YU-ISSN 0352-5139

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YU-ISSN 0352-5139
J.Serb.Chem.Soc. Vol 68, No 7(2003)
CONTENTS
Organic Chemistry
S. @. Drmani}, B. @. Jovanovi}, A. D. Marinkovi} and M. Mi{i}-Vukovi}: The kinetics of the reactions
of 2-substituted nicotinic acids with diazodiphenylmethane in various alcohols
515
N. V. Valenti} and G. S. U{}umli}: Effects of substituents on the 1H-NMR chemical shifts of 3methylene-2-substituted-1,4-pentadienes
525
V. W. Bhagwat, J. Tiwari, A. Choube and B. Pare: Kinetics and mechanism of cetyltrimethylammonium
bromide catalyzed oxidation of diethylene glycol by chloramine-T in acidic medium
535
B. Todorovi}-Markovi}, Z. Markovi}, N. Marinkovi} and T. Nenadovi}: Experimental study of physical
parameters significant in fullerene synthesis (Short communication)
543
Physical Chemistry
I. Gutman, B. Arsi} and B. Furtula: Equiseparable chemical trees
549
D. @. Mijin, D. G. Antonovi}, G. Bon~i}-Cari~i}, B. @. Jovanovi} and O. S. Rajkovi}: Gas
chromatographic retention indices for N-substituted amino s-triazines on capillary columns. Part IV.
Influence of column polarity on retention index
557
T. J. Janji}, G. Vu~kovi} and M. B. ]elap: Investigation of the compatibility between one-dimensional
system parameters and the multidimensional Solvation parameter model in RP liquid column
chromatography
565
S. D. Pawar and P. M. Dhadke: Extraction and separation studies of Ga(III), In(III), and Tl(III) using the
neutral organophosphorous extractant, Cyanex-923
581
A. Cecal, A. Paraschivescu, K. Popa, D. Colisnic, G. Timco and L. Singenerean: Radiolytic splitting of
water molecules in the presence of some supramolecular compounds (Short communication)
593
J.Serb.Chem.Soc. 68(7)515–524(2003)
UDC 547.831+541.45:531.3+661.725
JSCS – 3068
Original scientific paper
The kinetics of the reactions of 2-substituted nicotinic acids with diazodiphenylmethane in various alcohols
SA[A @. DRMANI], BRATISLAV @. JOVANOVI]#, ALEKSANDAR D. MARINKOVI]# and MILICA
M. MI[I]-VUKOVI]#
Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade,
Karnegijeva 4, P. O. Box 3503, 11001 Belgrade, Serbia and Montenegro
(Received 15 November 2002)
Abstract: The rate constants of 2-substituted nicotinic acids in reaction with diazodiphenylmethane (DDM)
in eight alcohols at 30 ºC have been determined. In order to explain the obtained results through solvent
effects, the second order reaction rate constants (k) of the examined acids were correlated using the
appropriate solvent parameters by the equation:
log k = log k0 + af(e) + bs* + c ngH
where f(e) is the measure of solvent ability as a dielectric to stabilize the separation of opposite charges in
the activated complex, s* is the measure of solvent ability to stabilize proton in the initial state and ngH
represents the ability of protic solvents to form hydrogen bond with the negative end of the ion-pair
intermediate. These constants were correlated also by using solvatochromic equation of the form:
log k = log k0 + sp* + aa + bb
where p* is the measure of the solvent polarity, a represents the scale of the solvent hydrogen bond donor
acidities (HBD) and b represents the scale of the solvent hydrogen bond acceptor basicities (HBA). The
correlations of the kinetic data were carried out by means of multiple linear regression analysis. The results
obtained for 2-substituted nicotinic acids were compared with the results for ortho-substituted benzoic acid
under the same experimental conditions.
Keywords: 2-substituted nicotinic acids, kinetic measurements, protic solvents, solvent parameters,
diazodiphenylmethane.
