ? ??-??????? ????? ?????????? ??????? ?????? ?????????? ? ??????? 3629 ??-1
(????????? ????????? ????? ?-?), ??? ?????????? ??? ????????????? ????????????? ????????? ????????????? ??????. ?????? ??- ?
?-???-????????????? ???????????? ??????? ??????????? ???????. ????? ???????, ? ?????????? ???????????? ???????? ?????????????? 1-??????????????????? ??????? ???????
???????? ? 28-?-(1-?????????) ????????.
???????????? ???????? ??????????????
????????????? ??????? ??????? ? ??????????? ????????? ????????, ??? ??????? ?? ??????? ?????? ??- ? 1?-???-????????????? ?
?????? ??????????? ???????. ? ??-???????
??????????? ?????????? ?????????? ??????
??? 1728,4 ??-1, ??????????????? ?????????
?????????? ???????????? ?????? ????????
?????, ? ????? ??????? ?????? ??? 1180 ??-1-,
??????????????? ????????? ?????????? ???
????????????? ?????. ??? ?????? ?????????? ??????? ????????????? ??? 745 ??-1 ?
698,8 (?????????????? ????????? ?-? ?????
? ?????????????? ?????????????? ????????? ?-? ????? ??????????? ??????) ????????????? ?????????????? ??????????? ???????.
? ???-?????? ???????? ?????????????? ???????? ? ????????????? ????????????? ??????? ??????????? ????? ???????? ????????
1
# 203 #
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?????? ?. ?????. ?????? ??????? ?????? ????????
??????????? ?????? ??? ?28 ? ??????? ??????? ???? (4,32 ?.?.; 4,26 ?.?.; 3,86 ?.?.; 3,81
?.?.) ?? ????????? ? ???????? ???? ????????
? ????????. ?????? ???-??????? ???????????
???????? ??????? ?????, ??? ?? ???????? ?????????? ???????? ? ????????????? ???????:
??????????? ????? ???????? ???????? ??? ?3
?? ????????? ? ????????? ???? ???????? ? ????????. ?????????? ???????? ?????? ??? ?3
?????????????? ??????? ??-?????????????:
?????? ?????????? ? ??????? 3629 ??-1 ??????????????? ? ??????? ????????? ????????????? ??????, ????????? ? ???????????????
????????. ??????????? ????????? ???????? ?
????????????? ??????? ???????????? ??????? ??????????? ???????.
????? ???????, ?? ????????? ?????? ??? ???-????????????? ? ?????? ???????????
??????? ??????? ??????????, ??? ???????????
?????????? ???????????? 28-?-?????????????
????????.
???????? ???????????????????, ??? ?
????????? ???????, ???????? ????????????
?????????? ???????. ???-?????? ???????????? ???????? ??????? ??????????? ??????
?????????? ????????? ????????. ? ??-???????
?????????? ??????? ????????????? ???????????? ????????????? ?????????? ??????????? ?????? ?????????? ??? 1745,5 ??-1 ?
??? 1247 ??-1, ??? ????????????? ?????????
?????????? ?????? ????? ?=? ? ??? ???????
??????. ? ???-??????? ????? ?????????? ??????????? ????? ???????? ???????? ????????-
??? ?????? ??? ?28 (4,32 ?.?.; 4,26 ?.?.; 3,86
?.?.; 3,81 ?.?.) ? ??????? ??? ?3 (4,50 ?.?.) ?
??????? ??????? ???? ?? ????????? ? ????????? ????? ??????? ? ???????? (3,21 ?.?.). ?????
??????? ??????? ??? ?3 ??????? ? ??????? ????? ???????????????? ???????????, ??? ????????, ??? ????? ???? ????????? ?????????
???????? ?????? ? ??? ?????????. ???? ?????
?????????????? ??????????? ? ??-??????? ?????? ?????????? ? ??????? ????????? ????????? ????? ?-?. ????? ???????, ?? ?????????
???????????? ?????????? ? ?????? ??????????? ??????? ????? ??????? ????? ? ???, ???
?????????? ?????????? ???????????? ??????
?????????? ??????? ? ???????? ? 3,28-??????????? ????????.
??????????
???????? ???????????? ???????? ??????????????? 1-???????????????????, ????????????? ? ?????????? ?????? ? ????? ???????
? ??????????? ?????????? ???????? ??? 0 є?
???????? ????? ??????? ????- ? ???????
????????. ???????? ?????????? ??????????
??????????? ?? ????????? ?????? ??- ? 1????-????????????? ? ??????????? ??????????? ???????.
????????, ??? ??? ??????? ????????? ???????? ? ????????????? ???????, ?????? 1:2,
?????????? ?????????: 28-?-(1-?????????)
???????? ? 28-?-????????????? ????????.
???????????? ?????????? ??????? ????????
