ISSN 0352-5139
J.Serb.Chem.Soc. Vol. 69, No. 1(2004)
CONTENTS
Organic Chemistry and Biochemistry
A. Yusufo—lu, H. Çelik and F. G. KirbaÕlar: Utilization of Lavandula angustifolia Miller extracts as
natural repellents, pharamaceutical and industrial auxiliaries
1
S. [eatovi}, Lj. Gligi}, @. Radulovi} and R. M. Jankov: Purification and partial characterization of
superoxide dismutase from the thermophilic bacteria Thermotrix sp.
9
Inorganic Chemistry
G. Vu~kovi}, Z. M. Midoragovi} and S. Tanaskovi}: Preparation and properties of Cu(II) complexes
with N,N’,N”,N’’’-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane (tpmc) and
pseudohalides (NCO- or NCSe-). Part II
17
Physical Chemistry
S. Zor: Investigation of the adsorption of anionic surfactants at different pH values by means of active
carbon and the kinetics of adsorption
25
Electrochemistry
L. Li, Sh. Chen, H. Wu and H. Cui: Chaotic, mixed-mode and periodic oscillations during electrooxidation of copper in trichloroacetic acid
33
Materials
K. I. Popov, S. B. Krsti}, M. ^. Obradovi}, M. G. Pavlovi}, Lj. J. Pavlovi} and E. R. Ivanovi}: The
effect of the particle shape and structure on the flowability of electrolytic copper powder. III. A model
of the surface of a representative particle of flowing copper powder electrodeposited by reversing
current
43
I. Rusu, M.-L. Craus, D. Sutiman and A. Rusu: On the possible formation of Aurivillius phases in the
oxide system Bi2O3 – ZnO – Nb2O5
53
A. Vu~kovi}, S. Bo{kovi} and Lj. @ivkovi}: Synthesis of in situ reinforced silicon nitride composites
59
Analytical Chemistry
Lj. Petrovi}, V. Piperski, S. Risti}, J. Tasi}, V. Matovi} and M. Jokanovi}: HPLC methods for the
determination of acetyl- and benzoyl-tiazofurin in rat plasma
69
Chemical Engineering
N. M. Nika~evi}, A. P. Dudukovi} and Z. J. Predojevi}: Dynamic holdup in countercurrent gas –
flowing solids – packed bed contactors
77
J.Serb.Chem.Soc. 69(1)1–7(2004)
UDC 582.949.26.004.12:661.12
JSCS – 3123
Original scientific paper
Utilization of Lavandula angustifolia Miller extracts as natural
repellents, pharmaceutical and industrial auxiliaries
AYÔE YUSUFO˜LU, HÜLYA ÇELIK and F. GÜLAY KIRBAÔLAR
Department of Chemistry, Faculty of Engineering, Istanbul University, 34850 Avcìlar, Istanbul, Turkey
(E-mail: hcelik@istanbul.edu.tr)
(Received 10 June 2002, revised 6 August 2003)
Abstract: Essential oils, absolutes and concretes were prepared from the flowers and leaves of the plant
Lavandula angustifolia Miller cultivated in the Bosphorus region of Istanbul, Turkey. The difference in
the chemical composition of the mentioned extracts was investigated and compared by using a
combination of capillary GC-MS with the aim of offering them as repellent, pharmaceutical and
industrial auxiliaries. The IR-spectra, the yields and the physico-chemical data of the extracts were also
analysed.
Keywords: Lavandula angustifolia Miller, essential oil, absolute, concrete, repellent, pharmaceutics,
industrial.
REFERENCES
1. Ullmanns Encyclopädie der Technischen Chemie, Verlag Chemie GmbH, D-6940 Weinheim (1981)
Band 20, p. 252
2. D. Arctander, N. J. Elizabeth, Perfume and Flavor Materials of Natural Origin, U.S.A. (1960)
3. H. Davis, Flora of Turkey, University Press, Edinburg, 1982, 7,76
4. T. Baytop, Türkiye’de Bitkiler ¤le Tedavi, ¤. g. Ecz. Fak. Yay., Istanbul (1984)
5. E. Gildemeister, Fr. Hoffman, Die Aetherischen Öle, Akademie Verlag Berlin (1961) Band VII, pp.
7–18
6. S. _zeriÕ, A. Yusufo™lu, G. KìrbaÕlar, Chim. Acta Turc. 23 (1995) 37
7. R. P. Adams, Identification of Essential Oil Components by Gas Chromatography Mass
Spectroscopy, Allured Publ. Corp., Carol Stream, Illinois, 1995
8. K. Schnaubelt, Medical Aromatherapy; Healing with Essential Oils, Frog Ltd, 1999
9. V. A. Worwood, The Complete Book of Essentials Oils and Aromatherapy, New World Library,
ISBN: 0931432820 (1991)
10. K. Schnaubelt, Advanced Aromatherapy; The Science of Essential Oil Therapy, Inner Traditions
Ltd., ISBN: 0892817436 (1998)
11. S. Price, Aromatherapy for Common Ailment, London, UK, 1991
12. AOAC, Official Methods of Analysis, 15th edn. 2200 Wilson, Boulevard Arglinton, Virginia
22201, USA, 1990.
J.Serb.Chem.Soc. 69(1)9–16(2004)
UDC 541.459:577.151.6
JSCS – 3124
Original scientific paper
Purification and partial characterization of superoxide dismutase from the thermophilic bacteria
Thermothrix sp.
SVETLANA [EATOVI]*, LJUBINKA GLIGI]*, @ELJKA RADULOVI]* and RATKO M.
