tesis

-

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XIII -

-2010

:

29 2

2010

001. 8:278 (043.2)

XIII - -2010 (29 2 2010 .) / . . .-. -. , 2010. 595 .

: .. , ..

( 10-08-06031-) - 2009-2013 ( 2.1 02.741.11.2224)

ISBN 978-5-9616-0261-6

- , 2010

:

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:

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.

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:

Trochimczuk A.W. Wroclaw University of Technology

Krawczyk J. Politechnika Krakowska

Rieger F. Czech Technical University in Prague

Ho-Suk Choi Chungnam National University, South Korea

:

.. ..., .,

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XIII - 6 -2010

546.9

..

. .. (), . , e-mail: [email protected]

.. , , . . , , .

, , (), , - , .

, , . , . . .. Pd(II) () ().

, , , , .

. .

, , , , , . , -.

7

541.183:544.7:546.824: 678.046

..

- ( ), . -, e-mail: [email protected]

() [1, 2]. , . , , , , . , .

( , , , , , ) , , , , , , - . . , , . (, ), , (, ), , .

, .

[1] .., .. . 1968. . 42. . 1210. [2] .. .- 2007.- .2, 3-4.- .87.

XIII - 8 -2010

.

.., .., .., ., .., .., ., .., .., ..

. ..

117393 , ., 70, e-mail: [email protected]

, - , .

, ( , , , ), . , , , , , .

, , .

, : (1) ; (2) () ( , , , .); (3) "" , , .

"" , .

, .

( 08-03-01074) (-21).

9

541.127:546.56:661.856

.., ..

- (), . , e-mail: [email protected]

() , . , ; ; .

-, . - - .

--- 25 100 C . , - , , , , , .

. , , , , , .

, , , , . , . , , .

XIII - 10 -2010

546.2+546.9+547.1+666.3

..

-

( ), . , e-mail: [email protected]

. 8-100 ( , CVD-). - : Al, Cu, Fe, Ni, Zr, Ti, Si, Zn, Mn, B, Mo, Mg, C, Al23, Fe23, ZrO2, AlN, BN, SiC, Cu*Ni, Cu*Sn, V- VIII .

, - , AlAl; AlSi; AlMg; AlTi; TiTi, .

.

11

544.4.032.7

..1, ..1, ..1, ..2, 1 , , . ,

e-mail: [email protected] 2 .

. , , , , , .. , , , .. , . . , . , . , : , , , , -, . , - , - . , . , , . , - - . .

XIII - 12 -2010

546.799

..

. .. , . , e-mail: [email protected]

( , , , ) . . , , , Ag . , Pt, Pd, Ru, , . U, Np, Pu Am , U(IV), H2, N2H4, HCOOH, H2CO, C2H5OH , Pt/Al2O3, Pt/SiO2,Pt/C, Pd/SiO2, Re2S7 . . , 137Cs, 90Sr, 99Tc . c . - - , - . , , , , . , . , - . 99 . U(VI), . , - , .

13

542.97:541.183

IN SITU

.., ..*, .., ..

. . (), . , e-mail: [email protected]

* . .. , .

( NOx). . , , , - . . , NOx , , , , ONO-CmHn O2N-CmHn. , , , , NO+O2 NO2, . - . , , . , NOx.

, , in situ NOx , -10-1, , Ni-Cr-, ZrO2 ( ZrO2, ZrO2 (ZrO2-)), , Pt u (Pt,u /ZrO2-).

XIII - 14 -2010

529.12

POLYMER IMMOBILIZED ANALOGUES OF IONIC LIQUIDS

Trochimczuk A.W.

Wrocaw University of Technology, Faculty of Chemistry, 50-370 Wroclaw, Poland, e-mail: [email protected]

Ionic liquids (IL) can be defined as salts having low melting points, usually

below 100oC. In recent years this new type of material, attracted a lot of attention of

chemists due to some unique properties such as negligible vapour pressure, good

thermal stability and, what is especially important, high polarity. These features

allowed the use of ILs as environmentaly friendly (no vapour pressure) and safe

alternative to organic solvents. Task-specific Ionic Liquids (TSILs) can be defined as ionic-liquids in which cation, anion or both of them have a functional group

attached covalently as a part of their structure. The group gives desired properties

(catalytic activity, ion-exchange).

Developments in catalysis using IL were widely studied and reviewed. By a

careful choice of the cation and anion it is possible to tune the properties of IL, for

example its miscibility with water and ability to dissolve substrates and products of

the reaction carried in such medium. However, sometimes it is not possible to achieve

easy separation of the reaction products from the IL. In such case the obvious choice

is the heterogenization of the ionic liquid by, for example, its immobilization in or on

the solid support. One of the first examples of such work was immobilization of the

imidazolium salts on the Merrifield type polymeric resin. In such a way it was

possible to prepare an efficient catalytic system for the nucleophilic substitution

reactions, which could be used many times with no loss of activity and it was easily

removable from the after reaction mixture. The supported ionic liquid phases were

also reviewed.

In this work we would like to present some results of research on solid

polymeric analogues of ionic liquids (IL-analogues), in which polarity of the material

is due to the presence of cations and anions known from the chemistry of ionic

liquids: imidazolium and anions like trifluoromethylsulfonate, trifluoroacetate, p-

toluenosulfonate. Such materials are obtained by modification of lightly crosslinked

vinylbenzyl chloride-divinylbenzene copolymers with alkyl substituted imidazol,

followed by subsequent ion-exchange of suitable anions. By an introduction of an

additional function, such as for example sulfonic group, it was also possible to obtain

a catalytically active polymer immobilized IL. Additionally, this material, as

crosslinked ones, is totally insoluble in any solvent. The last feature makes possible a

range of applications such as reactive chromatography, column-continous processes.

15

..

. .., , . , 86, e-mail: [email protected]

(, ) ( ). (), , .

, , .

- , ( , ). ( ) - . , , : , . .

, , , . . , , , .. 1960- , . (),

XIII - 16 -2010

, , , .

( ) , . , ( ). , , .

08-03-00976, ( 2.1.2/6880).

17

110 .. : -

.., ..

. .., , . , 86, e-mail: [email protected]

, , alma mater. () .. 2010 110 , 1 1900 ., () , , .

1918 . 2- , - -. 1930 . 2- , - - , 1931 . - .

7 1940 . .. , 1971 . , 1993 . () . ...

- - , 4000 , , , 1000 , 440 130 . : , , - . , .

, , .

, ,

XIII - 18 -2010

. .

, , , . 2009 1 (570 .), 59 . 2009 200 250 ., 53 62 .

- 25 . 8 . 60-70%. .

, , , , 16 - , , . , 90 .., , .

- .

2008 . , -- - , , , . , .

19

..


, , , , . ( Hulls, ).

, . . .

:

1. , , , , , ;

2. , ; 3.

;

4. .

, . , , , , , .

XIII - 20 -2010

541.133 +544.6.018.47-036.5

.., .., .., ..

. .. , , e-mail: [email protected]

, , , . . , , . , , . . , /, .

, , , , .

-4 , , (, ). 2-5 . , . ( ).

. , . -. , . .

XIII - 22 -2010

542.952.6.691.175.5/8

Pd(PPh3)2Cl2 PPh3 -

.., .., ..

. .. ( . .. ), . , e-mail: [email protected]

, , , [1]. , , . , . -. . . -, . -, - - [2]. -, , .

- . - . - TsO-, , . . , HI HClO4 , I- , ClO4

.

( 09-08-00890).

[1] Kiss Q. // Chem. Rev. 2001. V.101. 11. P. 3435-3456. [2] .., .., .., ..

. .: , 2007. 487 .

23

621.315.592:548.25

InAs/GaAs -

.., ..


InAs/GaAs () . - . GaAs - () InAs .

GaAs In . - ().

(100-350) . GaAs , , 310 160 ~ 40% (~11,4 ~16,1). , In .

200 500 6,1 10

-16 5,3 10-6 .

. GaAs In-Ga-As. , 350-500

( ~ 1 10-2 ~1,4 10

-1 .%) .

XIII - 24 -2010

MATHEMATICAL MODELING OF THE RAPID EXPANTION OF

SUPERCRITICAL FLUIDS

Anikeev V.I., Stepanov D.A., Yermakova A.

Boreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russian Federation,

e-mail: [email protected]

Mathematical modeling of the rapid expansion of supercritical fluid leading to the

formation and growth of nanoparticles of a solid substance predissolved in the fluid was

performed. According to the scheme of fluid motion, the mathematical model describes

three characteristic segments of the flow motion and a shock wave at the Mach disk: (1)

flow in a capillary; (2) supersonic expansion of a stream; (3) flow motion in subsonic

expansion region. To simulate normal shock wave, the equations of conservation of

mass, momentum and enthalpy were derived. Thermophysical and thermodynamic

parameters and phase state of the mixture were calculated for each isolated segment of

the flow motion using the RedlichKwongSoave equation of real gas state. Algorithms and a program were developed for solving the model equations.