?????? ? 3,28-?-?????????? ????????.
?????? ??????????
1.
2.
3.
?????????, ?.?., ???????, ?.?., ??????? ?.?., ??????? ? ??? ??????????? // ????? ? ????????? ??????????? ????????. 2005. ?.13. ?6. ?. 1-30.
??????, ?.?. ?????? ??????????? ?????. ?.: ?????? ?????, 2001. 248 ?.
???????, ?.?., ????????? ?.?., ?????????? ?.?., ??????? ?.?., ????????? ?.?. ?????? ?
????????????????? ?????????? ?????? ????????, ??????????? ??????? ? ????????????//
??????-????. ????. 2005. ?.39. ?8. ?. 9-12.
# 204 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
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4.
5.
6.
???????-?????????. ?????? ???????????? ? ???????????? ?????. ?.: ?????, 1969. ?. 232.
?????????, ?.?., ?????, ?.?. ??????????????? ?????. ?.: ????????, 1991. 358 ?.
??????, ?.?. ????????????? ??????????????????? ?????? ??? ??????????? ????????????? ??????? ? ???????????? ???????? ??????????// ??????-????. ??????. 1987. ?.21. ?.
931-940.
Synthesis of Ester of Betulin
Tamara I. Kogay
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Novel ester of betulin ? betulin-28-O-(1-adamantat), betulin-28-O-hydrocinnamat, betulin-3, 28-Odikaprilat were produced from betulin and appropriate chlorangidrids of carbon acid in absolute
benzene at 0 єC. The IR-, 1H-NMR- and elementary analysis evidence support this structure of these
esters of betulin.
Keywords: esters of betulin ? betulin-28-O-(1-adamantat), betulin-28-O-hydrocinnamat,, betulin-3,28O-dikaprilat, synthesis, betulin, chlorangidrids of carbon acids, structure, IR-, 1H-NMR-spectroscopy.
# 205 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
Journal of Siberian Federal University. Chemistry 2 (2008 1) 206-211
~~~
??? 542.182.024:546.98
?????? ???????? ??????????? ???????? ???????? ???????
??????????? ?????????????????
???? ?. ?????????,?, ????? ?. ????????,
???????? ?. ?????????, ???? ?. ?????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 2.06.2008, received in revised form 25.08.2008, accepted 27.08.2008
??????? ??????????? ????????????????? ??????????? ??????? ???????? ? ??????-??????
?????????. ???????? ?????, ??????????? ???????? ???????? ???? ?? ???-?????? ?
?????????????? ? ???????? ???????? ????????? ???????? ???????? ? ????????? ????????
????????????. ?? ??????? ???????? ????? ???? ?????????? ???????? ??????? ???????????
??????????? ????????, ???????? ??????? ?????? ??????????? ? ???????????? ?? ???????
?????????.
???????? ?????: ??????? ????????, ??????????? ?????????????????.
????????
???? ?? ?????????? ??????? ????????????????? ??????? ? ??????????? ????????????????? (???) ? ??????? ???????????? ???????? ?????, ????????? ????????? ????????
????????? ????????????????? ??????????
? ???????? ? ????????????? ?????? ?????????? ??????. ????????????? ?????? ??? ???????? ? ?? ??????????? ?????? ???????? ?
?????? [1].
??? ???????, ? ?????? ??? ?????????
???????? ????????, ?? ??????? ???????????
?? ??? ???? ????????????-?????????????????
???????. ??? ???????????? ??? ?????, ????? ?? ??????????? ???????? ??????????
?????????. ?? ???? ??????? ???????? ?????*
1
?????? ???????? ?????????? ???????, ?????????? ????????? ????????? ??????????
??????? ?????, ??? ???????, ? ???????, ??? ??
?????????? ???????? ???????.
???????????????? ??????? ??????????
??????, ? ????????? ????????, ??????? ??????? ?????????? ?? ?????? ???????? ????????? ?????????? ?????????, ????????? ??
??????????? ????????????? ?????????? ??????????, ??? ??????????? ??????? ???????????? ???????????????????, ??????????????????????????, ????????????? ? ??????
??????. ?????? ?????? ????? ??????? ?????????? ??????????????, ?? ?????? ?????????? ???????????? ? ? ???? ??????? ??????? ??????? ????????? ????????????????? ??????.
Corresponding author E-mail address: ov_bel@icct.ru
© Siberian Federal University. All rights reserved
# 206 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
??????? ?????????? ?????????????? ???????,
? ????????? ?????????????????, ?????????????? ?????????? ?????????????.
????? ???? ???????? [2], ??? ???????????????? ????????? PdCl42-/Pd0 ??????? ?? ???????????? ?????????????? ????????. ??????????? ?????????? ?? ??????? ?????? ??????
??????????? ?????????? ???????.
? ??????? ??????????? ????? ???? ??