JANKOV**
*Galenika a.d., Institute, Batajni~ki drum b.b., 11080 Belgrade, Serbia and Montenegro and **Faculty
of Chemistry, University of Belgrade, Studentski trg 16, 11000 Belgrade, Serbia and Montenegro
(Received 20 June, revised 8 August 2003)
Abstract: Superoxide dismutase (SOD; EC 1.15.1.1.), a high molecular weight component of the
antioxidant defense system, provided promising results in the treatment of oxidative damage.
Thermothrix sp., isolated from thermal spa water in Serbia, showed high superoxide dismutase activity.
The SOD, from cell free extract, was purified to homogenity by ammonium sulfate precipitation,
Sephadex G 75 gel filtration chromatography and QAE Sephadex ion exchange chromatography. The
specific activity of the purified enzyme was 9191 U/mg. The purified enzyme was analyzed and
partially characterized. SOD was localized in polyacrylamide gel by activity staining, based on the
reduction of nitroblue tetrazolium (NBT) by superoxide. The enzyme molecular weight determined by
gel chromatography is 37 kD. According to SDS PAGE it is composed of two subunits of equal size,
joined by noncovalent interactions. The isoelectric point, assessed by isoelectric focusing is 5.3. The
optimum pH for enzyme activity was in the range of 8 to 10. The optimum temperature for SOD
activity was 60 ºC. After one hour of incubation at 40, 50 and 60 ºC the SOD activity increases, but at
80 ºC, the SOD is denaturated. After 24 hours of incubation at 25 ºC SOD activity only slightly
decreases.
Keywords: superoxide dismutase, Thermothrix sp., isolation, purification, characterization.
REFERENCES
1. Z. G. Zeikus, Enzyme. Microb. Technol. 1 (1979) 243
2. M. McCord, I. Fridovich, Free Radical Biol. Med. 5 (1988) 363
3. I. Fridovich, Annu. Rev. Biochem. 64 (1995) 97
4. I. Fridovich, J. Biol. Chem. 272 (1997) 18515
5. E. Parcer, C. Blake, FEBS Lett. 229 (1988) 377
6. J. Chun, H. Youn, Y. Yim, H. Lee, M. Kim, Y. Hah, S. Kang, J. Syst. Bacteriol. 47 (1997) 492
7. Lj. Gligi}, @. Radulovi}, G. Zavi{i}, Enzyme Microbial Technol. 27 (2000) 789
8. M. Bradford, Anal. Biochem. 72 (1976) 248
9. C. Winterbourn, E. Hawkins, M. Brain, W. Carrell, J. Lab. Clin. Med. 85 (1975) 337
10. C. Beauchamp, I. Fridovich, Anal. Biochem. 28 (1977) 362
11. U. Laemmli, Nature 227 (1970) 680
12. B. Leach, J. Collawn, W. Fish, Biochemistry 19 (1980) 5374
13. R. Cannio, G. Fiorentino, A. Morana, M. Rossi, S. Bartiolucci, Frontiers in Bioscience 5 (2000)
768
14. T. Oury, J. Crapo, Z. Valnickova, J. Ehghild, Biochem. J. 317 (1996) 51
15. L. McCord, I. Fridovich, J. Biol. Chem. 244 (1969) 6049
16. Y. Hakamada, K. Koike, T. Kobayashi, S. Ito, Extremophiles 1 (1997) 74
17. W. Dos Santos, I. Pacheco, M. Liu, M. Teixeira, A. Xavier, J. LeGall, J. Bacteriol. 182 (2000) 796.
J.Serb.Chem.Soc. 69(1)17–23(2004)
UDC 546.171.1–036.8:622.785
JSCS – 3125
Original scientific paper
Preparation and properties of Cu(II) complexes with N,N’,N",N’’’-tetrakis(2-pyridylmethyl)-1,4,8,11tetraazacyclotetradecane (tpmc) and pseudohalides (NCO– or NCSe–). Part II
GORDANA VU^KOVI]1, ZORAN M. MIODRAGOVI]1 and SLADJANA TANASKOVI]2
1Faculty of Chemistry, University of Belgrade, P. O. Box 158, 11001 Belgrade and 2Faculty of
Pharmacy, University of Belgrade, Vojvode Stepe 450, 11000 Belgrade, Serbia and Montenegro
(e-mail: gordanav@helix.chem.bg.ac.yu)
(Received 11 June, revised 2 September 2003)
Abstract: Two new Cu(II) complexes with N,N’,N",N’’’-tetrakis(2-pyridylmethyl)-1,4,8,11tetraazacyclotetradecane (tpmc) and pseudohalides (NCO- or NCSe-) were isolated. Elemental analyses
(C, H, N, Cu) corresponded to the formulas: [Cu2(NCO)tpmc](ClO4)3 . 2CH3CN and [Cu2(NCSe)2
tpmc](ClO4)2 . 2H2O . C2H5OH. The coordination mode of tpmc and these ambidentate
pseudohalides, geometries, spectral characteristics (VIS, IR) and other properties were compared with
those of the previously described [Cu2(NCS)2tpmc](ClO4)2. Antimicrobial activity towards selected
bacteria and yeast was tested and found for the NCSe but not the NCO complex.
Keywords: copper(II) complexes, octaazamacrocycle, isocyanato ligand, isoselenocyanato ligand,
antimicrobial activity.