Choice of the solving methods was determined by specificity of the flow motion and

expansion in each of isolated regions. Thus, as the condition of critical outflow at the

capillary outlet should be satisfied, hydrodynamics of the flow motion in a capillary was

calculated by an iterative method.

Supersonic region of stream expansion is limited by the Mach disk, where all

parameters of the flow undergo an abrupt change, and transition from supersonic

expansion region to subsonic one occurs. In subsonic region of stream expansion the

motion is isobaric, thus the geometry of supersonic region forms so that at the normal

shock wave the post-shock pressure is equal to ambient pressure.

In subsonic isobaric segment of stream expansion the flow rate virtually vanishes;

temperature of the flow tends to ambient temperature. A model of this segment is

supplemented with the equations of nucleus formation and growth of the solid phase

particles along the expansion axis.

A parametric analysis of the mathematical model showed that critical radius and

size of the particles that form during rapid expansion of supercritical fluid depend both

on the parameters of reactor mixture and on the capillary geometry. Size of the nascent

particles can be varied in a wide range by changing the temperature and pressure of

reactor and/or environment at a fixed capillary geometry. Calculation was made for the

composition: 2 solvent 90 mol %, ethanol co-solvent 7.5 mol %, phenanthrene as dissolved substance 2.5 mol %. Effect of the mixture composition on the outflow

hydrodynamics and particles growth was studied. Components of the mixture and their

percentage were varied. It is worthy of note that for some compositions solution of the

system does not exist. For instance, in some cases, a solid substance dissolved in

supercritical 2 becomes completely soluble in co-solvent under precritical conditions. We tested several co-solvents: methanol, ethanol and isopropyl alcohol, in combination

with dissolved solid substances: naphthalene, biphenyl, phenanthrene and anthracene.

25

541.182:536.461

..


() , , .

[M.P. Anisimov. J.Aerosol Sci., V.21, suppl.1, P. 23-25 (1990); ... , 352(6), 816-818 (1997)]. [M. P. Anisimov, Hopke P.K., Rasmussen D.H. et al. J. Chem. Phys. V. 109(4) P.1435-1444 (1998)]. . , [.. . . ., , 1975], , . . , ,

, [L. Anisimova, M. Anisimov, P. Turner, and P.K. Hopke. Journal of Colloid and

Interface Science V. 290, 107-116 (2005)]. , . , , , , [.. , .. , .. . , 417(2), 209-212 (2007)], . . . , .

10-08-00124-.

XIII - 26 -2010

544.47:544.344

:

.., .., ..

. .. ( ), . , e-mail: [email protected]

. , , () . ( SiO2 Al2O3), .

, ; , . , , , -Al2O3.

, , , . . , . , , . , , . , - . , .

27

547.979

A NEW APPROACH IN APPLICATION OF LUMINOL REACTION FOR

TRACE BLOOD ANALYSIS

Balantseva E.V.*, Priante S., Vincenti M., Coluccia S. Martra G.,

University of Turin, Department of Inorganic, Physical and Materials Chemistry,

Turin, Italy, e-mail: [email protected] *Ivanovo State University of Chemistry and Technology (ISUCT), Ivanovo, Russia

The emission of light observed when a solution containing luminol and hydrogen

peroxide is sprayed on dried bloodstains has been utilised by forensic scientists in

investigations involving violent crime for more than 40 years. During our investigation

of different nanopowders (NPs) (e.g., SiO2, TiO2, Al2O3, hydroxyapatite) we observed

an interesting phenomenon when the NPs were being added to system containing

luminol and H2O2 and blood, resulting in a significant increase of both intensity and

duration of CL [Patent. No. PCT/IB2009/055454].

To explain this phenomenon we started an investigation of the interaction

between hemoglobin (Hb) and inorganic powders mentioned above based on an

integrated approach resulting from the use of IR-/Vis-/EPR-spectroscopies and TGA-

analysis. It is known that binding of Hb to a surface is a spontaneous molecular event

where entropic effects and enthalpic ones play a major role in stabilizing the NPsHb complexes. But these weak interaction can greatly change a conformation of protein

adsorbed and consequently the structure of heme groups. But in which manner is Hb

structure being changed? On the base of IR-measurements of NPs/Hb pellets the extent

of protein folder was researched. At the same time, from the UV/VIS absorption and

reflectance spectra obtained for all NPs/Hb systems in solid and slurry states the affect

from addition of NaOH and H2O2 to NP/Hb have been observed. The data obtained by

this method can provide information about specific changes in heme group, iron state

and close its surroundings. The Al2O3/Hb and TiO2/Hb shown quite different behavior

and particular profile of its spectra in comparison with other NPs/Hb. Though UV/VIS-

spectra allowed us to determine that Hb is adsorbed on NP surface predominantly as

MetHbFeIII

(H2O) and MetHbFeIII

(OH) the details about iron state can be taken from

EPR measurements. Moreover this method can provides additional data respond to free

radicals which could be formed during redox reaction involving a protein and/or heme.

We also involved the TGA analysis to estimate the amount of Hb irreversible adsorbed

on NP surface and determined that independence on nature of NPs, specific surface

area and size of nanoparticles we have mono layer of Hb for all studied systems. An

integrated analysis of the various type of data collected, giving information on both

quantitative and structural data, allowed to conclude that a relevant role is played by

the capability of NPs to act as efficient adsorbers (resulting in a spatial concentration of

the proteins containing the metal centers responsible for the activation of the Luminol

oxidation), combined with the level of unfolding of the protein structure, with opening

of the hydrophobic pockets where the heme groups are hosted, with a consequent

higher accessibility of the metallic catalytic centers.

XIII - 28 -2010

519.673:620.9.97

CHEMCAD

.., . .

- () . . . , . , e-mail: [email protected]

, , CHEMCAD.

CHEMCAD : , , , , , , , , , , . , , .

, . , .

, , , [1-2].

[1] .. , .. , .. , .. , ..

. .// . 1. 2009 . . 40-50.

[2] .. , .. , .. . - // . 12. 2009 . . 29-31.

29

544.431.8

..


, . 50 [1]. . PdBr2 PPh3 HBr -1 , , , pH [2]. - , PdI2 KI MeOH [3-5]. PdBr2LiBrCH3CN . PCO:PC2H2>3 PO2 0,2 . , PCO:PC2H2

XIII - 30 -2010

66.048:548

.., .., ..

. .. , . , , e-mail: [email protected]

, (, , ), ( ), (-, - ). - -- , , / .

. . . , . , . .

, G. G>0, ; G0 . , . 1, , G>0, G

31

66.048:548

.., .., ..


() (), () (), () () , (). NRTL.

, , ( ). , , () ().

, , , , , .

, ,

1. , . , .

, , , . , , .

( 08-03-00976-).

[1] .. -

. . . . . .: , 1992. 193 .

XIII - 32 -2010

628.34

.., .., .., ..


- . , , . , ,

: Rrsf

Rr

s CC

r

D

.

. ,

sVs

33

541.128.12

N- ,

..*, ..**, ..**, ..*, ..*, ..**

* . ..

( . .. ), . , e-mail: [email protected] **


. . , N- : (Ph2P(O)H)2PdCl2 Ph2P(O)H, (Ph2P(O)H)2PdCl2 (C6F5)2P(O)H, (Ph2P(O)H)2PdCl2 PPh3, PdCl2 PPh3, PdCl2 (C6F5)2P(O)H, PdCl2 C4H6(CH2PPh2)2, (6-Mes)Pd(cinnamyl)Cl, (7-Mes)Pd(cinnamyl)Cl, (SiPr)Pd(cinn)Cl, (7-Dipp)Pd(cinn)Cl, (IPr)Pd(3,5-). - , N- -. - -. , , N- , (6-Mes)Rd(D)Cl . PdCl2 PPh3 PdCl2 C4H6(CH2PPh2)2 , . PPh3 C4H6(CH2PPh2)2 ( 4-5 ) , , , 3 . . C4H6(CH2PPh2)2 , .

- 2009-2013 , 02.740.11.0266, , 09-08-00890.

XIII - 34 -2010

: 532.785

.., ..

. .., . , e-mail: [email protected]

, . . - , , . . . , .

. , .

, ( ) - , , . , , , , , .

, . , . (30 - 40 %) .

35

66.015.4:541.121.001

.., ..

.. ( . .. ), .


, .

. , , , , .. .

( ), , . . , 100%- , .

. , 100%- , , .

XIII - 36 -2010

546.92:66.094.37:543.42

..1, ..1, ..1, ..2, ..1 1 , , ,

e-mail: [email protected] 2 .

