YU-ISSN 0352-5139
J.Serb.Chem.Soc. Vol 68, No 2(2003)
CONTENTS
Organic Chemistry
N. V. Valenti}, @. Vitnik, S. I. Kozhushkov, A. De Majere, G. S. U{}umli} and I. O. Jurani}: Effect of
substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1,4-pentadienes. Part I.
67
V. Leskovac, S. Trivi} and D. Peri~in: Isomerization of an enzyme-coenzyme complex in yeast alcohol
dehydrogenase-catalysed reactions
77
Inorganic Chemistry
L. Larabi, Y. Harek, A Reguig and M. M. Mostafa: Cynthesis, structural study and electrochemical
properties of copper(II) complexes derived from benzene- and p-poluenesulphonylhydrazone
85
Physical Chemistry
P. I. Premovi}: Thermochemical equilibrium calculations of high-temperature O2 generation on the early
Earth: Giant asteroid impact on land
97
M. Ra{kovi}, I. Holclajtner-Antunovi}, M. Tripkovi} and D. Markovi}: Excitation and analytical
characteristics of an ethanol loaded U-shaped arc
109
Electrochemistry
B. Blizanac, S. Mentus, N. Cvjeti}anin and N. Pavlovi}: Temperature effect on graphite KS44 lithiation in
ethylene carbonate + propylene carbonate solution: galvanostatic and impedance study
119
Anaytical Chemistry
A. I. Igov, R. M. Simonovi} and R. P. Igov: Kinetic determination of ultramicro amounts of As(III) in
solution
131
Chemical Engineering
M. Ili}, B. Grubor and V. Manovi}: Sulfur retention by ash during coal combustion. Part I. A model of char
particle combustion
137
J.Serb.Chem.Soc. 68(2)67–76(2003)
UDC 547.41+547.51:66.091.6
JSCS – 3022
Original scientific paper
Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1,4-pentadienes. Part
I.
NATA[A V. VALENTI],1 @ELJKO VITNIK,2# SERGEI I. KOZHUSHKOV,3 ARMIN DE MEIJERE,3
GORDANA S. U[]UMLI]1# and IVAN O. JURANI]2#
1Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P. O. Box 3503, YU11120 Belgrade, Yugoslavia, E-mail: naca@elab.tmf.bg.ac.yu, 2Faculty of Chemistry, University of
Belgrade, Studentski trg 12-16, P. O. Box 158, YU-11001 Belgrade, Yugoslavia, E-mail:
zvitnik@helix.chem.bg.ac.yu or ijuranic@helix.chem.bg.ac.yu, and 3Institut für Organische Chemie der
Georg-August-Universität Göttingen, Tammannstrasse 2, D-37077 Göttingen, Germany, Fax: ++49 551
399475; E-mail: skozhus@gwdg.de or Armin.deMeijere@chemie.uni-goettingen.de
(Received 17 September 2002)
Abstract: The principles of linear free energy relationships were applied to the 13C substituent chemical
shifts (SCS) of the carbon atoms in the unsaturated chain of 3-methylene-4-substituted-1,4-pentadienes.
Correlations of the SCS with the substituent parameters of Swain and Lupton provide a mutually consistent
picture of the electronic effects in these compounds. The pattern of the electronic effects can be fully
rationalized by a model based on the direct transmission of substituent effects through-space (direct
through-space field effects), and via conjugative interactions (resonance effects), or by substituent-induced
polarization of the p-system in the unsaturated chain (p-polarization effect). Semi-empirical MNDO-PM3
calculations suggest the s-cis conformation of 3-methylene-4-substituted-1,4- -pentadienes as the one with
minimal heat of formation.
Keywords: [3]dendralenes, unsaturated chain carbon 13C SCS, substituent effects, reverse 13C SCS effect,
MNDO-PM3 calculations.