REFERENCES
1. N. M. Senozan, J. Chem. Educ. 51 (1974) 503
2. J. P. Collman, R. R. Gagne, C. A. Reed, T. L. Halbert, G. Lang, J. Am. Chem. Soc. 97 (1975) 1427
3. K. P. Wainwright, Coord. Chem . Rev. 166 (1997) 35
4. (a) E. Asato, H. Toflund, S. Kida, M. Mikuriya, K. S. Murray, Inorg. Chim. Acta 165 (1989) 207; (b)
H. Harada, M. Kodera, G. Vu~kovi}, N. Matsumoto, S. Kida, Inorg. Chem. 30 (1991) 1190; (c) G.
Vu~kovi}, D. Opsenica, S. P. Sovilj, D. Poleti, M. Avramov-Ivi}, J. Coord. Chem. 42 (1997) 241; (d)
Z. M. Miodragovi}, G. Vu~kovi}, S. P. Sovilj, D. D. Manojlovi}, M. J. Malinar, J. Serb. Chem. Soc.
63 (1998) 781; (e) G. Vu~kovi}, D. Opsenica, S. P. Sovilj, D. Poleti, J. Coord. Chem. 47 (1999) 331;
(f) Z. M. Miodragovi}, G. Vu~kovi}, V. M. Leovac, V. M. Buzash, Synth. React. Inorg. Met.-Org.
Chem. 30 (2000) 57; (g) Z. M. Miodragovi}, G. Vu~kovi}, V. M. Leovac, J. Serb. Chem. Soc. 66
(2001) 597; (h) G. A. Bogdanovi}, Z. M. Miodragovi}, G. Vu~kovi}, R. Markovi}, A. Spasojevi}-de
Biré, Synth. React. Inorg. Met.-Org. Chem. 31 (2001) 1189; (i) G. Vu~kovi}, M. Antonijevi}, D.
Poleti, J. Serb. Chem. Soc. 67 (2002) 677
5. G. Vu~kovi}, E. Asato, N. Matsumoto, S. Kida, Inorg. Chim. Acta 171 (1990) 45
6. G. Vu~kovi}, M. T. [umar, I. D. Br~eski, V. M. Leovac, D. S. Miti}, J. Serb. Chem. Soc. 64 (1999)
191
7. S. P. Sovilj, G. Vu~kovi}, V. M. Leovac, D. M. Mini}, Polish J. Chem. Soc. 74 (2000) 945
8. J. Narayanan, M. E. Sosa-Torres, R. A. Toskano, J. Chem. Crystal. 31 (2001) 129
9. G. R. Watkins, R. Shutt, Inorg. Synth. 2 (1946) 186
10. Handbook of Chemistry, 10th Ed., McGraw-Hill, New York, 1961
11. V. K. Voronkova, G. Vu~kovi}, J. Jezierska, J. Mrozinski, Yu. V. Jablokov, Inorg. Chim. Acta 262
(1997) 147
12. A. M. Golub, H. Keler, V. V. Skopenko, Khimiya Pseudogalogenidov, Kievski Gosudarstvenni
Universitet, Kiev, 1981, translated from German
13. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 5th Ed.,
Wiley New York, 1997, p. 116
14. A. H. Norbury, Adv. in Inorg. Chem. and Radiochem. 17 (1975) 382
15. Ho-Ksiang, Lie-Zen Ho, Inorg. Chem. 23 (1984) 624
16. (a) R. g. Pearson, J. Am. Chem. Soc. 85 (1963) 3533; (b) R. G. Pearson, J. Chem. Educ. 45 (1968)
581; (c) ibid. 45 (1968) 643; (d) B. V. \or|evi}, @. D. Bugar~i}, Hem. pregled (in Serbian) 39 (1998)
130
17. F. Valach, M. Dunaj-Jur~o, J. Caraiand, M. Hvastijova, Coll. Czech. Chem. Commun. 39 (1974)
380
18. C. R. Mahon, G. Manuselis, Textbook of Diagnostic Microbiology, W. B. Saunders Company,
Philadelphia, 1995, p. 67.
J.Serb.Chem.Soc. 69(1)25–32(2004)
UDC 541.183+531.3:665.183.1:541.132.3
JSCS – 3126
Original scientific paper
Investigation of the adsorption of anionic surfactants at different pH values by means of active carbon
and the kinetics of
adsorption
SIBEL ZOR
Kocaeli University, Faculty of Science and Arts, Department of Chemistry, 41300, Kocaeli, Turkey (Email: merve@kou.edu.tr)
(Received 14 April, revised 8 September 2003)
Abstract: In this study, the effect of pH on the removal of anionic surfactants, such as linear alkyl
benzene sulfonate (LABS) and dodecyl benzene sulfonate (DBS) by means of adsorption by activated
carbon was investigated. For this purpose activated carbon was used as adsorbent. Anionic surfactant
solutions with initial pH values of 3, 6, 8 and 12 were used. The adsorption isotherms for the
adsorption of anionic surfactants by active carbon at different pH were determined. These adsorption
isotherms were seen to be consistent with Freundlich’s adsorption isotherm. k and n constants were
determined from Freundlich’s linear equation. Adsorption rate constants were determined from the
obtained kinetic curves which were suitable for the first order of rate kinetics.
Keywords: surfactant, active carbon, adsorption kinetics.