, , , . : 1) . , , , , . 2) . , (, ) . , , .

- : 1) -, 2) (), 3) . , , , .

, , , , (, ), . - 1 3 . , - .

37

541.123

--

..

- (), , . -,


, . , - , , . , - , , , . , .

, , . , [1], . , [2, 3], , ( ) . - , , . - .

( 09-03-00812).

[1] .., .., .., ... . . . 2009 (43) 141-154.

[2] .., .., ... . . . 2008 (81) 234-240.

[3] A.Toikka, M.Toikka. Pure and Appl. Chem, 2009 (81) 1591-1602.

XIII - 38 -2010

544.032.73

- 186

..1, ..1, .2

1 - (), . , e-mail: [email protected]

2 - , . , e-mail: [email protected]

. - d- , Ac- Gly- , [1]. - 18--6 (186) .

18K6

(LogK, rH, rS) , 298.15 K . [Gly186] - . , 186 .

- [2]. , . 186 [Gly186].

[1] . . . // . 71 (2001) 1452. [2] .. , .. , .. .

( ). .:.1989. 256 .

(2009-2010) 2.1.1/5593, - 2009-2013 ( 02.740.11.0253)

39

541.128.3:542.952

.., ..

. .. , e-mail: [email protected]

. Ni(I) , , , (), .

Niall2 (all 35, 1-CH3C3H4, 2-CH3C3H4, 1-C6H5C3H4) Ni (), 77 K g. () , . , . Ni () Niall2. Niall2 Ni () , 298 10

-3 - 10

-6 .

() . Niall2 Ni() .

Ni(). Niall2 Ni()2. . Ni () . . , Ni-H. ,- Ni().

DFT/PBE . , .

. , Ni () .

( 08-03-00743).

XIII - 40 -2010

541.182:536.461

.., ..*


* (), . , e-mail: [email protected]

.

, , , . , , , . , , . . [. . . , . 72, 7, . 664-705 (2003)] .

, - - . [L. Anisimova, M. Anisimov, P. Turner, and P.K. Hopke. Journal of Colloid and Interface Science V. 290, 107-116 (2005)], , () . . , .. . .

10-08-00124-.

41

665.658.4

9-14

.., ..

, . , e-mail: [email protected]

(, , / . .) [1].

9-14 , : , , , , Pt-, , .

. (Gr, r, Sr) 753 0,2 - [3].

. ( k0 Ea) , Delphi 7.

. 4 %, .

. . , , 2 3,5 / 2,9 % . 5 %.

XIII - 42 -2010

541.182:541.128

-

.., . .

... , , e-mail: [email protected]

- , , , , . , , .

, - .

, 4--3--4-() (2.45 ) , , ().

0 2 4 6 8 100.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

3

2

1

A, . .

,

. 4--3--4-() ( 30 , 170 , 18 ) (1). 33 (2) 23 (3).

, .

.

43

: 66.065.5:621.577

.., ..


. . . . , , [1].

2-. , , .

, , .

, , . , .

[1] .., .., .., .. //

, 2, 6, 2007, . 75-82

XIII - 44 -2010

541.123

.., .., ..

.. , ., e-mail: [email protected]

, .

, , . () - .

, . ( , ) , .

-, - - ( , , , , ). , () , .

( , ) .

, ( ). , , -, , . , , .

( 08-03-00976-).

45

66.023.2+532.5

:

.., ..

- ( ) (()), . -,


, 10-15 , , , , , , ( ), (lab on a chip) . , .

[1] - , - . - . : ; ; ; ( , Ca < 3); . [2, 3].

, 355 0.92 . , 230 . - , . , . , , : 0.17 0.73 /, 0.09 0.56 /. .

[1] Abiev, R.Sh. //Theor. Found. Chem. Eng., 2008, vol. 42, no. 2, p. 105. [2] Kreutzer, M.T., Kapteijn, F., Moulijn, J.A., et al. //AIChE J., 2005, vol. 51, p.

2428. [3] Liu, H., Vandu, C.O., and Krishna, R.// Ind. Eng. Chem. Res., 2005, vol. 44, p.

4884.

XIII - 46 -2010

HYDROTHRMAL SYNTHESIS METAL OXIDE NANOPARTICLES

Anikeev V.I.

Boreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russian Federation,


Metal and metal oxide nanoparticles, differing from their bulk analogs in

chemical, thermal, optical, magnetic and other properties, are widely used in

catalysis, medicine, electronics and other fields. Continuous hydrothermal synthesis

has the best advantages and possibilities among the methods suggested for synthesis

of metal and metal oxide nanoparticles. This method is simple to implement and scale

up, it allows controlling the particles size and properties. However, an essential

drawback of the method consists in low control of nanoparticles aggregation.

Hydrothermal syntheses of the following metal oxide nanoparticles: LiMeOn (LiCoO2, LiNiO2, LiZnO2, LiCuO2), MeOn (CdOn, GaOn, CeOn, ZrOn), were

performed in supercritical water in a continuous flow reactor.

The HRTEM and SAXS methods were used for morphological and

compositional characterization of the samples. The syntheses of LiCoO2, LiNiO2,

LiZnO2, LiCuO2 , GaOn, CeOn, ZrOn were the most efficient.

Example of CeyOx synthesis

A 0.2 M water solution of Ce(NO3)3 salt was prepared for the synthesis. The

reaction temperature was 373-391C, pressure 260 atm. Water flow rate: flow 1 10 ml/min, reactant flow rate: flow 2 3 ml/min. The reaction products of whitish yellow color, with further precipitation of the solid phase.

Figure a, b. TEM images of CeyOx compound

Solid products of the synthesis were represented by a homogeneous mixture of

well-cut isometric crystals ~ 100 nm in size, Figure a, b. Dendrite aggregates of these

crystals prevail. The crystals are of dislocation block structure. According to XRD

data, CeO2 is the main synthesized phase.

47

541.182:536.461

-

.., ..


- [Michael P. Anisimov, Elena G. Fominykh, Sergey V. Akimov, Philip K. Hopke. Vapor-Gas/Liquid

Nucleation Experiments: A Review of the Challenges. J. Aerosol Sci. 40, 733-746,

2009; .. , .. . : . , 29(1), 75-85 (2010)]

, . 1980-. (FDC) [1]. FDC , [2], , [3], , .

, [4], - . , , , . [5] - . , .

10-08-00124-.

[1] M. P. Anisimov, and A.G. Cherevko, J.Aerosol Sci. 1985, 16(2), 97-107. [2] M. P. Anisimov, K. Hameri, M. Kulmala, T.E. Ovchinnikova, Report Series in

Aerosol Sci. 1993, 23, 19-24.

[3] L. Anisimova, P. K Hopke, J. Terry, J. Chem. Phys. 2001, 114(20):9852. [4] M.P. Anisimov, J. A. Koropchak, L. V. Timoshina, J. Chem. Phys. 1998,

112(22):9917-9928.

[5] M.P. Anisimov, P. K Hopke, S.D. Shandakov, I. Shvets, J. Chem. Phys. 2000, 113(5):1971.

XIII - 48 -2010

TRANSFORMATIONS OF MONOTERPENE EPOXIDES IN

SUPERCRITICAL SOLVENTS

Volcho K.1, Il`ina I.

1, Salakhutdinov N.

1 Anikeev V.

2

1 Vorozhtsov Novosibirsk Institute of Organic Chemistry, Novosibirsk 630090,

Russian Federation 2 Boreskov Institute of Catalysis, Novosibirsk 630090, Russian Federation


Introduction

Monoterpenes and their epoxides are valuable renewable starting materials for

pharmaceutical and cosmetic industries, production of flavorings, pesticides, etc [1].

However, the transformations of these compounds, especially epoxides, in acid media

may give due to isomerization and polymerization reactions not only the target

products, but also a number of undesirable compounds [2]. Moreover, serious

environmental problems are caused by large amount of toxic acid-containing waste.

Reactions based on the transformations of monoterpene epoxides in supercritical

solvents can be considered as an alternative to the conventional methods.

Experimental

In the present work, we have studied the transformations of some monoterpene

epoxides (-pinene, verbenone and verbenol epoxides (Fig. 1)) in various supercritical solvents for the first time.

Figure 1 : The epoxides structures

OH

O

verbenoneepoxide

O

OO

verbenolepoxide

-pineneepoxide

The transformations of epoxides in composite supercritical solvents that

contain 2, lower alcohols (ethanol, isopropanol) with or without water were studied in the temperature range of 387-575 at pressure 13.5-21.5 MPa. The addition of water to supercritical solvent will impart acidic properties to the system

and thus make expectable the formation of products of acid-catalyzed transformations

of the epoxide.

Results

Campholenic aldehyde and carveol were shown to be the main products of -pinene epoxide reactions in supercritical solvents containing water (Fig. 2). Both

these compounds are valuable feedstock for fragrance industry.

