ISSN 0352-5139
J. Serb. Chem. Soc. Vol. 69, No. 10 (2004)
CONTENTS
Organic Chemistry
D. @. Mijin, M. M. Mi{i}-Vukovi} and S. D. Petrovi}: Alkylation of N-substituted-2-phenylacetamides
(Review)
711
G. Petrovi}, R. N. Sai~i}, Lj. Do{en-Mi}ovi} and @. ^ekovi}: Stereoselective free radical
phenylsulfenylation of a nonactivated d-carbon atom
737
S. Sinadinovi}-Fi{er and J. Jovanovi}: MS analysis of biindenylidenes
749
D. @. Mijin and D. G. Antonovi}: Temperature dependence of the Kovats retention indices for alkyl 1,3diketones on a DB-5 capillary column
759
T. Kop, G. Pocsfalvi and B. [olaja: Synthesis of a steroidal dendrimer core (Preliminary communication)
769
Physical Chemistry
I. Gutman, D. Stevanovi}, S. Radenkovi}, S. Milosavljevi} and N. Cmiljanovi}: Dependence of the total pelectron energy on large number of non-bonding molecular orbitals
777
L. Luo, H. Zhong and X. Yang: Oxidative performance and surface properties of Co-containaing mixed
oxides having the K2NiF4 structure
783
Electrochemistry
G. Li, H. Ma, Y. Jiao and S. Chen: An impedance investigation of corrosion protection of copper by selfassembled monolayers of alkanethiols in aqueous solution
791
J. B. Bajat, V. B. Mi{kovi}-Stankovi}, M. D. Maksimovi}, D. M. Dra`i} and S. Zec: Electrochemical
deposition and characterization of Zn-Fe alloys
807
Materials
K. I. Popov, S. B. Krsti}, M. G. Pavlovi}, Lj. J. Pavlovi} and V. M. Maksimovi}: The effect of the particle
shape and structure on the flowability of electrolytic copper powder. IV. The internal structure of the
powder particles
817
Chemical Engineering
M. Kijev~anin, B. Djordjevi}, O. Oci}, M. Crnomarkovi}, M. Mari} and S. [erbanovi}: Energy and
economy savings in the process of methanol synthesis unsig Pinch technology
827
J. Serb. Chem. Soc. 69 (10) 711–736 (2004)
UDC 66.095.253.097:547-327
JSCS – 3199
Review
REVIEW
Alkylation of N-substituted 2-phenylacetamides
DU[AN @. MIJIN1, MILICA M. MI[I]-VUKOVI]1# and SLOBODAN D. PETROVI]1,2#
1Department of Organic Chemistry, Faculty of Technology and Metallurgy, Universitiy of Belgrade, P. O.
Box 3503, 11120 Belgrade and 2Hemofarm group, Beogradski put bb, Vr{ac, Serbia and Montenegro
(Received 24 February 2004)
Abstract: Various N-substituted phenylacetamides were alkylated using different alkylating agents under
neutral and basic conditions. Reactions were performed at different reaction temperatures and in various
solvents. Also, a number of various catalysts were used including phase-transfer catalysts. Reactions were
followed using GC or GC-MS technique and the presence as well as the yields of the alkylation products
were established. Generally, the best yield and high selectivity in the studied reactions were achieved under
basic conditions where in the certain cases some products, mostly N-product, were obtained solely in
quantitative yields.
Keywords: alkylation, amides, phenylacetamides, alkylation under neutral conditions, alkylation under
basic conditions, phase-transfer conditions.