REFERENCES
1. S. Zor, B. Yazìcì, M. Erbil, H. Galip, Wat. Res. 32 (1998) 579
2. J. B. Weber, H. D. Coble, J. Agric. Food. Chem. 16 (1968) 475
3. H. B. Gala, S. H. Chiang, G. E. Klinzing, J. W. Tierney, Int. Conf. on Coal Sci., Pittsburgh (1983)
260
4. M. M. Saleh, A. A. Atia, Adsorption Science & Technol. 17 (1) (1999) 53
5. A. L. Ayub, S. L. Roberts, J. C. T. Kwak, Colloids and Sufaces 16 (1985) 175
6. R. W. Perry, F. F. Aplan, Separation Science and Technol. 23 (1998) 2097
7. Z.Q. Ou, A. Yediler, Y.W. He, L.Q. Jia, A. Kettrup, T.H. Sun, Chemosphere 32 (1996) 827
8. W. Rudzinski, A. Dabrowski, J. Naikiewicz Michalek, P. Padkoscielny, S. Partyka, Pol. J. Chem. 70
(1996) 231
9. H. Arai, K. Yoshizaki, J. Colloid Interface Sci. 35 (1971) 149
10. R. A. Garcia-Delgado, L. M. Cotoruelo, J. J. Rodriguez, Sep. Sci. Technol. 27 (1992) 1065
11. W. Brown, J. Zhao, Macromolecules 26 (1993) 2711
12. C. Paulo Pavan, L. Eduarrdo Crepaldi, A. De Gilmar Games, B. Joao Valim, Colloids and Surfaces
154 (1999) 399
13. N. Calace, E. Nardi, B. M. Petronio, M. Pietroletti, Environmetal Pollution 118 (2002) 315
14. X. Zeng, K. Osseo-Asare, Colloids and Surfaces 17 (2001)247
15. Riaz Qadeer, Abdul Hameed Rehan, Turk J. Chem. 26 (2002) 357
16. K.E. Bremmell, G. J. Jameson, S. Biggs, Colloids and Surfaces 146 (1999) 75
17. P. Samasundaran, D. W. Fuerstenau, J. Phys. Chem. 70 (1966) 91
18. D. Bitting, J. H. Harwell, Langmuir 3 (1987) 500
19. J. H. Harwell, J. C. Hoskins, R. S. Schechter, W. H. Wade, Langmuir 1 (1985) 251
20. J. M. Cases, Bull. Mineral. 102 (1979) 684
21. P. Somasundaran, D. W. Fuerstenau, Society of Mining Engineers, AIME 252 (1973) 275
22. M. Dominic, Di Toro, J. Lauro Dodge, C. V. Hand, Environ. Sci. Tech. 24 (1990) 1013
23. T. Wakamatsu, D. W. Fuerstenau, in Advances in Chemistry Series, No, 79, American Chem.
Society, Washington DC, 1968, p. 161
24. K. Urano, M. Saito, Chemosphere 13 (1984) 285
25. E. Matthijs, H. De Henau, Tenside Deterg. 22 (1985) 299
26. F. Tiberg, J. Brinck, L. Grant, Current Opinion in Colloid & Interface Sci. 4 (2000) 411
27. L. M. Grant, W.A. Ducker, J. Phys. Chem. 101 (1997) 5337
28. H. N. Patrick, G. G. War, S. Mame, I. A. Aksay, Langmuir 13 (1997) 4349
29. L. M. Grant, F. Tiberg, W. A. Ducker, J. Phys. Chem. B 102 (1998) 4288
30. N. B. Holland, M. Ruegsegger, R. E. Marchant, Langmuir 14 (1998) 2790.
J.Serb.Chem.Soc. 69(1)33–42(2004)
UDC 66.087.3+621.3.018:546.54
JSCS – 3127
Original scientific paper
Chaotic, mixed-mode and periodic oscillations during the electro-oxidation of copper in trichloroacetic
acid
LIANG LIa, SHENHAO CHENa,b, HONGTAI WUc and HAITAO CUIa
aDepartment of Chemistry, Shandong University, Jinan 250100, P. R. China (e-mail:
shchen@sdu.edu.cn), bState Key Laboratory for Corrosion and Protection, Shenyang 110015, P. R.
China and cMaterial Evidence Test and Research Center of Shandong Province, Jinan 250100, P. R.
China
(Received 26 May, revised 12 September 2003)
Abstract: The current oscillations of a copper electrode in trichloroacetic acid solutions were studied in
this paper. The Cu/CCl3COOH system is a new electrochemical oscillator, showing rich dynamic
behaviour on two controllable parameters: the trichloroacetic acid concentration (cCCl3COOH) and the
imposed potential (E). Phase trajectories were reconstructed from time series using time delay methods
in order that the complex oscillations could be analyzed. Five kinds of oscillations, periodic and
quasiperiodic, mixed-mode, aperiodic, small amplitude and chaotic current oscillations, were observed.
The EDS (energy dispersive spectroscopy) technique was used to analyze the elemental composition of
the film formed on the surface of the copper electrode after the current oscillations.
Keywords: current oscillations, copper, trichloroacetic acid.