Figure 2 : The -pinene epoxide transformations

49

O

-pineneepoxide

pinocamphonecampholenic aldehyde

CHO

O

carveol

OH

+ + + ...

In the absence of water, thermolysis of -pinene epoxide in supercritical solvent yields campholenic aldehyde and pinocamphone, with their total amount in

the reaction mixture attaining 80%. In this case, judging from the composition of

products being formed, the occurrence of two parallel processes can be assumed:

thermal isomerization of -pinene epoxide and its acid-catalyzed isomerization. The transformations of verbenone and verbenol epoxides led to another types

of the products. For example, the main identified products of verbenone epoxide

isomerization in composite supercritical solvent containing 2, isopropanol with or

without water were -ketoalcohols 1 and 2 with camphane and p-menthane skeletons accordingly (Fig. 3).

Figure 3 : The verbenone epoxide transformations

verbenoneepoxide

O

O

+ + ...O

HOO

OH

21

The epoxide conversion and products distribution were dependent on the

reactions conditions to a great extent.

Conclusion

The transformations of monoterpene epoxides in supercritical solvents of

different compositions can be considered as new methods of obtaining the target

isomerization products at short (up to 4 min) residence time in a continuous mode in

ecologically friendly conditions.

References

[1] Monteiro, J.L.F.; Veloso, C.O. Topics in Catal., 27, 2004, 169-180. [2] Ilina, I.V.; Volcho, K.P.; Salakhutdinov, N.F. Russ. J. Org. Chem., 44, 2008, 1-

23.

XIII - 50 -2010

544.3:547.962.9-022.532(043.2)

PHYSICAL-CHEMICAL TOOLS FOR THE ASSESSMENT OF INDOOR

ENVIRONMENTAL EFFECTS ON ARCHIVAL PARCHMENT HERITAGE

IN A CHANGING CLIMATE

Badea E.1, Della Gatta G.

1, Odlyha M.

2, Larsen R.

3, Usacheva T.

4

1 University of Turin, Italy, e-mail: [email protected]

2 Birkbeck College, University of London, United Kingdom

3 Royal Danish Academy of Fine Arts, Copenhagen, Denmark

4 Ivanovo State Chemistry & Technology University, Ivanovo, Russia

Environmental pollution, climate change, limited energy consumption and lack

of standardisation of best practices, principles, protocols in conservation science are

the challenges that nowadays the science for conservation has to face for securing the

protection of collections in public and private libraries, archives and museums. The

almost entire heritage of the European and Mediterranean civilisations, from classical

times to 15th

century, has been delivered to us on parchment in form of scrolls,

manuscripts, codices, book covers, etc.

In this paper, the applications of optical and thermal microscopy, scanning

electron microscopy and atomic force microscopy to surface characterisation of

historical parchments are presented. As parchment is a biomaterial with hierarchical

structure characterised by the intimate relationship and connectivity between

individual molecules and their organisation in micro-fibrils, fibrils and fibres, a micro

to nano-scale investigation protocol was developed for an in-depth assessment of its

deterioration enabling diagnostics, ranking and monitoring of damage of archival

parchments. To answer the sampling ethical requirement and to meet the demand set

by the high variability of historical samples non-invasive and micro-destructive

techniques were used. This innovative tool will significantly improve strategies for

the sustainable preservation of parchment heritage.

The results reported have been obtained within the framework of the EU

Commission Project Improved Damage Assessment of Parchment (IDAP, EVK4-CT-

2001-00061, 2002-2005) and Italian Project Old Parchment Evaluation: Restoration

and Analysis (OPERA, CIPE-2004-D39, 2006-2009).

References

[1] Della Gatta G., Badea E., Mai A., Ceccarelli R., in Improved Damage Assessment of Parchment (IDAP) Collection and Sharing of Knowledge, R.

Larsen (Ed.), Luxembourg, L, 2007, ISBN 987-92-79-05378-8, p. 89-98.

[2] Badea E., Miu L., Budrugeac P., Mai A., Della Gatta G., J. Therm. Anal. Calorim., 2008, 91, 17-27.

[3] Budrugeac P., Badea, E., Della Gatta G., L. Miu, Thermochim. Acta, 2010, 500, 51-62.

[4] Badea E., Della Gatta G., Usacheva T. Polym. Degrad. Stab., in preparation

51

547.979.733

.., .., .., .., - (),

. , e-mail: [email protected] , .

. , , . (Pzc(COOH)8M), -2,3-(5,6-) [1]. [2]. (Pyc(COOH)8M) . - . Pyc(COOH)8M , Pzc(COOH)8M

-, - -. - , - . , - - - , , , -

.

[1] Kudrevich S.V., Galpern M.G., van Lier J.E. Synthesis 1994, 779-781. [2] Kudrevich S.V., Galpern M.G., van Lier J.E. Chem. Abstr. 1996, 125, 58203.

HOOC

HOOC

Y

X

X

Y

Y X

X Y

N N

N

N

NN

NN

M

COOH

COOH

COOH

COOHHOOC

HOOC

NC

NC

N

N

N

N

N N

N N

N N

N

N

NN

NN

M

CN

CN

CN

CN

NC

NC

N

NCN

CN

NC

NC

N

N

N

N

N N

N

N

NN

NN

M

CONH2

CONH2

CONH2

CONH2

H2NOC

H2NOC

H2NOC

H2NOC

N

CN

CN

NC

NCN

CONH2

CONH2H2NOC

H2NOC

X=N, Y=C - Pyc(COOO)8M

X=N, Y=N - Pzc(COOO)8M

XIII - 52 -2010

529.12

.., .., .., ..

- , 111123, , , 38,


PhSi(O)3 , , (), - . - - , PhSi(O)3 -.

1- 29Si- , PhSi(OR)3 (), PhSi(OR)2(O-) (), PhSi(OR)(O-)2 (), PhSi(O-)3 (D). B C

, PhSi(O)3 - - . Mw/Mn = 2,0 1,5 - . Mw = 2800 600 , 1950 - . , - -, - - .

53

66.015.4:541.121.001

.., .., ..

. .. ( . .. ), .


, . , , . . , , , ( ).

. , . ( ) . , . , .

, . , , , . .

, , . , 100%- .

XIII - 54 -2010

547.53:541.121:544.424.2:544.183.25

.., .., .., ..

() , . , e-mail: [email protected]

, , , . . , (), [1], , , , [2]. , .

, H2SO4 , DFT/B3LYP 6-311G** FireFly v.7.1.G [3]. , , , , , (, ). 1-4 . ( ) ( ). , N- , . -, , , . ( 0.01 %) .

55

( Ac2O) -. AcOH - . H2SO4 , B3LYP/6-311+G**/PCM , H2SO4 . [4] -, .

[1] Chemical Reactivity Theory. A Density Functional View. / Chattaraj P.K., Ed.

N.-Y.: CRC Press. 2009. Ch. 18. P. 255 267. [2] Xiao H., Chen L., Ju X., Ji G. // Science in China. B. 2003. Vol. 46. No. 5. P.

453-464.

[3] A.A. Granovsky, FireFly ver. 7.1.G. http://classic.chem.msu.su/gran/firefly/index.html

[4] Methods and reagents for green chemistry. / Tundo P., Ed. Hoboken: Wiley J. 2007. 314 p.

XIII - 56 -2010

547.979.733

5,15-

.., .., ..


5,15-- (I), 5,15--10- (II), 5,15-10,20- (III), 5,15(4-) (IV), 5,15-(4-)-10,20- (V) (7:3) . , (I-V) , , . - (III V), , - . (V) , (III). , N-H, - - . (I-V) (7:3). - (III). , , . (V) (III), -, , I- .

- 2009 - 2013 02.740.11.0106 -1105 ( 09-03-00927, 10-03-00967)

57

532.783

..1, . 1,2 , .. 1,2 1 , , ()

2 . .. ,

, 117571, . , , 86, -mail: [email protected]

(), .

), .

, , (2 2). , . , . , --, - . , , . , (l) , .

- - , . , . , .

. Colh 42 243 .

, , .

XIII - 58 -2010

541. 572. 128 (043.2)

(-)

.., .., ..

- , . , e-mail: [email protected]

, , - . , , .

, NH- (--) (2(64F3)8) ( (Py), 2- (MePy), (Mor), (BzNH2), - (BuNH2), - (t-BuNH2), (Et2NH), (Et3N), (Pipy)).

, 2(64F3)8 Mor, BzNH2, BuNH2, t-BuNH2 Pipy NH- 1:2.

, NH- 2(64F3)8 Mor, BzNH2, BuNH2, t-BuNH2 Pipy , (k

298=10

-6 /).