REFERENCES
1. B. C. Challis, J. A. Challis, in The Chemistry of Amides, Interscience Publishers, London, 1970, p. 731
2. S. D. Petrovi}, N. D. Stojanovi}, D. @. Mijin, Hem. Ind. 50 (1996) 456
3. S. D. Petrovi}, N. D. Stojanovi}, O. K. Stojanovi}, N. L. Kobilarov, J. Serb. Chem. Soc. 51 (1986) 395
4. S. D. Petrovi}, N. D. Stojanovi}, O. K. Stojanovi}, N. L. Kobilarov, J. Serb. Chem. Soc. 53 (1988) 633
5. B. C. Challis, A. D. Frenkel, J. Chem. Soc. Perkin Trans. II (1978) 192
6. S. D. Petrovi}, N. D. Stojanovi}, O. K. Stojanovi}, N. L. Kobilarov, J. Serb. Chem. Soc. 55 (1990) 575
7. A. W. Chapman, J. Chem. Soc. 127 (1925) 1992
8. A. L. Garner, G. C. McCurty, The Chemistry of Amidines and Imidates, S. Patai, Ed., Interscience, New
York, 1975, p. 190
9. D. G. Antonovi}, D. @. Mijin, N. D. Stojanovi}, Lj. A. Jeremi}, S. D. Petrovi}, J. Serb. Chem. Soc. 59
(1994) 967
10. H. Muxfeldt, J. Behling, G. Grethe, W. Rogalski, J. Am. Chem. Soc. 89 (1967) 4991
11. R. Kantlehner, Advanced Org. Chem. 9 (1979) 181
12. S. D. Petrovi}, N. D. Stojanovi}, Lj. A. Jeremi}, M. B. Blagojevi}, J. Serb. Chem. Soc. 60 (1995) 749
13. C. Wong, L. M. Jackman, R. G. Portman, Tetrahedron Lett 11 (1974) 921
14. P. Beak, Jae-Kem Lee, B. G. McKinnie, J. Org. Chem. 43 (1978) 1367
15. S. D. Work, D. R. Bryant, C. R. Hauser, J. Org. Chem. 29 (1964) 722
16. K. Sukata, Bull. Chem. Soc. Jpn. 58 (1985) 838
17. D. @. Mjijin, B. M. Bo`i}, N. D. Stojanovi}, S. D. Petrovi}, J. Serb. Chem. Soc. 61 (1996) 1137
18. D. @. Mijin, B. M. Bo`i}, D. G. Antonovi}, N. D. Stojanovi}, S. D. Petrovi}, J. Ind. Chem. 36B (1997)
934
19. D. @. Mijin, B. M. Bo`i}, V. D. Jankovi}, D. G. Antonovi}, N. D. Stojanovi}, S. D. Petrovi}, J. Serb.
Chem. Soc. 64 (1999) 83
20. V. D. Jankovi}, D. @. Mijin, S. D. Petrovi}, J. Serb. Chem. Soc. 67 (2002) 373
21. D. @. Mijin, V. D. Jankovi}, S. D. Petrovi}, J. Serb. Chem. Soc. 68 (2004) 85
22. D. @. Mijin, V. D. Jankovi}, S. D. Petrovi}, Nauka, Tehnika, Bezbednost 1 (2004) 29 (in Serbian)
23. M. Rabinovitz, Y. Cohen, M. Halpern, Angew. Chem. Int. Ed. Engl. 25 (1986) 960
24. D. @. Mijin, N. D. Stojanovi}, S. D. Petrovi}, J. Serb. Chem. Soc. 59 (1994) 811
25. C. Starks, J. Am. Chem. Soc. 93 (1971) 195
26. M. Makosza, Pure Appl. Chem. 43 (1975) 439
27. D. @. Mijin, M. M. Mi{i}-Vukovi}, N. D. Stojanovi}, S. D. Petrovi}, Ind. J. Chem. 35B (1996) 1201
28. D. @. Mijin, N. D. Stojanovi}, S. D. Petrovi}, Zh. Org. Khjim. 34 (1998) 1876
29. D. @. Mijin, D. G. Antonovi}, V. V. Vajs, S. D. Petrovi}, Nauka, Tehnika, Bezbednost 2 (1997) 45 (in
Serbian)
30. G. O. Torossian, S. A. Grigor, G. Gekchyan, A. T. Babayan, Arm. Khim. Zh. 37 (1984) 740
31. D. @. Mijin, N. D. Stojanovi}, S. D. Petrovi}, Zh. Org. Khim. 34 (1998) 1578.
J. Serb. Chem. Soc. 69 (10) 737–747 (2004)
UDC 547.541+541.124:541.515
JSCS – 3200
Original scientific paper
Stereoselective free radical phenylsulfenylation of
a nonactivated d-carbon atom
GORAN PETROVI]a, RADOMIR N. SAI^I]a,b#, LJILJANA DO[EN-MI]OVI]a# and
@IVORAD ^EKOVI]a,b#
aFaculty of Chemistry, University of Belgrade, Studenski trg 16, P.O. Box 158, 11000 Belgrade and
bCentar for Chemistry, Institute of Chemistry, Technology and Metallurgy, Njego{eva 12, 11001 Belgrade,
Serbia and Montenegro
(Received 15 March 2004)
Abstract: A stereoselective free radical introduction of a phenylthio group onto a nonactivated methyl
group in the d-position, adjacent to a prochiral carbon atom, was achieved by photolysis of (-)-menthyl
benzenesulfenate in the presence of hexabutylditin and (1R, 3R, 4S, 8S)-9-phenylthiomenthol (4) was
obtained with 91 % optical purity. High stereoselectivity of the reaction was calculated (ab initio MP2/631G**) to be the consequence of the difference in the transition state eneregies (DDG# = 5.08 kJ/mol)
favouring 4 relative to (1R,3R,4S,8R)-9-phenylthiomenthol (5). The absolute configuration of a the new
chiral carbon atom was confirmed by its correlation with the corresponding menthane-3,9-diol of known
stereochemistry.
Keywords: radical reactions, stereoselective reactions, C-H activation, absolute configurations, ab initio
calculations, menthyl benzenesulfenate, 9-phenylthiomenthol.
REFERENCES
1. a) G. Petrovi}, R. N. Sai~i}, @. ^ekovi}, Tetrahedron Lett. 38 (1997) 710; b) Tetrahedron 59 (2003)
186; c) D. J. Pasto, G. Gottard, Tetrahedron Lett. 35 (1994) 4303
2. a) G. Petrovi}, R. N. Sai~i}, @. ^ekovi}, Synlett. (1999) 635; b) S. Uemura, Comprehensive Organic
Synthesis, B. M. Trost, I. Fleming, Eds., Pergramon Press, Oxford, 1991, Vol. 7, p. 757; c) K. Ogura,
Comprehensive Organic Synthesis, B. M. Trost, I. Fleming, Eds., Pergamon Press, Oxford, 1991, Vol. 1, p.
505; d) M. Kennedy, M. A. McKervey, Comprehensive Organic Synthesis, B. M. Trost, I. Fleming, Eds.,
Pergamon Press, Oxford, 1991, Vol. 7, p. 193
3. a) J. Hartung, F. Gallou, J. Org. Chem. 60 (1995) 6706; b) A. L. J. Beckwith, B. P. Hay, G. M. Williams,
J. Chem. Soc. Chem. Commun (1989) 1202
4. a) G. Petrovi}, @. ^ekovi}, Tetrahedron Lett. 38 (1997) 627; b) Tetrahedron 55 (1999) 1377
5. S. Bogen, M. Gulea, L. Fensterbank, M. Malacria, J. Org. Chem. 64 (1999) 4920
6. Based on the MM2 method, N. L. Allinger, J. Am. Chem. Soc. 99 (1977) 8127
7. a) J. S. Binkley, J. A. Pople, W. J. Hehre, J. Am. Chem. Soc. 102 (1980) 939; b) P. C. Hariharan, J. A.
People, Theor. Chim. Acta 28 (1973) 213
8. a) C. Moller, M. S. Plesset, Phys. Rev. 46 (1934) 616; b) J. A. Pople, J. S. Binkley, R. Seeger, Int. J.