REFERENCES
1. P. Parmananda, H. D. Dewald, R. W. Rollins, Electrochim. Acta 39 (1994) 917
2. H. D. Dewald, P. Parmananda, R. W. Rollins, J. Electrochem. Soc. 140 (1993) 1969
3. J. L. Hudson, T. T. Tsotsis, Chem. Eng. Sci. 49 (1994) 1493
4. H. D. Dewald, P. Parmananda, R. W. Rollins, J. Electroanal. Chem. 306 (1991) 297
5. S. H. Glarum, J. H. Marshall, J. Electrochem . Soc. 132 (1985) 2872
6. S. H. Glarum, J. H. Marshall, J. Electrochem. Soc. 132 (1985) 2878
7. K. F. Bonhoeffer, H. Gerischer, Z. Elektrochem. 52 (1948) 149
8. R. S. Cooper, J. M. Bartlett, J. Electrochem. Soc. 105 (1958) 109
9. H. P. Lee, K. Nobe, A. J. Pearlstein, J. Electrochem. Soc. 132 (1985) 1031
10. A. J. Pearlstein, H. P. Lee, K. Nobe, J. Electrochem. Soc. 132 (1985) 2159
11. M. R. Bassett, J. L. Hudson, J. Phys. Chem. 92 (1988) 6963
12. M. R. Bassett, J. L. Hudson, J. Phys. Chem. 93 (1988) 2731
13. M. R. Bassett, J. L. Hudson, J. Electrochem. Soc. 137 (1990) 922
14. M. R. Bassett, J. L. Hudson, J. Electrochem. Soc. 137 (1990) 1815
15. J. L. Hudson, M. R. Bassett, Rev. Chem. Eng. 7 (1991) 109
16. D. Sazou, Elecyrochim. Acta 42 (1997) 627
17. F. N. Albahadily, J. Ringland, M. Schell, J. Chem. Phys. 90 (1989) 813
18. M. T. M. Koper, P. Gasbard, J. H. Sluyters, J. Chem. Phys. 97 (1992) 8250
19. H. M. An, S. H. Chen, H. T. Cui, X. G. Yang, J. Electrochem. Soc. 149 (2002) B174
20. S.-Y. Zhao, S.-H. Chen, H.-Y, Ma, D.-G. Li, F.-J. Kong, J. Appl. Electrochem. 32 (2002) 231
21. G. Charlot, L’analyse qualitative et les reaction en solution, Masson & Cie, Paris, 1957, p. 225
22. A. Karantonis, Y. Shiomi, S. Nakabayashi, J. Electroanal. Chem. 493 (2000) 57
23. J. K. McCoy, P. Parmananda, R. W. Rollins, A. J. Markworth, J. Mater. Res. 8 (1993) 1858
24. D. Sazou, A. Diamantopoulou, M. Pagitsas, J. Electroanal. Chem . 489 (2000) 1
25. M. Itagaki, T. Mori, K. Watanabe, Corros. Sci. 41 (1999) 1955.
J.Serb.Chem.Soc. 69(1)43–51(2004)
UDC 54–72.001.57:541.135.2:546.56.0343
JSCS – 3128
Original scientific paper
The effect of the particle shape and structure on the flowability of electrolytic copper powder. III. A
model of the surface of
a representative particle of flowing copper powder
electrodeposited by reversing current
KONSTANTIN I. POPOV1, SNE@ANA B. KRSTI]1#, MILUTIN ^. OBRADOVI]1#, MIOMIR G.
PAVLOVI]2#, LJUBICA J. PAVLOVI]2 and EVICA R. IVANOVI]3
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade,
2ICTM-Department of Electrochemistry, Njego{eva 12, 11000 Belgrade and 3Faculty of Agriculture,
University of Belgrade, Nemanjina 6, 11080 Zemun-Belgrade, Serbia and Montenegro
(E-mail: kosta@elab.tmf.bg.ac.yu)
(Received 21 July 2003)
Abstract: The structure of the surface of copper powder particles is discussed and correlated with the
lowest apparent density at which copper powder can still flow. It is shown that such structures can be
easily obtained in the electrodeposition of powders in reversing current regimes.
Keywords: copper powder flowability, surface structure of particles of flowing copper powder.
IZVOD
UTICAJ OBLIKA I STRUKTURE ^ESTICA NA TE^QIVOST ELEKTROLITI^KOG BAKARNOG
PRAHA. III. MODEL POVR[INE REPREZENTATIVNE ^ESTICE TE^QIVOG BAKARNOG
PRAHA DOBIJENOG ELEKTOHEMIJSKIM TALO@EWEM REVERSNOM STRUJOM
KONSTANTIN I. POPOV1, SNE@ANA B. KRSTI]1, MILUTIN ^. OBRADOVI]1, MIOMIR G.
PAVLOVI]2, QUBICA J. PAVLOVI]2 i EVICA R. IVANOVI]3
1Tehnolo{ko-metalur{ki fakultet, Univerzitet u Beogradu, Karnegijeva 4, 11000 Beograd, 2IHTM Odsek za elektrohemiju, Wego{eva 12, 11000 Beograd i 3Poqoprivredni fakultet, Univerzitet u
Beogradu, Nemawina 6, 11080 Zemun-Beograd
Razmatrana je struktura povr{ine ~estica bakarnog praha i korelisana s najmawom nasipnom masom
pri kojoj bakarni prah jo{ uvek mo`e da te~e. Pokazano je da se takva struktura mo`e lako dobiti
elektrohemijskim talo`ewem praha u re`imu reversne struje.
(Primqeno 21. jula 2003)
REFERENCES
1. K. I. Popov, S. B. Krsti}, M. G. Pavlovi}, J. Serb. Chem. Soc. 68 (2003) 511
2. K. I. Popov, S. B. Krsti}, M. Obradovi}, M. G. Pavlovi}, Lj. J. Pavlovi}, E. R. Ivanovi}, J. Serb.
Chem. Soc. 68 (2003) 771
3. K. I. Popov, M. G. Pavlovi}, Lj. J. Pavlovi}, E. R. Ivanovi}, S. B. Krsti}, M. Obradovi}, J. Serb.
Chem. Soc. 68 (2003) 779
4. E. Peisseker, J. of Powder Metallurgy and Powder Technology 20 (1984) 27
5. M. G. Pavlovi}, Lj. J. Pavlovi}, E. R. Ivanovi}, V. Radmilovi}, K. I. Popov, J. Serb. Chem. Soc. 66
(2001) 923
6. K. I. Popov, Lj. J. Pavlovi}, E. R. Ivanovi}, V. Radmilovi}, M. G. Pavlovi}, J. Serb. Chem. Soc. 67
(2002) 61
7. K. I. Popov, M. D. Maksimovi}, J. D. Trnjan~ev, M. G. Pavlovi}, J. Appl. Electrochem. 11 (1981)
239
8. K. I. Popov, M. D. Maksimovi}, M. G. Pavlovi}, D. T. Luki}, J. Appl. Electrochem. 10 (1980) 299
9. K. I. Popov, M. S. Krstaji}, M. I. ^ekerevac, The Mechanism of Formation of Coarse and Disperse
Electrodeposits, in Modern Aspects of Electrochemistry, No 30, R. E. White, B. E. Conway and J.