REFERENCES
1. B. Jovanovi}, S. Drmani}, M. Mi{i}-Vukovi}, J. Chem. Res. (S) (1998) 554
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4. M. H. Aslam, A. G. Burden, N. B. Chapman, J. Shorter, M. Charton, J. Chem. Soc. Perkin Trans. 2
(1981) 500
5. N. B. Chapman, J. Shorter, J. H. P. Utley, J. Chem. Soc. (1962) 1824
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8. K. Bowden, Can. J. Chem. 43 (1965) 3354
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11. R. W. Taft, Steric Effects in Organic Chemistry, M. S. Newman, Wiley, New York, 1956, p. 13
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J.Serb.Chem.Soc. 68(7)525–534(2003)
UDC 547.538+547.361.2:66.08
JSCS – 3069
Original scientific paper
Effect of substituents on the 1H-NMR chemical shifts of 3-methylene-2-substituted-1,4-pentadienes
NATA[A V. VALENTI] and GORDANA S. U[]UMLI]#
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, P. O. Box 3503, 11120
Belgrade, Serbia and Montenegro, E-mail: [email protected]
(Received 26 November 2002, revised 21 February 2003)
Abstract: The principle of linear free energy relationships was applied to the 1H chemical shifts of the bvinyl proton atoms of 3-methylene-2-substituted-1,4-pentadienes. The correlations of the proton chemical
shifts with Swain and Lupton substituent parameters provide a mutually consistent picture of the electronic
effects in these compounds. The overall pattern of proton chemical shifts can be largely accounted for by a
model of substituent effects based on field, resonance and p polarization effects. Owing to the particular
geometric arrangement of the vinyl group in 3-methylene-2-substituted-1,4-pentadienes, the b-vinyl
protons HB and HC have different sensitivities to polar and resonance effects. The different sensitivities of
the 1H chemical shifts to resonance effects reveals some effects not predicted by the model outlined above.
Evidence is presented that demonstrates that both the 1H and 13C chemical shifts for these compounds
reflect their ground-state charge densities.
Keywords: cross-conjugated trienes, ring substituted a-(s-cis-2-butadienyl)styrenes, b-vinyl proton
chemical shifts, substituent effects.
REFERENCES
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J.Serb.Chem.Soc. 68(7)535–542(2003)
UDC 547.422+546.13–304.2:541.128
JSCS – 3070
Original scientific paper
Kinetics and mechanism of cetyltrimethylammonium
bromide catalyzed oxidation of diethylene glycol by chloramine-T in acidic medium
V. W. BHAGWAT1, J. TIWARI1, A. CHOUBE2 and B. PARE3
1School of Studies in Chemistry, Vikram University, Ujjain-456010, India, 2IPCA Laboratories, Ratlam,
India, and 3Madhav Science College, Vikram University, Ujjain-456010, India
(Received 15 October 2002, revised 18 February 2003)
Abstract: The kinetics and mechanism of the C16TAB catalyzed oxidation of diethylene glycol (2,2’oxydiethanol) by chloramine-T in acidic medium has been studied. The reaction has a first-order
dependence on chloramine-T. With excess concentrations of other reactants, the reaction rate follows
fractional order kinetics with respect to [diethylene glycol]. The micellar effect due to
cetyltrimethylammonium bromide, a cationic surfactant, has been studied. The reaction is catalyzed by
chloride ions as well. The small salt effect and increase in the reaction rate with increasing dielectric
constant suggest the involvement of neutral molecules in the rate determining step. Addition of ptoluenesulfonamide retards the reaction rate. On the basis of product analysis, a pertinent mechanism is
proposed.
Keywords: diethylene glycol, chloramine-T, micellar catalysis.
REFERENCES
1. B. S. Lele, M. G. Kularni, J. Appl. Polym. Sci. 70 (1998) 883; R. A. Singh, R. S. Singh, Oxid. Commun.
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J.Serb.Chem.Soc. 68(7)543–547(2003)
UDC 547.422+546.13–304.2:541.128
JSCS – 3071
Short communication
SHORT COMMUNICATION
Experimental study of physical parameters significant in fullerene synthesis
B. TODOROVI]-MARKOVI], Z. MARKOVI], M. MARINKOVI] and T. NENADOVI]
Vin~a Institute of Nuclear Sciences, P. O. Box 522, Belgrade, Serbia and Montenegro
(Received 29 October 2002, revised 8 March 2003)
Abstract: In this work, the effect of physical parameters on the yield of fullerene, synthesized in a hollow
cathode plasma reactor is investigated. The experimental investigations done previously have shown that
the fullerene yield depended on tehcnical parameters - the current intensity, inert gas pressure, type of gas
and interelectrode gap. The aim of this work was to show that the fullerene yield depends on physical
parameters - carbon concentration, carbon flow rate from the interelectrode gap, axial temperature and
temperature gradient between the arc channel and the chamber walls as well. It was found that fullerene
synthesis occurs in an inert heat bath with dimensions determined by the temperature gradient. The lower
temperature limit is around 2000 K and the value of the upper limit is the value of the axis temperature
which depends on the discharge conditions. The synthesis of fullerenes is more effective if the carbon
concentration in the heat bath is large and the carbon flow rate from that zone to colder parts of chamber is
small.
Keywords: fullerene, carbon arc, carbon concentration, temperature.