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J.Serb.Chem.Soc. 68(2)77–84(2003)
UDC 577.152:663.12:66.095.21.092
JSCS – 3023
Original scientific paper
Isomerization of an enzyme-coenzyme complex in yeast alcohol dehydrogenase-catalyzed reactions
VLADIMIR LESKOVAC1, SVETLANA TRIVI]2 and DRAGINJA PERI^IN1#
1Faculty of Technology Novi Sad and 2Faculty of Science Novi Sad, Yugoslavia
(Received 5 August, revised 8 November 2002)
Abstract: In this work, all the rate constants in the kinetic mechanism of the yeast alcohol dehydrogenasecatalyzed oxidation of ethanol by NAD+, at pH 7.0, 25 ºC, have been estimated. The determination of the
individual rate constants was achieved by fitting the reaction progress curves to the experimental data,
using the procedures of the FITSIM and KINSIM software package of Carl Frieden. This work is the first
report in the literature showing the internal equilibrium constants for the isomerization of the enzymeNAD+ complex in yeast alcohol dehydrogenase-catalyzed reactions.
Keywords: yeast alcohol dehydrogenase, kinetic mechanism of action.
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J.Serb.Chem.Soc. 68(2)85–95(2003)
UDC 542.913+54.02+541.13.004.12:546.56
JSCS – 3024
Original scientific paper
Synthesis, structural study and electrochemical properties of copper(II) complexes derived from benzeneand p-toluenesulphonylhydrazones
L. LARABIa, Y. HAREKa, A. REGUIGa and M. M. MOSTAFAb
aChemistry Department, Faculty of Science, Tlemcen University, Tlemcen, Algeria and bChemistry
Department, Faculty of Science, Mansoura University, Mansoura, Egypt
(Received 12 February, revised 9 September 2002)
Abstract: The synthesis and characterization of benzene- and p-toluenesulphonylhydrazones derived from
salicylaldehyde and 2-hydroxy-1-naphthaldehyde and their Cu(II) complexes are reported. The compounds
were characterized on the basis of elemental analyses, electronic and IR spectra, magnetic moments, and
conductance measurements. The electrochemical behavior of the Cu(II) complexes was investigated in
DMSO by cyclic voltammetry (CV), rotating disc electrode (RDE) and coulometry. The oxidative
polymerization of the copper complexes on a glassy carbon electrode was carried out in DMSO.
Keywords: sulphonylhydrazone-Cu(II) complex, cyclic voltammetry.
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J.Serb.Chem.Soc. 68(2)97–107(2003)
UDC 550.348+523.44:551.510+541.11
JSCS – 3025
Original scientific paper
Thermochemical equilibrium calculations of high-temperature O2 generation on the early Earth:
Giant asteroid impacts on land
PAVLE I. PREMOVI]
Laboratory for Geochemistry, Cosmochemistry and Astrochemistry, University of Ni{, P. O. Box 91, YU18000 Ni{, Serbia, Yugoslavia
(Received 29 October, revised 17 November 2002)
Abstract: Earth’s atmosphere is composed primarily of N2 and O2. The origin of free O2 in the early
Earth’s atmosphere is still subject of considerable debate.1 Theoretical models suggest that the initial form
of free O2 in the atmosphere has been oceanic H2O. Recent computation modelling has suggested that a
superheated (ca. 2000 K) H2O vapor atmosphere of 1.4´1021 kg (the present mass of the oceans) lasting for
about 3000 y could probably have been formed on Earth by an enormous (ca. 1028 J) asteroid impact. In
this report, the occurrence of the thermochemical dissociation of the vapor, creating a primitive oxygenic
(ca. 0.1 of the present level (PAL) of free O2) atmosphere.
Keywords: oxygen, atmosphere, thermochemistry, photochemistry, Earth, asteroid, impact.
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J.Serb.Chem.Soc. 68(2)109–118(2003)
UDC 547.262:543.004.12:66.088
JSCS – 3026
Original scientific paper
Excitation and analytical characteristics of an ethanol loaded U-shaped arc
MARIJA RA[KOVI]1, IVANKA HOLCLAJTNER-ANTUNOVI]1,, MIRJANA TRIPKOVI]2 and
DRAGAN MARKOVI]2,#
1Faculty of Physical Chemistry, University of Belgrade, P. O. Box 137, YU-11001 Belgrade and 2Institute
of Physics, P. O. Box 57, 11001 Belgrade, Yugoslavia
(Received 26 June 2002)
Abstract: The effect of the ethanol load on the discharge and analytical parameters of an argon stabilised Ushaped DC arc has been recorded. Measurements of the radial distribution of the apparent temperatures and
the electron number density of the DC plasma showed that ethanol addition causes a decrease in both
plasma parameters. The changes in the plasma characteristics, as well as in transport and atomisation
processes of the analyte cause a general change in the spectral line intensities, which depends on the
physical characteristics of the analyte and the quantity of ethanol loaded into the plasma. Improved
detection limits were obtained for V and Mn when a 10 % (v/v) water–ethanol solution was nebulized into
the plasma.