???-?????? ?? ???????????? ???????? ??????? ? ?????? ????????? ??????. ?????? [3],
???????? ????????????????? ???????? ?? ???????????? ??????????? ????????? ? ?????????????????? ???????????? ???????? ???????
???, ??????????, ??? ???????? ????????? ??
??????????? ???????? ?? ??????? ????. ??????? ????????????????? ?????????? ???????? ?????? ??????? ? ??? ????? ??????? ?????????????? ? ???????????? ??? ???????????.
? ?????? [4] ????????, ??? ?????????????????
???????? ????? ???????? ??????????? ?? 0,3
?? 5 ?2/? ? ??????????? ?? ??????????????
???????????? ? ??????????? ?????????. ???????????, ??? ?????????? ??????????? ???????? ? ???? ??????? ????????? ??????????
??????????? ? ??????? ? ??????? ???????? ????????????.
?? ?????? ??????, ??????? ???????
??????? ??????????? ????????????? ????????
????????? ?? ????? ???-??????, ? ?????????
?? ????????? ????????? ? ??????? ????????? ????.
????? ???????, ????? ????????? ??????
???????? ???????????? ??????????? ?????????? ????????????? ??????????? ?????????????????????? ?????? ??? ?????? ???????? ??????????? ???????? ???????? (0).
????????????????? ?????
????????, ?????????????? ? ??????, ?????
???????????? ?? ???? ?.?. ???????? H2PdCl4
???????? ???????????? ???????????????? ??-
???????? PdCl2 ? ???????? ??????? ???????.
??????? ???????? ???????? ????? ???????????
?????????? ?????? ????????? ???????? H2PdCl4
? 1 ? HCl. ???????????? ???????? (II) ? ???????? ?????????? ??????-????????????? ?
?????????????????????? ????????. ???????
???????? ? ??????????? ???????? ???????????? (???????? ????? ?? ??????????????
??????????? ?????? ???????????????? ???????????? [2]) ??????? ??????? ???????????????? ???????? ? ????????? ?????? ???
1000?. ??????????? ????? ????????????? ??
?????????, ????????? ? ?????? [5].
??????????? ??????? ????????? ????? ???
??????????? ???????? ???????? ???? ????????? ? ??????? ??????????? ASAP-2420
(Micromeritics, USA) ??? 77?. ?????? ???????? ??????????? ???????? ?????????? ? ?????????????? ?????? BET [6]. ?? ?????????
????????? ????????? ? ????????? ????????
????????????? ????? ?????? ????????? ???
????????? 353 ?, ????????????????? ??????
? 10-12 ?. ????????????? ???????? ??? ??????????? ??????? ???????? ? ????????? ?? 0,01
?? 0,99 P/P0.
????????????????? ???????????? ????????? ? ????????????? ???? ???????????,
???????????????? ??????????????? ??????
??????? 35 ??3 ??? ??????????? 333 ?. ???
?????????????????????? ????????? ????????????? ???????????? ??-50-1-1 ? ?????????????? ??-8 ? ???????????????? ?????????????? ???????? ???1. ????? ???????????,
??? ???? ???????? ????? [2], ????? ????????????? ?????????????? ???????????? ??????????, ? ?????? ? ???????????? ?????????
??????????? ????????????? ????????????
????????. ? ???????? ???????? ? ????????????????? ????????? ????????????? ????????, ?????????? ? ?????????? ???????????
????????. ???????? ???????????? ????????
(???????) ? ???? ?????????????, ?? ??????
# 207 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
??? ????-?????????????, ?? ???????????. ?
???????? ???????????????? ?? ???? ?????????? ???????????? ?????????? ??????????
????????, ???????? ??????????? ???? ??????????? ???????. ?????????? ?????????
?? ???? ??????? ?????? ???????? ?????????????? ????????. ? ???? ???? ?????????????
????? ??????? ?????????? ?????.
?????????? ? ??????????
????????????? ?????????? ????????????????? ?????? ????????? ?? ?????????? ?????? ????????????? ????????? ??????????
??????? ??????????? ??????????. ??????????? ???????? ??? ??????????? ???-??????
???? ????????? ??????????? ????????? ????
??? ????????? ???????? ????????, ????????????? ?? ?????? ?? ?????, ?? ? ?? ???????
????????????.
????????????? ??? ?????? ???????????
??????? ??????????? ???-?????? ?????????? ???? ?????????? ??????? ? ?????? ??????? ????????? ??????????, ? ????? ???????????? ? ??????? ?????????? ????????. ? ????????
?????????? ???????? ???? ??????? ?????? 1?
HCl. ???? ????????, ??? ??? ?????????????
????????? H2PdCl4 ? ????????? ????????????
10-4 ? 10-2 ????/? ???????? ????? ?? ???????????. ???????????????? ??????????????