Quant. Chem. S10 (1976) 1
9. A. E. Dorigo, K. N. Houk, J. Am. Chem. Soc. 109 (1987) 2195
10. a) K. H. Schulte-Elite, G. Ohloff, Helv. Chim. Acta 50 (1967) 153; b) C. W. Jefford, Y. Li, Y. Wang,
Org. Synth. Coll. Vol. IX, 1998, p. 462
11. B. M. Trost, T. N. J. Salzmann, K. J. Hiroi, J. Am. Chem. Soc. 98 (1976) 4887
12. a) R. Tanikaga, Y. K. Yabuki, K. Ono, A. Kaji, Tetrahedron Lett. (1976) 2257; b) W. E. Parham, L. D.
Edwards, J. Org. Chem. 33 (1968) 4150
13. a) B. M. Trost, T. N. J. Salzmann, J. Org. Chem. 40 (1975) 148; b) P. A. Grieco, M. Miyashita, J. Org.
Chem. 39 (1974) 120
14. G. Schmidt, W. Hofheinz, J. Am. Chem. Soc. 105 (1983) 624.
J. Serb. Chem. Soc. 69 (10) 749–757 (2004)
UDC 66.092–977+547.915:543.51
JSCS – 3201
Original scientific paper
MS analysis of biindenylidenes
SNE@ANA SINADINOVI]-FI[ER1# and JOVAN JOVANOVI]2
1Faculty of Technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad and 2Faculty of
Technology and Metallurgy, University of Belgrade, P. O. Box 3503, 11120 Belgrade, Serbia and
Montenegro (e-mail: jajovan@drenik.net)
(Received 17 February 2004)
Abstract: Biindenylidene isomers are components of pyrolysis oils. The mass spectra were recorded and the
fragmentation of the following biindenylidene isomers: (E)-2,3,2’,3’-tetrahydro-[1,1’]biindenylidene, (Z)2,3,2’,3’-tetrahydro-[1,1’]biindenylidene, 1,3,1’,3’-tetrahydro-[2,2’]biindenylidene and 2,3,1’,3’tetrahydro-[1,2’]biindenylidene, as well as of spiro[1,1a,6,6a-tetrahydrocyclopropa[a]indene-1,1’-2’,3’dihydro-1’H-indene] is discussed.
Keywords: mass spectrometry, fragmentation, biindenylidenes.
REFERENCES
1. M. Spiteller, J. A. Jovanovi}, Fuel 78 (1999) 1263
2. J. Jovanovi}, M. Spiteller, W. Elling, J. Serb. Chem. Soc. 67 (2002) 393
3. P. Spiteller, J. Jovanovi}, M. Spiteller, Magn. Reson. Chem. 41 (2003) 475
4. J. Jovanovi}, M. Schürmann, H. Preut, M. Spiteller, Acta Cryst. E57 (2001) o1100
5. J. Jovanovi}, W. Elling, M. Schürmann, H. Preut, M. Spiteller, Acta Cryst. E58 (2002) o35
6. J. Jovanovi}, M. Schürmann, H. Preut, M. Spiteller, Acta Cryst. E57 (2001) o1139
7. J. Jovanovi}, W. Elling, M. Schürmann, H. Preut, M. Spiteller, Acta Cryst. E58 (2002) o815
8. J. Jovanovi}, W. Elling, M. Schürmann, H. Preut, M. Spiteller, Acta Cryst. E58 (2002) o67
9. D. Lenoir, P. Lemmen, Chem. Ber. 113 (1980) 3112
10. C. D. Czogalla, F. Boberg, Phosphorus and Sulfur GE 33 (1987) 83
11. F. Bell, J. Spanswick, J. Chem. Soc. (C) (1966) 1887.
J. Serb. Chem. Soc. 69 (10) 759–767 (2004)
UDC 547.313.442:66–948.3:536.74
JSCA – 3202
Original scientific paper
Temperature dependence of the Kovats retention indices for alkyl 1,3-diketones on a DB-5 capillary
column
DU[AN @. MIJIN and DU[AN G. ANTONOVI]#
Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, P. O.
Box 3503, 11120 Belgrade, Serbia and Montenegro (e-mail: kavur@elab.tmf.bg.ac.yu)
(Received 20 January, revised 19 April 2004)
Abstract: A series of alkyl 1,3-diketones were used to study the temperature dependence of the Kovats
retention indices in the temperature range 130–190 ºC (403–463 K). The temperature dependence is
described by the empirical equation I = B + B/T + ClnT. On the basis of this equation, the activation
enthalpy, DH¹, and the chemical potential of the partitioning of one methylene group between the two
phases of the chromatographic system, Dmp(CH2), were calculated. Also, the Kovats retention indices –
boiling point correlations (linear and reciprocal) for alkyl 1,3-diketones were studied and Dmp(CH2) was
calculated.
Keywords: retention indices, alkyl 1,3-diketones, temperature dependence.