, Mor BzNH2 BuNH2 Pipy 2(64F3)8Mor, 2(64F3)8BzNH2, 2(64F3)8BuNH2 2(64F3)8Pipy .

, - NH- 2(64F3)8 t-BuNH2.

, Py, MePy, Et2NH Et3N 2(64F3)8.

, 2(64F3)8Mor, 2(64F3)8BzNH2, 2(64F3)8BuNH2, 2(64F3)8t-BuNH2 2(64F3)8Pipy . - , .

( 10-03-00305-).

59

544.34:549.73:543.554.4

- , Cu -

. ., . .


- . . .

, 30 - T=450 C. . , . - 0,1M HCl 0,1M NaOH.

, . ( - , n/m, ), - , + . , n/m = f (pH) : n(OH

-)/m=f(pH) n(H+)/m=f(pH). nb(pH) -

. - , . , (/) . , -; 4 . , .

XIII - 60 -2010

542.973.6

.., .., ..

(), ., e-mail: [email protected]

, 2008 , 2013 10 ppm. , .

12- ( SnMo12-), 12- (VMo12-), 11--1- (PVMo11-). Shimadzu EDX-800 . , 12- (SiMo12-) (..) 12- (PMo12-) (..) 110 - . .

-Al2O3. . 0.125 400. .

. 4.0 (0.1 ), 320, 340, 360, 380 (1), 2 -1 (0.01 -1), / 600 / (25 /). ( 1.14% ., : 3.17 % ., 1.37 % .).

( ): Co-SiMo12(S)/Al2O3 < Co-SnMo12(S)/Al2O3 < Co-VMo12(S)/Al2O3 < Co-PVMo11(S)/Al2O3 < Co-PMo12(S)/Al2O3,

( ): Co-PVMo11(S)/Al2O3 < Co-SnMo12(S)/Al2O3 < Co-VMo12(S)/Al2O3 < Co-SiMo12(S)/Al2O3 < Co-PMo12(S)/Al2O3. , .

61

544.032.73

THERMODYNAMICS OF COMPLEX FORMATION BETWEEN

CROWN ETHER 18C6 AND D,L-ALANINE

IN WATER-ACETONE MIXTURES AT 298.15 K

Matteoli E.a, Usacheva T.R.

b, Chernov I.V.

b, Kuzmina I.A.

b, Sharnin V.A.

b

aInstitute of Physical-Chemical Processes of National Research Council

(IPCF), Pisa, e-mail: [email protected] bIvanovo State University of Chemistry and Technology (ISUCT),

Ivanovo, e-mail: [email protected]

This study is necessary to create a scientific basis for using the solvent as a universal driver for processes in the liquid phases.

The determination of thermodynamic reaction parameters and thermodynamic

solvation parameters of reagents and products (G, H, TS), the setting up of the predictive models for complex formation, the estimation of the influence of mixed solvent composition on the reactions allow to use solvents to drive the processes of complex formation in solutions.

As a continuation of our studies here we present the results of investigations of complex formation reaction between crown ether 18-crown-6 (18C6) and D,L-Alanine (Ala) in water-acetone mixed solvents and examine the applicability of previously established patterns for reactions of ions [1] and molecular [2] complex formation in solution.

The standard thermodynamic parameters of the complex [Ala18C6] were calculated from thermochemical data at 298.15 K obtained by titration calorimetry at 0.0, 0.08, 0.17, 0.22 and 0.30 mole fraction of acetone. Titration of one reagent by the other and dilution of the reagents were carried out using the TAM calorimeter MOD 2277 by Thermometric. The calorimetric data were treated using a least-square method

to obtain K and H. The range of used concentrations of acetone was limited by a low solubility of D,L-Alanine in mixed solvents.

The complex stability and exothermicity of complex formation reaction increase steeply with increasing the fraction of the non-aqueous components in mixed solutions. A similar but less marked influence of mixed solvents on the thermodynamic parameters for complex formation reaction between 18C6 and glycine was found previously [2].

The thermodynamic data were discussed on the basis of the solvation thermodynamic approach [1] and the enthalpic contributions of the reagents and of the complex to the enthalpy of complex formation reaction were analyzed.

References [1] V.A.Sharnin // J. General Chemistry. 71 (2001) 1452. [2] E. Matteoli, L.Lepori, T.R.Usacheva, V. A. Sharnin // J.Therm.Anal.Cal. 97

(2009) 811. This work was supported by the program "Development of Scientific Potential of

Higher School (2009-2010)" project 2.1.1/5593, and the Federal Program "Researchers and Scientific-Pedagogical Staff of Innovations of Russia" for 2009-2013 (State number 02.740.11.0253).

XIII - 62 -2010

66.015.4:541.121.001

.., .., ..

. .. ( . .. ), .


, . ( ) , . ,

, , 100%- .

, . 100%- .

. , , 100%- .

63

691:546

.., ..

., e-mail: [email protected]

. , (, .) . , , , .

, 150 .

.

, , .

- .

.

:

, /3 120-150 , 1,5 ,

/() 0,05

24 , %

4

1200600l00 .

XIII - 64 -2010

66.965.5: 621.577

.., .., ..

. .., . , e-mail: [email protected]

. , , - , . . , . .

, , , . , .

. : , , . : , .

( , , , , .) - . , .

65

541. 572. 128 (043.2)

(3--5--)-

.., .., ..


, . , . .

, (3--5--) (H2Pc(NO2)4(t-Bu)4) () (). (Py), 2- (2-MePy), (Mor), - (BuNH2), (Et2NH) (Pipy).

, H2Pc(NO)4(t-Bu)4 NH- - H2Pc(NO2)4(t-Bu)42.

, (Py, 2-MePy, Mor), H2Pc(NO2)4(t-Bu)42 . , (BuNH2, Pipy) H2Pc(NO2)4(t-Bu)42, - .

H2Pc(NO2)4(t-Bu)42. .

, Pipy BuNH2 H2Pc(NO2)4(t-Bu)42 ~ 2 , .

, BuNH2 Et2NH. BuNH2 Et2NH H2Pc(NO2)4(t-Bu)42.

( 10-03-00305-).

XIII - 66 -2010

541.64:547.979.733

---

.., .., .., .., ..


, . , , .

-- 1 -- 3 2 4, .

NH N

HN N

Me Me

MeMe

Me Me

Am Am

OH

O H2 H CH2CH2 HBr CH2

1 2

O

NH

N2

NH N

HN N

Me Me

MeMe

Me Me

Am Am

H CH2CH2 CH

O

Cl

3 4

2 4 . , 1 , , -, -.

, , -.

- 2009 - 2013 02.740.11.0106 -1105 ( 09-03-00927, 10-03-00967)

67

661.183.122

-

.., .., ..


, , / .

, . , . , . , , . .

514.

. , - 10.5-11.5. 514 - 3-4.

, 4, 10, 514 .

, , .

, .

XIII - 68 -2010

661.183.2

.., .., ..

- (), ., e-mail: [email protected]

, .

- .

514 7535-86

15-60

- V-4 c 930 -1

5,4 /. ,

, . .

- . - AVATAR 360.

, 1-2/ 5-6/ . , - . =2.3-2.7, - =11-12. pK=11-12.5. , , , , , .

69

541.128:542.97:547-326:547-305.2

-

.., .., ..


Pd(PPh3)2Cl2 PPh3 - (TsOH). , , . , .

, [1]. .

363-383 TsOH , . TsOH S- . , , -. TsOH [2] , TsOH :

TsOHk'

iCPPhhPPh

OHHCg

PPh

PfePOHHCdTsOHa1

OHHCTsOHHCPkCr

M2

3

3

116

3

CO2CO

2116

116106COM

.

, 09-08-00890.

[1] .. . . . . : . 2005. [2] .., .., .., .. //

, 2006, . 46, 6, . 435-445.

XIII - 70 -2010

660:51.001.57+66

..

. .. (),. , e-mail: [email protected]

, - , n- .

- n- .

. n- . , . .

. , . n. [1,2].

( 08-08-00318-).

[1] .., ..

// . . . 2001. . 35. 6. . 603.

[2] .., .., .. // . 2001. 6. . 36.

71

660:51.001.57+66

..

. .. (),

. , e-mail: [email protected]

, , n- .

n- A1,,Am, Am+1,,An (1m

XIII - 72 -2010

66.093.48

-

.., .., .., ..

() . , e-mail: [email protected]

26 . : ( 30% 20% . ( - ).

- , - s- I- d- VI-, V VII 4 .

( . . .. ). - ( . . .. - ).

(

220 300) . , -

, ( 2189 2195 -1, 33 36 /), . 220.

, (

0,5 1,0 ), , . 601 (328).

.

73

542.973.6

Co-XMo12(S)-

.., .., ..


, , , . . 12- .