???????????, ??? ???????? ? ???? ???????????? ?????????? ??????????? ? 1? c??????
???????, ??????? ? ?????????? Pd(II) ? ???????? ? ????????? 10-6?10-5 ????/?, ? ??????????? ?? ???? ????????? ? ??? ?????. ??? ??????
???????? ????????? ?????????? ??????????,
????? ?????????? ????????????? ? ??????????? ? ???? ????? ???????? ???? ?????????,
???????? ??? ??? ??????????? ???????, ?
????? ?? ??????????? ??????????? ?????????? ??????????? ?????????. ?????? ????????
? ??????????????? ????????????? ?????????
???????????? ???????? ?????????: ??????
?????? ???????? 200 ??, ??????? ? 400 ??, ???????????? ??????????????? ????????? ?????????.
???????????????? ????????, ??? ??? ????????????? ??????? ?????? ? 1? HCl ???????? ???? ????? ????????????? ??? ????????
? ??????? ????????? ????????????.
? ????????? ?????? ??????? ??? ?????????: 1 ? ??? ??????????? ??????????? ?????????? ???????? ??????????????; 2 ? ????????
??????????? ??????????? ????????? ????? ??
?????????????? ???????????.
??? ??????? ???????? ????????? ??? ?????????? ???????? ?? 5 ??/? ?? 200 ??/?. ????????? ?????? ?? ?????????? ????????? 10,
20 ? 50 ??/? ??? 20,2 ?? ?????????????????
???????? ? 1M HCl ????????? ?? ???. 1. ???????????, ??? ???????? ????????? ???????????
?????? ?? ????????? ????????? ?????????
????, ? ?????? ?? ???? ?? ?????????? ???????? ?????????? ? ??????? ???????? ???????? ??????????. ???????? ????? ??????????
???. 1. ???-?????? ??? ?????????????????
???????? ??? ????????? ????????? ?????????
(20,2 ??): 1 ? 50 ??/?; 2 ? 20 ??/?; 3 ? 10 ??/?
# 208 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
???? ?? ???-?????? ??????????? ??? ???????? 20 ??/? ? ??????????? ??????????? ???
???? ???????????? ??????????? ??????????.
?? ???? ??????? ??? ??????????? ?????????
??????????? ? ?????? ????????? ?????????.
?? ???. 2 ???????? ???-?????? ??? 100
?? ??????????? ????????. ????? ?? ???????????? ????? ? ?????? ?????? ?????????? ?
??????? 20-25 ??????, ??? ??????????? ?????
???????? ??????????? ??????????? ?????????. ???????????, ??? ??????????? ??????????
??????????? ????????, ??????????? ??? ??????????? ???? ?? ???-??????, ?????????? 20
??.
? ??????? ?? ??????????? ?????? ?????
?? ???????????? ????? ??? ?????????????
????????????????? ???????? ??????????????
?? 1-2 ?????. ??????????? ?????????? ????????????????? ????????, ??? ???????? ??? ???????????? ?????????? ??? ?? ???-??????,
????????? 4 ??. ?? ???. 3 ????????? ????????? ?????????? ??????? ????????????????? ????????. ??? ????? ?? ???????, ???????? ???? ? ??????????? ??????? ?????????? ?
??????? ????? ?????? ???????????, ??? ????
??????? ????????? ???? ?????????????.
???????? ????????????????? ?????????
? ???????? ??????????? ????????? c ???????? 8 ??2 ????????, ??? ???????? ???????? ?
??????? ??????? ??????????? ??????????? ??
????????? ? ???????????????? ???????????.
???????????? ????????? ????? ???????? ???????? ? ??????????? ????????? (???????). ??????? 1 ? 2 ???????? ???????????????
??????????????? Pd(II) ?????????? ???????????? ? ????????? ?????? ??????????????.
??????????? ????????? 1 ? ????????? ?? ????? ????????????? ???????? [5] ? ?????????
1? HCl ??? 453 ? ? ??????? 2 ? 8 ????? ???????? ??????? 3 ? 4. ???????? 5 ???????
??????? ??????????? ?????.
???. 2. ???-?????? ??????????? ????????
(100 ??): 1 ? ???? ?1; 2 ? ???? ?20
???. 3. ??????????? ????? ???-?????? ?? ?????
??????? ????????????????? ????????: 1 ? 8,3 ??;
2 ? 15,6 ??; 3 ? 21,9 ??
# 209 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ????????, ????? ?. ???????? ?????? ???????? ??????????? ???????? ???????? ????????
?????? ??????? ????????? ???? (? ???????? ????????) ?????????????? ?? ??? ??????
??????????. ??????????? ??????????? ??????? ????????? ???? ?? ?????????? ???????????? ???????? ? ??? ???????????? (????????
??????? ???????????), ??????? ????????????
?? ???. 4.
??????????? ???????????
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