REFERENCES
1. A. T. James, A. J. P. Martin, Biochem. J. 50 (1952) 679
2. E. Kovats, Helv. Chim. Acta 41 (1958) 1915
3. E. Tudor, J. Chromatography A 779 (1997) 287
4. K. Heberger, M. Gorgenyi, J. Chromatography A 845 (1999) 21
5. D. @. Mijin, D. G. Antonovi}, B. @. Jovanovi}, J. Serb. Chem. Soc. 68 (2003) 825
6. M. V. Budahegyi, E. R. Lombosi, T. S. Lombosi, S. Y. Meszaros, Sz. Nyiredy, G. Tarjan, I. Timar, J. M.
Takacs, J. Chromatography A 271 (1983) 213
7. G. Tarjan, Sz. Hyiredy, M. Gyor, E. R. Lombosi, T. S. Lombosi, M. V. Budahegyi, S. Y. Meszaros, I.
Timar, J. M. Takacs, J. Chromatography A 421 (1989) 1
8. K. Ciazynska-Halarewicz, E. Borucka, T. Kowalska, Acta Chromatograph. 12 (2002) 65
9. T. Kowalska, K. Heberger, M. Gorgenyi, Acta Chromatograph. 13 (2003) 60
10. K. Ciazynska-Halarewicz, T. Kowalska, Acta Chromatograph. 13 (2003) 69
11. L. Claisen, E. F. Erdhardt, Chem. Ber. 22 (1889) 1009
12. D. @. Mijin, D. G. Antonovi}, M. M. Mi{i}-Vukovi}, Indian J. Chem. Sec. B 33B (1994) 309
13. T. Kowalska, K. Heberger, Chemometr. Intell. Lab. Syst. 47 (1999) 205.
J. Serb. Chem. Soc. 69 (10) 769–775 (2004)
UDC 547.47+547.92:542.913
JSCS – 3203
Preliminary communication
PRELIMINARY COMMUNICATION
Synthesis of a steroidal dendrimer core
TATJANA KOP1, GABRIELLA POCSFALVI2 and BOGDAN A. [OLAJA1#
1Faculty of Chemistry, University of Belgrade, P. O. Box 158, 11001 Belgrade, Serbia and Montenegro (Email: bsolaja@chem.bg.ac.yu) and 2Istituto di Scienze dell’Alimentazione, Consiglio Nazionale delle
Ricerche, Avellino, Italy
(Received 26 February 2004)
Abstract: Synthesis of a steroidal dendrimer core possessing various functional termini, such as ester,
carboxy and hydroxy, is presented. The approach described enables further simple manipulations for the
introduction of more complex functionalities.
Keywords: deoxycholic acid, trimesoyl trichloride, core, dendrimer.
REFERENCES
1. G. R. Newkome, C. N. Moorefield, F. Vogtle, Dendritic Molecules: Concepts, Syntheses and
Perspectives; VCH: Weinheim, 1996
2. T. Nagasaki, O. Kimura, M. Ukon, I. Hamachi, S. Shinkai, S. Arimori, J. Chem. Soc. Perkin Trans. 1
(1994) 75
3. J. Barbera, B. Donnio, R. Gimenez, D. Guillon, M. Marcos, A. Omenat, J. L. Serrano, J. Mater. Chem.
11 (2001) 2808
4. W. Devonport, M. R. Bryce, G. J. Marshallsay, A. J. Moore, L. M. Goldenberg, J. Mater. Chem. 8
(1998) 1361
5. G. R. Newkome, V. V. Narayanan, L. A. Godinez, J. Org. Chem. 65 (2000) 1643
6. S. Sengupta, S. K. Sadhukhan, Tetrahedron Lett. 42 (2001) 3659
7. K. L. Wooley, C. Hawker, J. M. J. Fréchet, F. Wudl, G. Srdanov, S. Shi,C. Li, M. Kao, J. Am. Chem.
Soc. 115 (1993) 9836
8. G. R. Newkome, E. F. He, C. N. Moorefield, Chem. Rev. 99 (1999) 1689
9. S. Hecht, J. M. J. Fréchet, Angew. Chem. Int. Ed. Engl. 40 (2001) 74
10. a) N. Todorovi}, M. Stefanovi}, B. Tinant, J.–P. Declercq, M. Makler, B. [olaja, Steroids 61 (1996)
688. b) D. Opsenica, G. Pocsfalvi, Z. Jurani}, B. Tinant, J.–P. Declercq, D. E. Kyle, W. K. Milhous, B. A.
[olaja, J. Med. Chem. 43 (2000) 3274. c) B. A. [olaja, N. Terzi}, G. Pocsfalvi, L. Gerena, B. Tinant, D.
Opsenica, W. K. Milhous, J. Med. Chem. 45 (2002) 3331. d) D. Opsenica, D. E. Kyle, W. K. Milhous, B.
A. [olaja, J. Serb. Chem. Soc. 68 (2003) 291. e) D. Opsenica, G. Angelovski, G. Poscfalvi, Z. Jurani}, @.
@i`ak, D. Kyle, W. K. Milhous, B. A. [olaja, Bioorganic & Medicinal Chemistry 11 (2003) 2761
11. a) S. R. Meschnick, Artemisinin and Its Derivatives, in Antimalarial Chemotherapy, P. J. Rosenthal,
Ed., Humana Press Inc., N. J., 2001, p. 19. b) For recent development in this field see: U. Ecksteln-Ludwig,
R. J. Webb, I. D. A van Goethem, J. M. East, A. G. Lee, M. Kimura, P. N. O’Neill, P. G. Bray, S. A. Ward,
S. Krishna, Nature 424 (2003) 957
12. Trimesoyl-trichloride was synthesized according to Bennet and Wain, J. Chem. Soc. (1936) 111
13. Methyl deoxycholate (2) was prepared by refluxing either sodium deoxycholate or deoxycholic acid
with HCl/MeOH. 12a-Monoacetate 3 was prepared from the corresponding 3a,12a-diacetate according to
ref. 10b
14. S. Kohmoto, D. Fukui, T. Nagashima, K. Kishikawa, M. Yamamoto, K. Yamada, Chem. Commun.
(1996) 1869
15. M. Node, K. Nishide, M. Sai, E. Fujita, Tetrahedron Lett. 52 (1978) 5211, M. Node, K. Nishide, M.
Sai, K. Fuji, E. Fujita, J. Org. Chem. 46 (1981) 1991
16. Benzyl ester was synthesized from sodium deoxycholate using benzyl alcohol in the presence of DMF.
12a-Monobenzoate 8 was prepared directly in a TMSOTf catalyzed acylation reaction using mixed
anhydride prepared according to the procedure of J. A. Price, D. S. Tarbell, Org. Synthesis Coll. Vol. IV,