O’M. Bockris, Eds., Plenum Press, New York, 1996, p. 294
10. K. I. Popov, S. S. Djoki}, B. N. Grgur, Fundamental Aspects of Electrometallurgy, Kluwer
Academic / Plenum Publisher, New York, 2002, p. 78
11. K. I. Popov, E. R. Stoiljkovi}, V. Radmilovi}, M. G. Pavlovi}, Powder Technology 93 (1997) 55
12. K. I. Popov, P. M. @ivkovi}, S. B. Krsti}, J. Serb. Chem. Soc., 68 (2003) 903.
J.Srb.Chem.Soc. 69(1)53–58(2004)
UDC 542.919+541.12.01+543.57:621.317.3
JSCS – 3129
Original scientific paper
On the possible formation of Aurivillius phases in the oxide
system Bi2O3–ZnO–Nb2O5
IULIAN RUSU1, MIHAIL-LIVIU CRAUS2, DANIEL SUTIMAN1 and ALICE RUSU1
1Technical University “Gh. Asachi”, Faculty of Industrial Chemistry, Bd. D. Mangeron 71, Iasi 6600
and 2National Institute for Technical Physics, Bd. D. Mangeron 47, Iasi 6600, Romania
(e-mail: rusu_iulian@hotmail.com)
(Received 7 March, revised 8 August 2003)
Abstract: This paper presents results concerning the possible synthesis of double perovskite and
Aurivillius phases in the BZN system. A crystal chemical criterion based on an elastic model for the
structure was used in order to determine if the formation of layered bismuth compounds is favoured in
the above system. The tempeature seems to be the decisive factor influencing Aurivillius phase
formation.
Keywords: synthesis, phase transition, thermal analysis, XRD.
REFERENCES
1. H. C. Ling, M. F. Yan, W. W. Rhodes, J. Mater. Res. 5 (1990) 1752
2. D. Liu, Y. Liu, S. Q. Huang, X. Yao, J. Am. Ceram. Soc. 76 (1993) 2129
3. M. F. Fang, H. C. Ling, Mater. Chem. Phys. 44 (1996) 37
4. D. P. Cann, C. A. Randall, T. R. Shrout, Solid State Commun. 100 (1996) 529
5. X. Wang, H. Wang, X. Yao, J. Am. Ceram. Soc. 80 (1997) 2745
6. J. C. Nino, M. T. Lanagan, C. A. Randall, J. Appl. Phys. 89 (2001) 4512
7. Y. Hu, C. L. Huang, Mater. Chem. Phys. 72 (2001) 60
8. G. Jeanne, G. Desgardin, B. Raveau, Mat. Res. Bull. 9 (1974) 1321
9. H. Brusset, H. Gillier-Pandraud, P. Rajaonera, Mat. Res. Bull. 10 (1975) 209
10. I. Rusu, M. L. Craus, I. Rosca, E. Condiffe, M. J. Smith, D. Sutiman, M. Palamaru, A. Cailean, N.
Apostolescu, Proc. ISE 10, IEEE, Piscataway, 1999, p. 325
11. I. Rusu, M. L. Craus, Bull. IPI Chem. & Chem. Eng. 3/4 (2000) 17
12. M. L. Craus, I. Rusu, A. Rusu, N. Apostolescu, J. Phys. IV 90 (2001) 109
13. M. L. Craus, I. Rusu, A. Rusu, Proc. JEEP XXVII, R. M. marin-Ayral & M.C. Record, Eds.,
Montpellier, 2001, p. 103
14. P. E. Werner, Z. Krist. 120 (1964) 375
15. A. Boultif, D. Louer, J. Appl. Cryst. 24 (1991) 987
16. R. D. Shannon, C. T. Prewitt, Acta Cryst. B25 (1969) 925
17. C. D. Brandle, V. J. Fratello, J. Mater. Res. 5 (1990) 2160
18. Nouveau Traite de Chimie Minerale, P. Pascal, Ed., Masson et Cie, Paris, 1958, p. 449
19. V. G. Osipian, S. A. Igaune, I. A. Vitinia, E. J. Freidenfeld, Zh. Neorg. Khim . 27 (1982) 299
20. PCPDFWIN Version 2.0, JCPDS-ICDD, August 1998
21. P. M. De Wolff, J. Appl. Cryst. 1 (1968) 108
22. B. Aurivillius, P. H. Phang, Phys. Rev. 126 (1962) 893
23. T. Kikuchi, Mat. Res. Bull. 14 (1979) 1561
24. R. A. Armstrong, R. E. Newnham, Mat. Res. Bull. 7 (1972) 1025.
J.Serb.Chem.Soc. 69 (1)59–67(2004)
UDC 546.562+546.268.2:615.28
JSCS – 3130
Original scientific paper
Synthesis of “in situ” reinforced silicon nitride composites
ALEKSANDRA VU^KOVI]1, SNE@ANA BO[KOVI]1# and LJILJANA @IVKOVI]2
1Materials Science Laboratory, Vin~a Institute of Nuclear Sciences, P. O. Box 522,11001 Belgrade
and 2Faculty of Electronic Engineering, University of Ni{, Serbia and Montenegro (email:acavuc@vin.bg.ac.yu)
(Received 25 July 2003)
Abstract: The objective of this work was to investigate the effect of two different sintering additives
(CeO2 and Y2O3 + Al2O3), sintering time and amount of b-Si3N4 seeds on the densification,
mechanical properties and microstructure of self-reinforced Si3N4 based composites obtained by
pressureless sintering. Preparation of b-Si3N4 seeds, also obtained by a pressureless sintering
procedure, is described. Samples without seeds were prepared for comparison. The results imply that
self-reinforced silicon nitride based composites with densities close to the theoretical values and with
fracture toughness of 9.3 MPa m1/2 can be obtained using a presureless sintering procedure.