: 12- (BMo12-), 12- (TiMo12-), 12- (VMo12-), 12- (GeMo12-), 12- (ZrMo12-), 12- (SnMo12-), 12- (PMo12-), 12- (SiMo12-), 12- (ZnMo12-), 12- (CeMo12-). - -. -Al2O3. . 60, 80, 110 2 , 1 / 400 2 . MoO3 CoO Shimadzu EDX-800.

0,125 400. . (0,025 ) 320. 340, 360, 380. : < ZnMo12-< SnMo12-< SiMo12-< TiMo12-< VMo12-< GeMo12-< ZrMo12-< PMo12-< CeMo12-< BMo12-. , P, Ce.

XIII - 74 -2010

541.128; 541.49:546.74/121

-

3-

.., ..

() ...


3 . , .

(DFT) - PBE [1] SBK [2] ( .. . ..

[3]) 3

[3C3H5NiX2]

(X = F, Cl, Br, I).

, - . I-Br-Cl-F, Ni-C Ni-X ( ). Ni-X, -Ni: Ni 1 2.

.

[1] Perdew J.P., Burke K., Ernzerhof M. Phys. Rev. Lett. 1996. V.77. P.3865. [2] Stevens W.J., Basch H., Krauss M. J.Chem. Phys. 1984.V.81 P.6026. [3] Laikov D.N. Chem. Phys. Lett. 1997. V.281. P.151.

C 1

C 2

C 3

Ni

X X

H

H

H

H

H

, X = F, Cl, Br, I

75

549.752/.753

Li2OZnONb2O5

.., .., ..


. - .

Li2OZnONb2O5. ZnNb2O6LiNb3O8 : LiZnNb4O11.5 LiZnNb6O16.5, ~2.%. ZnNb2O6 LiNb3O8. (), - . . () LiZnNb4O11.5 : (3D) ((3+1)D) . , . P 21/b. , -PbO2 q=0.3a*+1.1b*. LiZnNb4O11.5 () , . - - . .

LiZnNb6O16.5, LiZnNb4O11.5, . (). LiZnNb4O11.5, : - -PbO2 q=2/7a*6/7b*.

- () LiZnNb4O11.5 LiZnNb6O16.5, , 251100 .

XIII - 76 -2010

541.182:536.461

- -

..1, ..1,2, ..1 1 ( ),

. , e-mail:[email protected]. 2 (),


- - . - - . , [1] :

, .. , , Tc

; c0 c7 , ; Z(, )

; cZ - [1].

- CO2, : 60 oC, 1 , 110 oC. , , 0,08 %, , , 0.1%. . 100 600% 4 % .

, 20 .

10-08-00124-.

[1] . ., . . . 392, 1, 2003 . 48 53

77

547.979.7

-

.., .., ..


, [1]. , , , , - [2].

- - , , , , .., . , - .

, - , . , , [3]. . .

2.1.1./2889

[2] S.C. Doan, S.Shanmugham, D.E. Aston, J.L. McHale. // JACS. 2005, V.127,

P.5885-5892. [3] F. Langa, M.J. Gomez-Escalonilla, P.de la Cruz. // J. Porph. Phthal. 2007.

V.11. P.348-358. [4] Fedulova I.N., Bragina N.A.et al. // Mendeleev. Commun. 2008. V.18, P.324-

326.

XIII - 78 -2010

66.048.3-932.2

.., ..


. . , , , . 3.1.0-2. .

( R,

, ) R 3.1.0-2 . .

( ) .

R , . ( )

R . ,

. . .

79

546.819.86.74.73.72

,

.., ..

(), . e-mail: [email protected]

- 3d- , . , - . , (Fe1,2 Sb)1-x (Pb0,825Sb0,175)x (NiSb)1-xPbx , (CoSb2)1-x.Pbx . , , , , . (

sH )

( 0TG ) .

(Fe1,2 Sb)0,98 (Pb0,825Sb0,175)0,02 sH =56,6 / 0

TG =-144

/, (NiSb)0,99Pb0,01 sH =54,8 / 0

TG =-69,3

/, (CoSb2)0,98.Pb0,02 sH =13,6 / 0

TG =214,5

/. , , . (Fe1,2 Sb)0,98 (Pb0,825Sb0,175)0,02 (NiSb)0,99Pb0,01. 0

TG

(CoSb2)0,98.Pb0,02 , , . . , , (CoSb2)0,98.Pb0,02. , , , .

XIII - 80 -2010

542.943-92:544.431.22:542.2232

.., .., ..


. , (~10-4 /) , . : , . . , , , . MemOm+1. (MnO2, Mn3O4, Mn3O4, Fe2O3 (, , - ), Fe3O4, PbO2, Pb3O4, ..) . ,

MemOm+1 + HSO3 Mem(OH)Om +

SO3

(1)

Mem(OH)Om + HSO3 Mem(OH)2Om1 +

SO3

(2)

SO3

+

SO3

S2O6

2, (3)

.

. MemOm+1 ; , , ; ( 1 ) ; , (1) (2) ; MemOm+1 , , .

81

.., .., ..

(), . , e-mail: [email protected]

- , , . , .

. , , , , , , .

, , , . .

20 20 /2 - ( ), ( ). - - (+20 +95 0) . , , .

, +20 0 , -5 0 .

, , , .

XIII - 82 -2010

546.831:66.097.5

..*, ..**, ..**, ..** * .

.. , . , e-mail:[email protected] ** -, . ,


, . , . , , () , . , NOx , . , , .

,

, , , -Al2O3.

Zr-Al-Ca-O , , -, , . , ( 100%) . , , . , , , , .

, .

83

533.9.07

..-., .., ..

- (), . -, e-mail: [email protected]

. , , , . .

, , : - , , . , . , ( - - I* , - I, - I) . U, d . , U(d) U(d) d=1,7 .(U , , U - ). , I, I

*, , I(U) , . .

XIII - 84 -2010

541.8

- -

.., ..

. .. () , . , e-mail: [email protected]

: , - (, , -, ).

(, , , , ) , , (I) - -, -, --2-, -, -, -, -.

- . - , - . . , "" - , . - - - - . , (- ) , , (- ). .

85

541.8

-

.., ..

. .. () , . , e-mail: [email protected]

ex

K

w w o oM A L LM A ex

K

o

ow w

LM A

M A Lex

K

= (w) (w)1,L +LM ass,LM A ,LM AD D

K K K K

,

,LD

K - (L) (w)

() ; (w)+LM

K -

; (w)ass,LM A

K

LM+A- ; ,LM AD

K

LM+A- . -

_+

o[LM A ]

2

o o_ + L+ M

o,L

[LM A ]1 1/

ex

D

K C C

K

_+o

+ _M + + +w w w

[LM A ]

[M ] [LM ] [LM A ]D

=

11,L

o o+ LM

11D

ex

K

K C C

-

_+o

o+M ,w

[LM A ]100%

=

+M

+M

100%1

D

D

.

-.

XIII - 86 -2010

677.11

.., ..


, , , . . , .

, .

. --. .

. 1,2-1,5 , , , (20-30%) . .

, 65-70 . .

, 35-45% - , .

87

546.271

--(12)

.., ..


(12)

. -. , 1,2-, 1,7-, 1,12-21012 a 22 27 [1].

(12) , : 1. , 2. (), , 3. , , 4. .

Gaussian 98 [2] (B3LYP/6-31G**, B3LYP/6-311++G**)

. -C2B10H12 > -C2B10H12 > -C2B10H12 > -C2H2B10Cl10 > -C2H2B10Cl10 - , .

pKa E, H,

G (B3LYP/6-311++G**) (12)

: HC-B10R10-CH HC-B10R10-C

+ H+ (R = H, Cl). ,

- 5.0 /, , .

(3;1)

(bCb),

. [1] L.I. Zakharkin, N.A. Ogorodnikova // J.Organometal.Chem. 1968. v.12. p. 13. [2] M. J. Frisch et. al., Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh (PA),

1998.

XIII - 88 -2010

547.466+54.052

.., .., ..


. , , .

-35 . : , , -35 +- - - .

. -35. , , , , . ( 2 /), .

, , , . , , , .

89

543.544.5.068.7

5(6)--2-(4-)

..1, ..1, ..1, ..2, ..3, ..1

1 . .. ( . .. ), .

2 (), . ; 3 , . , e-mail: [email protected]

5(6)--2-(4-) () , , . .

- -- (LCMS) -, () - (Na).

, (=224 ...) 252 .. : , 1, 2; Na : 2, 1, .

, 252 5(6)--2-(4-)-1-1,3- 4-(5--2-[d]--2-)-2,5-

N

N

NO

ON

H

N

N

N OH

ON

. , 1 2 , (~30% .). 1 2.

XIII - 90 -2010

669.15-194:678.675126.002.68

.., .., ..

., e-mail:[email protected]

() . n=60-80 ( - 3, - 50102 ).