285
17. M. K. Anwer, A. F. Spatola, Synthesis (1980) 929
18. A. G. Anderson, R. G. Anderson, T. S. Fujita, J. Org. Chem. 27 (1962) 4535.
J. Serb. Chem. Soc. 69 (10) 777–782 (2004)
UDC 54–724+537.872:519.17:54–12
JSCS – 3204
Original scientific paper
Dependence of the total p-electron energy on a large number of non-bonding molecular orbitals
IVAN GUTMANa#, DRAGAN STEVANOVI]b, SLAVKO RADENKOVI]a, SVETLANA
MILOSAVLJEVI]a and NATA[A CMILJANOVI]a
aFaculty of Science, University of Kragujevac, P. O. Box 60, 34000 Kragujevac (e-mail:
gutman@kg.ac.yu) and bDepartment of Mathematics, Faculty of Science, University of Ni{, Vi{egradska
33, 18000 Ni{, Serbia and Montenegro
(Received 8 March 2004)
Abstract: Using a recently developed method for computing the effect of non-bonding molecular orbitals
(NBMOs) on the total p-electron energy (E), it was found that the dependence of E on the number n0 of
NBMOs is almost perfectly linear. We now show that this regularity remains valid for very large values of
n0, in particular, to hold up to n0 = 20.
Keywords: total p-electron energy, non-bonding molecular orbitals, chemical graph theory.
REFERENCES
1. A. Graovac, I. Gutman, N. Tinajsti}, Topological Approach to the Chemistry of Conjugated Molecules,
Springer-Verlag, Berlin, 1977
2. C. A. Coulson, B. O’Leary, R.B. Mallion, Hückel Theory for Organic Chemists, Academic Press,
London, 1978
3. I. Gutman, O. E. Polansky, Mathematical Concepts in Organic Chemistry, Springer-Verlag, Berlin, 1986
4. I. Gutman, Uvod u hemijsku teoriju grafova; PMF Kragujevac, Kragujevac, 2003 (in Serbian)
5. I. Gutman, J. Serb. Chem. Soc. 43 (1978) 761
6. I. Gutman, Topics Curr. Chem. 162 (1992) 29
7. I. Gutman, D. Vidovi}, H. Hosoya, Bull. Chem. Soc. Japan 75 (2002) 1723
8. I. Gutman, N. Cmiljanovi}, S. Milosavljevi}, S. Radenkovi}, Chem. Phys. Lett. 383 (2004) 171
9. I. Gutman, N. Cmiljanovi}, S. Milosavljevi}, S. Radenkovi}, Monatsh. Chem. 135 (2004) 765
10. V. Brankov, D. Stevanovi}, I. Gutman, J. Serb. Chem. Soc. 69 (2004) 549
11. I. Gutman, B. Ru{~i}, N. Tinajsti}, C. F. Wilcox, J. Chem. Phys. 62 (1975) 3399
12. I. Gutman, Z. Phys. Chem. (Leipzig) 266 (1985) 59
13. M. D. Watson, A. Fechtenkötter, K. Müllen, Chem. Rev. 101 (2001) 1267.
J. Serb. Chem. Soc. 69 (10) 783–790 (2004)
UDC 546.65+546.73+547.477:66.094.3
JSCS – 3205
Original scientific paper
Oxidative performance and surface properties of
Co-containing mixed oxides having the K2NiF4 structure
LAITAO LUO, HUA ZHONG and XIAOMAO YANG
Institute of Applied Chemistry, Nanchang University, Nanchang, Jiangxi, 330047, P. R. China
(e-mail: Luolaitao@163.com.cn)
(Received 9 December 2003, revised 2 April 2004)
Abstract: The complexed oxides Nd2–xSrxCoO4 (0.4 £ x £ 1.2) and LnSrCoO4 (Ln = Pr, Nd, Eu) having
the K2NiF4 structure were synthesized by the citric-acid-complexion method. The results of XRD
confirmed that the complexed oxides have the K2NiF4 structure. Other phases were found when x = 0.4
and x = 1.2. The influences of Nd, Pr, Eu on the activities of LnSrCoO4 for CO oxidation and C3H8
oxidation were different. The oxidative activities, average crystalline size and lattice distortion of Nd2–
xSrxCoO4 increased with increasing x value in the oxides. When x > 0.8, the lattice distortion decreased
with increasing x. The results of O2–TPD showed that amount of desorption of lattice oxygen over Nd2–
xSrxCoO4 increased with x, however, the amount of chemidesorption of oxygen decreased. With
increasing x, the high-temperature reduction peak in H2–TPR of Nd2–xSrxCoO4 shifted to higher
temperatures, however, the low-temperature reduction peak shifted to lower temperatures, which showed
that the activity of the lattice oxygen and the thermal stability of Nd2–xSrxCoO4 increased with increasing
x.
Keywords: rare earths, Co-based mixed oxides, perovskite-like, oxidation.