Keywords: b-Si3N4 seeds, additive, pressureless sintering, self-reinforced composites, densification,
fracture toughness.
REFERENCES
1. G. Petzow, M. Hermman, Silicon Nitride Ceramics, Structure and Bonding Springer – Verlag,
Berlin, Heidelberg, Vol. 102 (2002) 80
2. J. Weiss, W. A. Kaysser, in Progress in Nitrogen Ceramics, F. L. Riley, Ed., 1983, p. 169
3. M. Mitomo, S. Uenosono, J. Mater. Sci. 26 (1991) 3940
4. P. Sajgalik, J. Dusza, M. Hoffman, J. Am. Ceram. Soc. 78 (1995) 2619
5. K. Hirao, M. Ohashi, M. E. Brito, S. Kanzaki, J. Am. Ceram. Soc. 78 (1995) 1687
6. P. F. Becher, E. Y. Sun, K. P. Pluncket, K. B. Alexander, C. H. Hsueh, H. T. Lin, S. B. Waters, C. G.
Westmoreland, J. Am. Ceram. Soc. 81 (1998) 2821
7. K. Hirao, T. Nagaoka, M. E. Brito, S. Kanzaki, J. Am. Ceram. Soc. 77 (1994) 1857
8. K. Hirao, A. Tsuge, M. E. Brito, S. Kanzaki, in Proceedings of Silicon Nitride-Based Ceramics,
Tranas. Tech. Publishers, Adermansdorf, Switzerland, 1994, pp. 63–66
9. M. Mitomo, Proc. of the 1st International Symposium on the Science of Engineering Ceramics, Oct.
21–23, Achi Japan, S. Kimura, K. Niihara, Eds., the Ceramic Society of Japan (1991) p. 101
10. D. E. Wittmer D. Doshi, T. E. Paulson: 4th International Symposium on Ceramic Materials and
Components for Engines, June 10–12, 1991, Sweden, R. Carlsson, T. Johansson, L. Kahlman, Eds.,
Elsevier Applied Science Pub., 1992, p. 594
11. K. Hirao, A. Tsuge, M. E. Brito, S. Kanzaki, Key Engineering Materials, Vol. 89–91 (1994) 63
12. T. I. Mah, K. S. Mazdiyashi, R. Ruh, J. Am. Ceram. Soc. 62 (1979) 12
13. K. H. Jack, J. Mat. Sci. 11 (1976) 1135
14. F. C. Peillon, F. Thevenot, J. Eur. Ceram. Soc. 22 (2002) 271
15. M. Belmonte, P. Miranzo, J. S. Moya, J. Am. Ceram. Soc. 78 (1995) 1661.
J.Serb.Chem.Soc. 69(1)69–75(2004)
UDC 543:541.24:547.78:537.5
JSCS – 3131
Original scientific paper
HPLC methods for the determinatiuon of acetyl- and benzoyl-tiazofurin in rat plasma
LJILJANA PETROVI]1, VESNA PIPERSKI1, SLAVICA RISTI]1, JELENA TASI]1, VESNA
MATOVI]2 and MILAN JOKANOVI]1
1Galenika a.d. Institute, Analytical and Stability Center, Batajni~ki drum b.b., 11080 Zemun and
2Faculty of Pharmacy, University of Belgrade, Vojvode Stepe 450, 11000 Belgrade, Serbia and
Montenegro
(E-mail address; japanac@yubc.net)
(Received 13 May 2003)
Abstract: Reverse-phase HPLC methods for determination of 5’-O-acetyl-tiazofurin (AT) and 5’-Obenzoyl-tiazofurin (BT) in rat plasma were developed and validated in terms of specificity, linearity,
precision, accuracy and sensitivity. Linear calibration curves were constructed in the concentration
range of 2.50 – 100.00 mmol/L for both compounds. The separations were achieved on a Supelcosyl
LC-18-DB analytical column (250 ´ 4.6 mm; 5 mm particle size) by isocratic elution, with a mixture of
0.1 M disodium hydrogen phosphate – methanol. UV detection was performed at a wavelength of 254
nm. The proposed methods enable the detection and quantification of nanomolar concentrations of AT
and BT in rat plasma.
Keywords: HPLC, acetyl-tiazofurin, benzoyl-tiazofurin, rat plasma.