(0,0085 / 0,01 /) 25-80 0 , Solver PRO .

. . 150 , 40-60 . 77,15 , (Ra , ISO 4287/1) 8,26 208,96 .

, : 25 0 (92 ) 80 0 (20 ) , 50-150 , 80 0 , 20 50-450 .

25 0 (92 ) Ra 25,02 287,13 ; 80 0 (20 ) Ra 20-45 89-99 .

, - , :

O

C

N

H2C

H2C

H

H2C

CH2

H2C

C

O N

H

- : I 1641 1 , II 1542 1 , III 1250 1 NH- 3108 1 .

91

547.128

.., .., .., ..


. N Si Ge . , , [1].

, ( 1) ( 2). , ( 3) , . R(CH2CH2)3N + 3H2O = . () + N(CH2CH2OH)3 (1), R(OR)3 + 3H2O = . () + 3 ROH (2), R(OR)3 + N(CH2CH2OH)3 = R(CH2CH2)3N + 3 ROH (3),

= Si Ge. () ()

, , , : () = ().

(2) (1), , 3 .

, , . 2 1 3: G(2) G(1) = G(3). (3) ( 4- 2- ), G(3), [1].

.

[1] .. , .. , .. , .. , .. ,

// , 2004, . 74, 1, c. 65-73.

XIII - 92 -2010

66.066.3

.., .., ..

- (), . -, e-mail: [email protected]

, , , .

, - . , . .., .

, , . . -3D , ( Flow Vision) .

. (Re 500), . , , (500

93

(III) (III) -

.., .., .., ..

- .. ( )


. - 50,05 0,5 . - . (III) (III) 0,070,2 /. (III) , (III), .

XIII - 94 -2010

541.49:(546.74.2+548.736)

[ReOL4Cl]Cl2 2H2O, L-1--2-

.., .., ..


[ReOL4Cl]Cl22H2O, L-1--2- (). 5%- 1 3,0 % . . . 2 mV. [ReOL4Cl]Cl22H2O .

.

[ReOL4Cl]Cl2 2H2O. 1-; 2-0,05%; 3-0,5%;4-1,5%; 5-2,0%; 6-3,0%.

, [ReOL4Cl]Cl22H2O . . 2% 47,7 11,2 . . 4,3 . , . 10. 47,7 31,4 . . 3% 5,5. .

95

541.64:539.(199+3)

1,3- -1 -

..1, ..3, ..1 1 , , e-mail: [email protected]

2 ,

: , () : , (B3LYP); , - 2- (2); () 2. 6-31+G**/6-311+G** aug-cc-PVDZ.

Gamess US, Pcgamess, Gaussian06, Moltran.

-1 , , . . , : , -1, . , . . 1:

1. (k1/k2) (k = nk1+nk2, .-1.-1). Gaussian06, pcgamess:

- k1/k2 k103

1,2- ub3lyp/aug-cc-pvdz 0,036 4640

H2C=CH- ub3lyp/aug-cc-pvdz 15,63 6,33

H2C=CH- ub3lyp/aug-cc-pvdz 4,6 28,4

CH3-CH2-CH=CH2 ub3lyp/aug-cc-pvdz 7,9 232

XIII - 96 -2010

66.022:621.929

-

.., .., .., ..


- . , - [1], : , , , , ..

- .

1 - - , . , . 4 . .

1 - -

[1] .., .., .. - - .: , 2009. 186 .

97

541. 64+548. 33

.., .., ..

. .. , . , 05010, . ., 106,

-mail: [email protected]

. .

, , - () NaB(C6H5)4. - (- NaB(C6H5)4), - 60:40,40:60 . %, ( =15000).

, (- NaB(C6H5)4 - (60:40 %) 1, 2 11:1 (=330 ), 7:1 (=436 ) 5:1 3 =450 ) 4:1 (=455 ). 15:1 (=326 ).

40% 60% 13:1 1 (=332 ), 3:1 (=461 ). 15:1 (=325 ) .

, . , - , , .

XIII - 98 -2010

669.712

.., .., ..


. . , , , , , . (Sc2O3 100/).

, . - . - , , .

, 17% 2 15% . Ti, Zr, Na Al, V, Fe, Si . . , . , - .

, , (>10) (

99

512.54: 579.11:541.62:548:12

D2D- (NH)4C10H24Ni:

.., .., ..

, 170002, , 35, e-mail: [email protected]

Ni2+ , . C-H N-H -(NH)4C10H24Ni (. ) . . Ni2+ 106

[Ni(NH2)4(CH2)4]. D2d (E, 3C2, 2S4, 2d) (NH)4C10H24Ni ,

,..., ml

ff , , ,...

l, m,... . l

f , , Z

: ZD2d= 1/8(f128

+3f214

+2f47+2f1

2f2

13).

ZD2d ...)( llll yxhf ,

D2d = 1/8{(h+x+)28

+3(h2+x

2+)14 +2(h4+x4+)7+2(h+x+)2(h2+x2)13}. (1) hkxlym (1) ( )

-NHqC24HkXlYm . 3718 : 14 , XY 65, XYZ 169 .. , X- : D2 = h

28+ 4x+ 56x

2+ 416x

3 +2618x

4+12324x

5

+47320x6+148148x

7+389144x

8+863720x

9+1641640x

10+2684916x

11+3804605x

12+468

1128x13

+5016720x14

+ 4681128x15

+ 3804605x16+ +416x25 +56x26 + 4x27 + x28.

: ZD2 = 1/4(f1

28 + 3f2

14), Z

. = 1/4(2f4

7+2f1

2f2

13).

, N.: Z.

(D2) 0,

Z(D2d) 38111043076464201013

, Z(D2)

76222086152928401013 . h2x2y2z2u2v2w2f2q2r2t2s2k2l2, , Z. (D2) 6227020800 .

X-,XY-, [1] .

[1] Smolyakov V.M., Sokolov D.V., Nilov D.Yu, Grebeshkov V.V., Fedin D.M. //

Journal Rare materials and technology. . China, Dzyasin, 2009. P. 626-636.

. (NH)4C10H24Ni

N

C

Ni

C

C

C

C

C

C

C

C

C

N

N

N

C

XIII - 100 -2010

66.017:542.61:546.63/64:548.75:537.533.35

.., .., ..


, , , . [1]. , [2-4]. -. XXI [5]. , , , , .

, . () . , . , , 12 40% (.) . 0,7% . . , , [6].

10-03-96039-__.

[1] .., .., .. . // , 1977. . 97. . 43-47.

[2] Small H.J. // Jnorg. Chem. 1961. 18. P. 232-238. [3] Barenova H., Nova-K M. // Coll. Czech. Chem. Comm. 1965. 30. P. 1073-1081. [4] .., .. // .

1960. . 39-40. [5] Yoshizawa H., Uemura Y., Kowano Y., Hatate Y. // J. Chem. Eng. Japan.

1993. 26. P.693-697.

[6] Shirokova A.G., Yatsenko S.P. // Abstracts Intern. conf. Functional Materials ICFM-2009, Ukrain, Crimea, Partenit. 2009. P. 436.

101

620.19

.., .., .., .., ..

- (), ., e-mail: [email protected]

. ( ), , - . , , , , .

(7421, 2, 20, 5, 71, 84) 4 . .

. 21,6 2. , 1,4104 2. .

-50-1 ( 0,5 ) -8. . .

, 5, . : 84>71>20>7421>2>5. , . , . , .

, , , .

XIII - 102 -2010

546.05

..1, ..2

1 . .. ( ), 2 , , e-mail: [email protected]

Zn2-xCoxSiO2, -1,5,10,20 %.

- 1 2 (1 ) (2 ). . Zn

2+ . . 9200 1 2 () () .

R3 (JCPDS 37-1485). . , . 1,5 ( ).

1-10% . 1000-1850 500-700 42

4T1 (

4F) 42

4T1 (

4P) (II). 20

% , (III), (2,5/0,1) .

( , 0,4 , - 1%) , 1 . 2 , , , .

, .

103

546. 264.,553. 682.

-

.., ..

- e-mail: [email protected]

- . , - , . . .

- . - 750

0, 1 . , - , Mg, 3. - CaO.

, , Ca(OH2) . C(OH2) . .. Ca(OH2) (Mg,Al) Si2O5 . - Mg3[Si4O11]nH20, 4CaOAl2O313H2O C2SH.

XIII - 106 -2010

66.023.2+665.6

.., .., ..

- ( ) (()), . -,


, . , (, , , ), (, .).

() "" , , , . - , , , , . (), (), () (), (). , 5 , , .

, , ( ), . , () (. 2184593, 2184594, 2184595). , 2-2.5 , 2.5-3.0 , .

() , , .

107

541.64:547.39

2-

.., .., ..

. .. , . .,


2- () () 2- () (), () () 28.