Keywords: U-shaped DC arc, emission spectroscopy, ethanol addition, radial temperature distribution,
electron number density distribution, equilibrium plasma composition, detection limits.
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J.Serb.Chem.Soc. 68(2)119–130(2003)
UDC 546.26–162+547.313.2/.3+661.834:541.135
JSCS – 3027
Original scientific paper
Temperature effect on graphite KS44 lithiation in ethylene carbonate + propylene carbonate solution:
galvanostatic and impedance study
B. BLIZANAC1, S. MENTUS1, N. CVIJETI]ANIN1 and N. PAVLOVI]2
1Faculty for Physical Chemistry, Studentski trg 12–16, Belgrade and 2The Military Technical Institute of
the Yugoslav Army, Katani}eva 15, Belgrade, Yugoslavia
(Received 18 August, revised 23 October 2002)
Abstract: Graphite Lonza KS44 in a solution 1 M LiClO4 in a propoylene carbonate + ethylene carbonate
(1 M:1 M) mixture was lithiated and delithiated galvanostatically at room temperature and at the elevated
temperature of 55 ºC. Voltage–time profiles and complex impedance diagrams were recorded and are
discussed for this particular system. It was confirmed that this type of graphite shows a relatively small
current loss consumed by exfoliation, if lithiated at room temperature. However, the voltage–time curve of
the first charging at 55 ºC shows a long voltage plateau at 0.7 V vs. Li/Li+, which corresponds to 540 mAh
g-1 of irreversible capacity attributed to exfoliation. The solid electrolyte layer formed at elevated
temperature, although less protecting in the sense of electrolyte reduction, shows a remarkably higher
electrical resistance than that formed at room temperature. A comparison of the impedance diagrams of
lithiated and delithiated samples allows the conclusion that mass transfer through the graphite, not that
through the solid electrolyte layer, plays a dominant role in the mass transfer limitations.
Keywords: graphite, lithiation, reversible capacity, galvanostatic charging, solid electrolyte layer.
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J.Serb.Chem.Soc. 68(2)131–135(2003)
UDC 546.19+541.8:547.216.131
JSCS – 3028
Original scientific paper
Kinetic determination of ultramicro amounts of As(III) in solution
ALEKSANDAR R. IGOV1, RANKO M. SIMONOVI]2 and RANGEL P. IGOV3
1“Nitex” Ni{, Yugoslavia, 2Faculty of Science, University of Pri{tina, Yugoslavia and 3Faculty of
Science, University of Ni{, Yugoslavia
(Received 26 August, revised 23 October 2002)
Abstract: A new catalytic reaction is proposed and a kinetic method developed for the determination of
ultramicro amounts of As(III) on the basis of its catalytic activity in the oxidation of ethylenediamineN,N’-diacetic-N,N’ dipropionic acid (EAP) by KMnO4 in the presence of hydrochloric acid. Under optimal
conditions, the sensivity of the method is 20 ng/cm3. The probable relative error is 7.6 – 14.5 % for the
concentration range 50 – 200 ng/cm3 As(III). The effect of certain foreign ions upon the reaction rate were
determined for the assessment of the selectivity of the method. The method has relatively good selectivity.
Kinetic equations were proposed for the investigated process.
Keywords: kinetic method, As(III) determination, ethylenediamine-N,N’-diacetic-N,N’-dipropionic acid.
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UDC 662.61/.62:66.046.59:66–948.3+546.22
JSCS – 3029
Original scientific paper
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A model of char particle combustion
MLADEN ILI]1, BORISLAV GRUBOR1, and VASILIJE MANOVI]2
1Institute for Nuclear Sciences “Vin~a”, P. O. Box 522, YU-11001 Belgrade and 2Faculty of Mining and
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combustion parameters. The parametric analysis of the enhanced model shows that the model represents a
good basis for the development of a model for the process of sulfur retention by ash during coal
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of reactions between sulfur compounds and mineral components in ash, primarily calcium oxide.
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