REFERENCES
1. Y. N. Armor, Appl. Catal. B: Environmental 2 (1992) 256
2. N. Guihaume, S. D. Peter, M. Primet, Appl. Catal. B: Emvironmental
10 (1996) 325
3. T. Y. Arakawa, S. I. Tsuchl, Shiolawa, J. Catal 74 (1982) 318
4. Y. G. Gangnl, J. Solid State Chem. 30 (1979) 358
5. Z. Zhao, X. Yang, Y. Wu, Science China (Series B) 40 (1997) 464
6. D. Ganguli, J. Solid State Chem. 30 (1979) 353
7. A. K. Ladavos, P. J. Pomonis, Appl. Catal. A: General 165 (1997) 73
8. H. Lou, H. Zhen, J. Yang, Z. Yao, X. Yu, W. Du, F Ma, J. Chin. Rare Earth Soc. 16 (1995) 107
9. Z. Zhao, X. Yang, Y. Liu, Y. Wu, J. Science China 41 (1996) 149
10. G. Shang, X. Ge, H. Zhang, J. Wuli, Huaxue Xubao 15 (1999) 568
11. L. Gao, B. Dong, Q. Li, X. Lv, Z. Yu, Y. Wu, J. Fuel. Chim. Soc. 22 (1994) 115
12. K. C. C. Kharas, J. H. Lunsford, J. Am. Chem. Soc. 111 (1989) 2334
13. S. George, B. Viswanathan, J. Colloid Chem. Sci. 95 (1983) 322
14. R. J. Voorhoeve, Advanced Materials in Catalysis, Academic Press, New York, 1977, p. 132.
J. Serb. Chem. Soc. 69 (10) 791–805 (2004)
UDC 546.56+541.123.21:537.311.6:543.42
JSCS – 3206
Original scientific paper
An impedance investigation of corrosion protection of copper by self-assembled monolayers of
alkanethiols in aqueous
solution
GUIYAN LI1, HOUYI MA1, YONGLI JIAO1 and SHENHAO CHEN1,2,
1Department of Chemistry, Shandong University, Jinan, 250100, P. R. China and 2State Key Laboratory
for Corrosion and Protection of Metals, Shenyang, 110015, P. R. China (e-mail: shchen@sdu.edu.cn)
(Received 18 August 2003, revised 1 March 2004)
Abstract: Self-assembled monolayers (SAMs) of three n-alkanethiols, 1-octadecanethiol (C18SH), 1dodecanethiol (C12SH), and 1-hexanethiol (C6SH), were formed on fresh, oxide-free copper surfaces
obtained by HNO3 etching. The corrosion protection abilities of the three alkanethiol SAMs were evaluated
in 0.2 mol cm-3 NaCl, 0.2 mol cm-3 HCl and 0.2 mol dm–3 H2SO4 solutions using the electrochemical
impedance spectroscopy (EIS) method. The SAMs act as a hydrophobic barrier layer, which effectively
prevents the copper substrate from contacting corrosive ions, thereby inhibiting corrosion of the copper to a
considerable degree. A general equivalent circuit for the SAM-covered electrodes was proposed, by means
of which the impedance behavior of the electrodes was interpreted and the corresponding electrochemical
parameters were acquired. In addition, the quality of the SAMs and development of defects in the SAMs
were also been evaluated based on the equivalent circuit. The dependence of the capacitance of the SAMs
on the applied potentials was used to determine the stability of the SAMs at the applied potentials.
Keywords: electrochemical impedance spectroscopy (EIS), self-assembled monolayers (SAMs),
alkanethiol, corrosion protection, equivalent circuit.