REFERENCES
1. P. Franchetti, L. Cappellacci, M. Grifantini, Farmaco 51 (1996) 457
2. R. K. Robins, P. C. Srivastava, J. Med. Chem. 25 (1982) 107
3. G. S. Ahluwalia, H. N. Jayaram, J. P. Plowman, D. A. Cooney, D. G. Johnes, Biochem. Pharmacol.
33 (1984) 1195
4. H. N. Jayaram, K. Pillwein, G. Weber, Nucleosides & Nucleotides 5 (1986) 503
5. G. Weber, N. Prajda, M. Abonyi, K. Y. Look, G. Tricot, Anticancer Res. 6 (1996) 3313
6. E. Olah, B. Csokai, N. Prajda, Z. Kote-Jarai, G. Weber, Anticancer Res. 16 (1996) 2469
7. V. Piperski, M. Vra~ar, M. Jokanovi}, P. Stukalov, Lj. Raki}, Apoptosis 3 (1998) 345
8. K. Drabek, M. Pe{i}, V. Piperski, S. Ru`diji}, Lj. Medi}-Mija~evi}, Z. Peitzkowski, Lj. Raki},
Anticancer Drugs 11 (2000) 765
9. M. Vitale, L. Zamai, E. Falcievi, Cytometry 30 (1997) 61
10. V. Pejanovi}, Lj. Medi}-Mija}evi}, D. Uglje{i}-Kilibarda, Z. Stoki}, V. Piperski, S. Ruzdiji}, Pat.
appl. YU 707/99
11. V. Piperski, J. Djurovi}, M. Vra~ar, S. Jovanovi}, M. Jokanovi}, V. Pejanovi}, Arch. Toxicol.
Kinet. Xenobiot. Metab. 6 (1998) 311
12. R. W. Klecker, J. M. Collins, J. Chromatogr. 307 (1984) 361
13. C. M. Riley, L. A. Sternson, A. J. Repta, J. Chromatogr. 276 (1983) 93
14. B. Chandrasekaran, B. Ardalan, J. Chromatogr. 276 (1983) 237
15. J. Tasi}, S. Risti}, V. Piperski, M. Da~evi}, V. Pejanovi}, M. Jokanovi}, Lj. Mandi}, J. Pharm.
Biomed. Analysis 30 (2002) 993.
J.Serb.Chem.Soc. 69(1)77–84(2004)
UDC 66.040.3/4:66.017
JSCS – 3132
Original scientific paper
Dynamic holdup in a countercurrent gas - flowing solids - packed bed contactors
NIKOLA M. NIKA^EVI]1, ALEKSANDAR P. DUDUKOVI]1 and ZLATICA J. PREDOJEVI]2
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade and
2Faculty of Technology, University of Novi Sad, Bul. cara Lazara 1, 21000 Novi Sad, Serbia and
Montenegro
(E:mail: duduhome@eunet.yu)
(Received 25 June 2003)
Abstract: Equations for the prediction of the holdup of dynamic solids in countercurrent gas – flowing
solids – packed bed contactors are presented in this paper. The correlations do not require the use of
parameters that need to be determined by experimental measurements in the actual system of interest.
They could be used for a wide range of operational conditions, different packing types and a variety of
flowing solids materials. The equations are compared with all available experimental data from the
literature.
Keywords: multiphase contactors, gas – flowing solids – packed bed contactors, gas – trickle solids
flow, dynamic solids holdup.
REFERENCES
1. Directie Staatsmijnen, French Patent 978287, 1948
2. Compagnie de Saint-Gobain. French Patent 1469109, 1965
3. G. D. Kaveckii, A. N. Planovskii, Khim. Tekhnol. Topl. Masel. 11 (1962) 8
4. G. D. Kaveckii, A. N. Planovskii, L. A. Akopyan, Khim. Prom. 6 (1963) 449
5. G. Claus, F. Vergnes, P. le Goff, Can. J. Chem. Eng. 54 (1976) 143
6. A. W. M. Roes, W. P. M. van Swaaij, Chem. Eng. J. 17 (1979) 81
7. A. W. M. Roes, W. P. M. van Swaaij, Chem. Eng. J. 18 (1979) 13
8. J. F. Large, M. Naud, P. Guigon, Chem. Eng. J. 22 (1981) 95
9. A. B. Verver, W. P. M. van Swaaij, Powder Technol. 45 (1986) 119
10. K. R. Westerterp, M. Kuczynski, Chem. Eng. Sci. 42 (1987) 1539
11. Z. J. Predojevi}, D. Lj. Petrovi}, A. Dudukovi}, Chem. Eng. Commun. 162 (1997) 1
12. Z. J. Predojevi}, Ph. D. Thesis, Faculty of Technology, Novi Sad, Yugoslavia, 1997
13. Z. J. Predojevi}, D. Lj. Petrovi}, V. Martinenko, A. Dudukovi}, J. Serb. Chem. Soc. 63 (1998) 85
14. O. P. Stanimirovi}, Diplome Thesis, Faculty of Technology, Novi Sad, Yugoslavia, 1998
15. A. W. M. Roes, W. P. M. van Swaaij, Chem. Eng. J. 18 (1979) 29
16. E. Saatdjian, J. F. Large, Eng. Sci. 40 (1985) 693
17. J. H. A. Kiel, W. Prins, W. P. M. van Swaaij, Chem. Eng. Sci. 47 (1992) 4271
18. K. R. Westerterp, M. A. Kuczynski, Chem. Eng. Sci. 42 (1987) 1871
19. M. Kuczynski, M. H. Oyevaar, R. T. Pieters, K. R. Westerterp, Chem. Eng. Sci. 42 (1987) 1887
20. A. B. Verver, W. P. M. van Swaaij, Chem. Eng. Sci. 42 (1987) 435
21. J. H. A. Kiel, W. Prins, W. P. M. van Swaaij, Chem. Eng. Sci. 48 (1993) 117
22. Z. J. Predojevi}, D. Lj. Petrovi}, A. P. Dudukovi}, Ind. Eng. Chem. Res. 40 (2001) 6039
23. J. H. A. Kiel, Ph. D. Thesis, University of Twente, Enschede, The Netherlands, 1990
24. M. Benali, K. Shakourzadeh-Bolouri, Int. J. Mulitphase Flow 20 (1994) 161.