, , (). . , , , , .

: . , 1:3 120 0, 80 %.

80, 100, 120 150 0, , , .

, , 93 % 90 %.

, , , . . .

(), , .

XIII - 108 -2010

AN INVESTIGATION INTO THE REMOVAL OF SO2 FROM EFFLUENT

STREAMS: NOVEL APPROACH TO MINIMIZE SO2 EMISSION FROM

POTENTIAL JORDANIAN OIL SHALE PROCESSING PLANT

Marwan M. Batiha

Chemical Engineering Department, Faculty of Engineering,

Al-Hussein Bin Talal University, Ma'an P.O.Box 20, Jordan.


SO2 gas is one of the major air pollutants in the world and the main sources of

this gas are the combustion of sulphur-containing fossil fuels. Therefore, the

environmental issues concerning oil shale exploitation in Jordan has been given

considerable attention due to high sulphur content in oil shale. By achieving the goals

of this work, it is expected to make a contribution toward solving the potential

problem of SO2 emission from oil shale processing plants in Jordan using the

available resources. These resources are available in abundant quantities which

include: kaoilinite, zeolitic tuff, Dead Sea water and oil shale ash produced from oil

shale combustion and retorting.

One of the primary environmental concerns of utilization of Jordanian oil shale

is the high S content which have to be removed from the off gas stream upon oil shale

combustion or during shale oil refining. A number of effluent gas desulphurization

techniques are available. These can be broadly classified into four categories:

absorption of SO2 in liquids, absorption by moist particles, gas phase conversion of

SO2, and sorption by solids. The later is considered on of the promising ways for SO2

removal. The current work has been focused on examining the Dead Sea water

capacity for SO2 removal and the utilization of Jordanian kaolin, available in huge

quantities in Jordan, as well as oil shale ash to remove SO2 from off gas streams.

Surface modification of kaolin will be carried out to increase its adsorption capacity

of SO2.

This work presents a kinetic study on the dissolution and solubility of SO2 in

pure and Dead Sea water and a mathematical model which describes these processes

taking into account all the possible reactions involved.

Secondly, an investigation into the adsorption capacity of various natural,

modified and waste materials for SO2 removal from effluent streams has been carried

out. These materials include: alumino-silicate minerals like Jordanian kaolinite, oil

shale ash produced after complete combustion, oil shale ash produced after

microwave and conventional retorting and natural and modified Jordanian zeolite.

109

628.3:658.512:66.011

.., .., ..

( )


.

. , . , . .

- 13X, LiLSX . - , , , , . , , .

- . , , - ; ; , . - , .

, ( NO 99,9%).

, .

XIII - 110 -2010

547.426.1

.., ..

- - . .,, ., , 10.

. e-mail: [email protected]

. . . . (). , . , .

() () .

. , , .

() (). , () (). , , . , . :

W1=6,29105EXP(-(585003000)/RT).C

.C

.HCl (1) W1=3,3410

5EXP(-(585003000)/RT).C.2

.CHCl (2)

1 = 1,9 W2=1,610

4EXP(-(533003000)/RT).CC. HCl (3)

W2=1.6104EXP(-(533003000)/RT).C

.2.CHCl (4)

2 = 1.0

111

:661.77+661.743.3

.., .., ..


, 90% . . , , .

.

60-98

, 30% ; /H2O2=1/(413) (.). .

, , , ( ), - - .

- ; .

4-6, - .

30% . , 90%: 90-98; 22/=5/1. (4-6) 73-75 %, - 43-45%.

, , - .

XIII - 112 -2010

529.12

.., .., .., ..

, . , e-mail: [email protected].

, . , .

[1] , "SAPO-34".

"SAPO-34" 400 500, 1,6 6,4 . : 425, 6,4., ~80% ~80%. .

"SAPO-34" . , 425 6,4 . ~13% 2 . , "SAPO-34" 550 90 . 2 .

-Al2O3 .

, -Al2O3 . 10% 30%. .

[1] .. , .. , . . .

. XII - 2008 09-11 2008 ., . , .73.

113

: 547.546

.., .., .., ..


. , 2,5 ./ . , . , , , , , .

, . , , : , , . , .

, . , , . , .

- . , . , , .

, . . , .

XIII - 114 -2010

544.47:544.344

PT/C .

.., .., ..

. .. ( ), . , e-mail: [email protected]

( ).

Pt/C , . Pt . , Pt/C , . Pt/C . : , , . , ( , - - , , ).

, Pt/C 1-2 . , . , (30-40%). Pt , (>98%, 2-, , 30, 1 . 2, 0.5-1 , /Pt 2000 /).

115

66.097.3.001

..*, .., .., ..**

, . , e-mail: [email protected] *

. .. () , . ** (),

.

- . : , , (-16, -16, -24, -28, -603); (); (-2207); . . , , , .

, : , , . , , .

XIII - 116 -2010

541.128-39

..1, . .2, ..1, ..3, ..4, .4.

1 , , 2 - . ..,

. , 3 , .,

4 - , .. e-mail: [email protected]

(), , , . -, - , , 6 - 32 (5,6+) - (5,8+).

, 92-96% . 78-80% , , , , , .

117

66.095.62:661.727.3

..1, ..1, ..1, ..2, ..2 1 - ., e-mail: [email protected], 2 , ., e-mail: [email protected]

, , 2-, .

140-180 ~30 . , [1].

, - [2], c 2-3 /. , .

.

. : 1,8-2,0 , 89-91, 0,10-0,25 /. [2], - 90% 90-95%.

[1] . 5367106. 20.09.1993. Jerry D. Unruh, Wendell L. Pieper, Milo

C. Pass. . [2] .., .., .., .. // ,

2009, .50, 4, .1-10.

XIII - 118 -2010

665.633

.., , ..


( , , ) (, , ). - . , , .

, .

, , : PbO2, Fe2O3, MnO2, , , , :

, (=250) (=750). . 1 , , , -4 Hitec-3000.

1

H, / S, /() G, / K

298 1023 298 1023 1023 1023 36,09 42,18 233,40 243,82 -207,25 1,0246 -4 54,28 58,24 258,50 266,35 -214,13 1,0254

Hitec-3000 -105,79 -99,20 247,60 257,81 -362,94 1,0435

, , . .[1] , , , .

[1] .. . .: , 2005. 288.

119

665.531:547.912:541.128:546.723

..1, ..2, ..1,2 1 (),

2 ( ), . , e-mail: [email protected]

, .

- - .

, , , , , .

() .

.

, , , . : , . , , . , , (83-94 % .) .

( ) .

CARL ZEISS.

XIII - 120 -2010

665.3.095.134.3:183.3

.., .., .., ..


, , . .

, , .

, . , . :

;

;

, .

, : 1) - (); 2) ( ); 3) ( -, ) (

); 4) ( ).

.

. , () - , .

121

662.757

.., .., .., ..*, ..*

. . (), . , e-mail: [email protected]

* ... , .

- . . , , .

, (, ) . 100% 300-450. 2-4 (3040%). 49 64%. 512, , 1% ., -4, -5. , , , , . , , , , - , . , , .

, . , .

XIII - 122 -2010

529.12

.., .., ..


, . 0,1-0,2% , , , .

: , .. /1/ . , .

, . , 500 15 , . , ; .

460 500 (, ) . , . , , , .

[1] Borsa A.G., Herring A.M., McKinnon J.T. et. al. // Ind. Eng. Chem. Res. 1999.

Vol. 38. P. 4259

123

: 661.725.68

.., .., ..


(), , , . , : ; ; ; ; ..

- , , , , , , , - .

. , , , - ( , , ), .

- 10-13 (TS-1). 10 13 (TS-1) .

-1. . .

, - , .

XIII - 124 -2010

661.723.612

..

- , . e-mail: [email protected]

- () , 1,5-2 , . , , , , , .

, , , , , , . 10-15%. 10 ~0,1/ , 10% 0,3/ . , ( ).

(1100-1400 /( .)) . ( - 3-5 ). 245-255. 1,5-2 . 98-98,5% , , , . , . 23-24%.

125

665.64

.., .C., .., ..


. . - . , , .

, , . .

. 1

R-98

. 2 R-98

, , (. 1), 20 % . 18,25 % (. 2). , - - , .

XIII - 126 -2010

547.472.3

,

.., ..

- ... (), ., e-mail: [email protected]

, . Dow Chemical Co .

, , - (51%). . , , . : , , , , , . .

, 450 . , , , , , . , .

127

547.245.07

.., .., ..

- ()


(H2=CH)2SiCl2 (I) , , (Cl, CH=CH2). I (II) : ) b)

(CH2=CH)4Si

a) + SiCl4 / Kat

(CH2=CH)2SiCl2

b) + HCl / Kat

Kat (AlCl3,

tesis

Documents