REFERENCES
1. C. Miller, P. Cuendet, M. Grätzel, J. Phys. Chem. 95 (1991) 877
2. P. E. Laibinis, G. M. Whitesides, J. Am. Chem. Soc. 114 (1992) 9022
3. F. P. Zamborini, R. M. Crooks, Langmuir 14 (1998) 3279
4. G. K. Jennings, J. C. Munro, T. –H. Yong, P. E. Laibinis, Langmuir 14 (1998) 6130
5. J. Scherer, M. R. Vogt, O. M. Magnussen, R. J. Behm, Langmuir 13 (1997) 7045
6. Y. Feng, W. –K. Teo, K. –S. Siow, Z. Gao, K.-L. Tan, A.-K. Hsieh, J. Electrochem. Soc. 144 (1997) 55
7. M. Itoh, H. Nishihara, K. Aramaki, J. Electrochem. Soc. 142 (1995) 1839
8. M. Itoh, H. Nishihara, K. Aramaki, J. Electrochem. Soc. 142 (1995) 3696
9. O. E. Barcia, O. R. Matoos, Electrochim. Acta 35 (1990) 1601
10. O. E. Barcia, O. R. Matoos, N. Pebere, B. Tribollet, J. Electrochem. Soc. 140 (1993) 2825
11. E. Boubour, R. B. Lennox, Langmuir 16 (2000) 7464
12. T. M. Nahir, E. F. Bowden, Electrochim. Acta 39 (1994) 2347
13. L. Sun, R. M. Crooks, Langmuir 9 (1993) 1951
14. O. Chailapakul, L. Sun, C. Xu, R. M. Crooks, J. Am. Chem. Soc. 115 (1993) 12459
15. X.-M. Zhao, J. L. Wilbur, G. M. Whitesides, Langmuir 12 (1996) 3257
16. E. Boubour, R. B. Lennox, J. Phys. Chem. B 104 (2000) 9004
17. X. Wu. H. Ma. S. Chen, Z. Xu, A. Su, J. Electrochem. Soc. 146 (1999) 1847
18. H. Ma, S. Chen, X. Cheng, X. Chen, G. Li, X. Yang, J. Serb. Chem. Soc. 62 (1997) 1201
19. E. Mccafferty, Corros. Sci. 39 (1997) 243
20. M. Touzet, M. Cid, M. Puiggali, M. C. Petit, Corros. Sci. 34 (1993) 1187
21. J. R. Park, D. D. Macdonald, Corros. Sci. 23 (1985) 295
22. U. Rammelt, G. Reinhard, K. Rammelt, J. Electroanal. Chem. 180 (1984) 327
23. D. D. Macdonald, M. C. H. Mckubre, in Modern Aspects of Electrochemistry, Vol. 14, J. O’M.
Bockris, B. E. Conway, R. E. White, Eds., Plenum Press, New York, 1982, p. 61
24. F. Deflorian, L. Fedrizzi, A. Locaspi, P. L. Bonora, Electrochim. Acta 38 (1993) 1945
25. R. P. Janek, W. R. Fawcett, J. Phys. Chem. B 101 (1997) 8550
26. R. P. Janek, W. R. Fawcett, Langmuir 14 (1998) 3011
27. H. Ma. X. Cheng, G. Li, S. Chen, Z. Quan, S. Zhao, L. Niu, Corros. Sci. 42 (2000) 1669
28. P. W. Atkins, Physical Chemistry, 4th ed., W. H. Freeman and Company, New York, 1990, p. 649
29. J. A. Dean, Lange’s Handbook of Chemistry, 14th ed., McGraw-Hill, New York, 1992, p. 1235
30. H. Y. Ma, C. Yang, B. S. Yin, G. Y. Li, S. H. Chen, J. L. Luo, Appl. Surf. Sci. 218 (2003) 143.
J. Serb. Chem. Soc. 69 (10) 807–815 (2004)
UDC 546.72–034.5:621.357:620.123
JSCS – 3207
Original scientific paper
Electrochemical deposition and characterization of
Zn–Fe alloys
JELENA B. BAJAT1,, VESNA B. MI[KOVI]-STANKOVI]1,#, MIODRAG D. MAKSIMOVI]1,
DAGUTIN M. DRA@I]2,# and SLAVICA ZEC3
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P.O. Box 3503, 11120
Belgrade, 2ICTM – IEC, P.O.Box 815, 11001 Belgrade and 3Vin~a Institute of Nuclear Sciences, P.O.
Box 522, 11001 Belgrade, Serbia and Montenegro (e-mail: vesna@tmf.bg.ac.yu)
(Received 7 May 2004)
Abstract: Zn–Fe alloy electrochemically deposited on steel under various deposition conditions were
investigated using anodic linear sweep voltammetry (ALSV) and X-ray diffraction (XRD) analysis for
phase structure determination, energy dispersive X-ray (EDX) analysis for determination of chemical
composition, and polarization measurements and open circuit potential measurements for determination of
corrosion properties. The influence of deposition current density on the chemical composition, phase
structure and corrosion stability of Zn–Fe alloys was studied. It was shown that deposition current density
strongly affects the corrosion stability of Zn–Fe alloys, while Zn–Fe alloy electrodeposited at 4 A dm-2
exhibited the lowest corrosion rate.
Keywords: electrodeposition, Zn–Fe alloy, corrosion, surface modification.
REFERENCES
1. R. Fratesi, G. Lunazzi, G. Roventi, in Organic and Inorganic Coatings for Corrosion Prevention Vol. 20,
L. Fedrizzi, P. L. Bonora, Eds., The Institute of Materials, London, 1997, p. 130
2. S. R. Rajagopalan, Met. Finish. 70 (1972) 52
3. M. Pushpavanam, S. R. Natarajan, K. Balakrishnan, L. R. Sharma, J. Appl. Electrochem. 21 (1991) 642
4. M. A. Pech-Canul, R. Ramanauskas, L. Maldonado, Electrochim. Acta 42 (1997) 255
5. W. Kautek, M. Sahre, W. Paatsch, Electrochim. Acta 39 (1994) 1151
6. Z. Zhang, W. H. Leng, H. B. Shao, J. Q. Zhang, J. M. Wang, C. N. Cao, J. Electroanal. Chem. 516
(2001) 127
7. V. Narasimhamurthy, B. S. Sheshadri, J. Appl. Electrochem. 26 (1996) 90
8. H. Park, J. A. Szpunar, Corros. Sci. 40 (1998) 525
9. S. K. Ze~evi}, J. B. Zotovi}, S. Lj. Gojkovi}, V. Radmilovi}, J. Electroanal. Chem. 448 (1998) 245
10. V. D. Jovi}, A. R. Despi}, J. Stevanovi}, S. Spai}, Electrochim. Acta 34 (1989) 1093
11. Metals Handbook, Vol. 8. Metallography, Structures and Phase Diagrams, American Society for
Metals, Ohio, 1973
12. Powder Diffraction File, Inorganic Volume PD/S 5iRB, Sets 1-5, American Society for Testing and
Materials, Philadelphia, PA, 1969
13. K. Kondo, T. Murakami, K. Shinohara, J. Electrochem. Soc. 143 (1996) L75
14. S. Swathirajan, J, Electrochem. Soc. 133 (1986) 671
15. J. B. Bajat, V. B. Mi{kovi}-Stankovi}, Z. Ka~arevi}-Popovi}, Prog. Org. Coat. 47 (2003) 49
16. M. R. Lambert, R. G. Hart, H. E. Townsend, SAE Tech. Pap. Series No 831817, Detroit, MI, 1983, p.
81
17. T. E. Graedel, J. Electrochem. Soc. 136 (1989) 193C
18. V. B. Mi{kovi}-Stankovi}, J. B. Zotovi}, Z. Ka~arevi}-Popovi}, M. D. Maksimovi}, Electrochim.
Acta 44 (1999) 4269
19. J. B. Bajat, Z. Ka~arevi}-Popovi}, V. B. Mi{kovi}-Stankovi}, M. D. Maksimovi}, Prog. Org. Coat. 39
(2000) 127
20. J. B. Bajat, V. B. Mi{kovi}-Stankovi}, M. D. Maksimovi}, D. M. Dra`i}, S. Zec, Electrochim. Acta 47
(2002) 4101
21. J. B. Bajat, V. B. Mi{kovi}-Stankovi}, Z. Ka~arevi}-Popovi}, Prog. Org. Coat. 45 (2002) 379.
J. Serb. Chem. Soc. 69 (10) 817–825 (2004)
UDC 54–72.006.57:541.135.2:62–492.2–034.3
JSCS – 3208
Original Scientific paper
The effect of the particle shape and structure on the flowability of electrolytic copper powder. IV. The
internal structure of the powder particles
KONSTANTIN I. POPOV1,, SNE@ANA B. KRSTI]1, MIOMIR G. PAVLOVI]2,#, LJUBICA J.
PAVLOVI]2,# and VESNA M. MAKSIMOVI]3
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade,
2ICTM – Department of Electrochemistry, Njego{eva 12, 11000 Belgrade and 3Vin~a Institute of Nuclear
Sciences, P. O. Box 522, 11000 Belgrade, Serbia and Montenegro (e-mail: kosta@elab.tmf.bg.ac.yu)
(Received 26 January 2004)
Abstract: The structure of powder particles was analysed by considering their cross sections. It was shown
that the structure of powder particles of nonsieved flowing powders is sufficiently dense to produce a
continuous surface, which does not allow the particles to jam and hence permits the free flow of nonsieved
powder. It was also shown that the representative powder particle, the elementary cell of which can be
presented by a 3D-cross, describes the properties of the powder relative to its flowability well.
Keywords: copper powder flowability, nonsieved flowing powder, cross section of powder particles.
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. K. I. Popov, S. B. Krsti}, M. ^. Obradovi}, M. G. Pavlovi}, Lj. J. Pavlovi}, E. R. Ivanovi}, J. Serb.
Chem. Soc. 69 (2004) No 1
5. M. G. Pavlovi}, Lj. J. Pavlovi}, E. R. Ivanovi}, V. Radmilovi}, K. I. Popov, J. Serb. Chem. Soc. 66
(2001) 923
6. E. Peisseker, Intern. J. Powder Metallurgy and Powder Technology 20 (1984) 27
7. K. I. Popov, N. D. Nikoli}, Z. Rako~evi}, J. Serb. Chem. Soc. 67 (2002) 861
8. K. I. Popov, E. R. Stoiljkovi}, V. Radmilovi}, M. G. Pavlovi}, Powder Technology 93 (1997) 55
9. K. I. Popov, P. @ivkovi}, S. B. Krsti}, J. Serb. Chem. Soc. 68 (2003) 903.
J. Serb. Chem. Soc. 69 (10) 827–837 (2004)
UDC 547.261+542.913:66.012.3
JSCS – 3209
Original scientific paper
Energy and economy savings in the process of methanol
synthesis using Pinch technology
MIRJANA KIJEV^ANIN1, BOJAN DJORDJEVI]1,#, OZREN OCI]2, MLADEN CRNOMARKOVI]1,
MAJA MARI]1 and SLOBODAN [ERBANOVI]1,#
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P. O. Box 35-03, 11000
Belgrade (e-mail: mirjana@tmf.bg.ac.yu) and 2Pan~evo Petroleum Refinery, Spoljnostar~eva~ka b.b.,
26000 Pan~evo, Serbia and Montenegro
(Received 21 October 2003, revised 6 April 2004)
Abstract: A heat exchanger network (HEN) for the process of methanol synthesis has been studied by pinch
design analysis. Great economic and energy savings were realized by the pinch analysis in comparison to
the existing plant. Also, it was found that it is possible to reduce the requirements for the consumption of
utilities. The HEN was reconstruded by adding new heat exchangers. In order to produce new HEN, the
capital costs had to be increased, but the total cost trade-off between the capital and energy costs will be
decrease by 30 %.
Keywords: energy recovery, pinch technology, HEN design, plant for methanol synthesis.
REFERENCES
1. I. E. Grossmann, M. M. Daichendt, Comput. Chem. Eng. 20 (1996) 665
2. T. Gundersen, L. Naess, Comput. Chem. Eng. 12 (1988) 503
3. J. Je`owski, Hung. J. Ind. Chem. 22 (1994) 279
4. J. Je`owski, Hung. J. Ind. Chem. 22 (1994) 295
5. B. Linnhoff, Chem. Eng. Res. Des. 71 (1993) 503
6. R. Smith, Appl. Therm. Eng. 20 (2000) 1337
7. F. X. X. Zhu, L. Vaideeswaran, Appl. Therm. Eng. 20 (2000) 1381
8. K. C. Furman, N. V. Sahinidis, Ind. Eng. Chem. Res. 41 (2002) 2335
9. L. Matija{evi}, H. Otma~i}, Appl. Thermal Eng. 22 (2002) 477
10. J. Klemes, Y. T. Kostenko, L. L. Tovazhnyanskii, P. A. Kapustenko, L. M. Ulev, A. Y. Perevertailenko,
B. D. Zulin, Theor. Found. Chem. Eng. 33 (1999) 379
11. H. M. Lababidi, I. M. Alatiqi, L. J. Nayfeh, Appl. Therm. Eng. 20 (2000) 1495
12. B. Linnhoff, W. D. Witherell, Oil Gas J. (1986) 54
13. C. Bengtsson, R. Nordman, T. Berntsson, Appl. Therm. Eng. 22 (2002) 1069
14. M. A. Phipps, A. F. A. Hoadley, Korean J. Chem. Eng. 20 (2003) 642
15. B. A. Al-Riyami, J. Klemes, S. Perry, Appl. Thermal Eng. 21 (2001) 1449
16. M. De Monte, E. Padoano, D. Pozzetto, Appl. Thermal Eng. 23 (2003) 1033
17. B. Linnhoff, D. W. Townsend, D. Boland, G. F. Hewitt, B. E. A. Thomas, A. R. Guy, R. H. Marsland,
User Guide on Process Integration for the Efficient Use of Energy, IChemE, UK, 1994
18. F. Mato, A. Martin, personal communications, 2003
19. Linnhoff-March, A Guide to Pinch Technology. Introduction to Pinch Technology, Linnhoff-March
UK, 1998
20. R. Smith, Chemical Process Design, McGraw – Hill, New Yor, 1995
21. B. Linnhoff, S. Ahmad, Comp. Chem. Eng. 14 (1990) 729
22. S. Ahmad, B. Linnhoff, R. Smith, Comp. Chem. Eng. 14 (1990) 751
23. K. K. Trivedi, B. K. O’Neill, J. R. Roach, Comput. Chem. Eng. 13 (1989) 291
24. J. Je`owski, Comput. Chem. Eng. 16 (1992) 129
25. H. P. Lee, I. Y. Lee, K. O. Yoo, Korean J. Chem. Eng. 12 (1995) 589.