REFERENCES
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J.Serb.Chem.Soc. 68(7)549–555(2003)
UDC 547.12:541.6:539.2
JSCS – 3072
Original scientific paper
Equiseparable chemical trees
IVAN GUTMAN,a BILJANA ARSI]b and BORIS FURTULAa
aFaculty ov Science, University of Kragujevac, P. O. Box 60, 34000 Kragujevac and bFaculty of Science,
University of Ni{, Vi{egradska 33, 18000 Ni{, Serbia and Montenegro
(Received 21 February 2003)
Abstract: Let n1(e|T) and n2(e|T) denote the number of vertices of a tree T, lying on the two sides of the
edge e. Let T1 and T2 be two trees with equal number of vertices, let e be an edge of T1 and f an edge of
T2. Then e and f are said to be equiseparable if either n1(e|T1) = n1(f|T2) or n1(e|T1) = n2(f|T2). If all
edges of T1 and T2 can be chosen so as to form equiseparable pairs, then T1 and T2 are equiseparable
trees. A number of molecular structure-descriptors of equiseparable chemical trees coincide, implying that
the corresponding alkane isomers must have similar physico-chemical properties. It is shown how
equiseparable chemical trees can be constructed in a systematic manner.
Keywords: Wiener index, variable Wiener index, chemical trees, alkanes, equiseparability.
REFERENCES
1. H. Wiener, J. Am. Chem. Soc. 69 (1947) 17
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6. D. Vuki~evi}, MATCH Commun. Math. Comput. Chem. 47 (2003) 87
7. D. Vuki~evi}, I. Gutman, MATCH Commun. Math. Comput. Chem. 47 (2003) 107
8. D. Vuki~evi}, J. @erovnik, MATCH Commun. Math. Comput. Chem. 47 (2003) 119
9. I. Gutman, D. Vidovi}, B. Furtula, I. G. Zenkevich, J. Serb. Chem. Soc., 68 (2003) 401
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J.Serb.Chem.Soc. 68(7)557–564(2003)
UDC 547–304.9:543.544.3:66–948.3
JSCS – 3073
Original scientific paper
Gas chromatograpic retention indices for N-substituted amino s-triazines on capillary columns. Part IV.
Influence of column polarity on retention index
DU[AN @. MIJIN1, DU[AN G. ANTONOVI]1,#, GORDANA BON^I]-CARI^I]1, BRATISLAV @.
JOVANOVI]1,# and OLGA S. RAJKOVI]2
1Department of Organic Chemistry, Faculty of Technology and Metallurgy, University of Belgrade, P. O.
Box 3503, 11001 Belgrade and 2High Chemical School, 37001 Kru{evac, Serbia and Montenegro
(Received 29 July, revised 26 November 2002)
Abstract: The retention index increment for the addition of a methylene group to the alkyl group of an
analyte molecule is shown to be lower than 100 i.u. for N-substituted amino s-triazines. In temperature
progammed gas chromatography, a linearly interpolated retention index I, determined from the linear
regression equation, I = AZ + (GRF)z, with the number of atoms (Z) in the molecule as variable, was used
to describe the retention of 25 N-substituted amino s-triazines, on DB-1, DB-5 and DB-WAX capillary
columns, divided into five series according to the similarity of the alkyl groups in the particular series. In
the above equation, A is the linear regression coefficient or the retention index increment per atom
addition, Z the number of C, N and Cl atoms in the molecule, and (GRF)z the group retention factor or
functionality constant for functional groups in the molecule, based on the number Z. It is possible to
estimate the retention indices of an unknown member of the series from the Z, A and (GRF) values.
Keywords: retention indices, retention index increment, s-triazines, group retention factors.
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J.Serb.Chem.Soc. 68(7)565–579(2003)
UDC 66.093.1+543.544:519.233.2:541.121/.123
JSCS – 3074
Original scientific paper
Investigation of the compatibility between one-dimensional system parameters and the multi-dimensional
Solvation
parameter model in RP liquid column chromatography
TOMISLAV J. JANJI],# GORDANA VU^KOVI], and MILENKO B. ]ELAP#
Faculty of Chemistry, University of Belgrade, P. O. Box 158, 11001 Belgrade, Serbia and Montenegro
(Received 21 November 2002)
Abstract: It has been established that in many cases the system constants used in the Solvation parameter
model as well as the corresponding log k values can be linearized in the same NSP and NSP’ scale,
respectively, which shows the compatibility of both models. NSP and NSP’ are one-dimensional system
parameters adapted to the chromatographic system used over the phase equilibrium constant.
Keywords: system parameters, NSP parameter, NSP’ parameter, Solvation parameter model, log k
linearization, system constants.
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J.Serb.Chem.Soc. 68(7)581–591(2003)
UDC 546.681/.683+66.061+620.168.3:547.448
JSCS – 3075
Original scientific paper
Extraction and separation studies of Ga(III), In(III) and Tl(III) using the neutral organophosphorous
extractant, Cyanex-923
S. D. PAWAR and P. M. DHADKE
Inorganic Chemical Laboratory, Institute of Chemical Technology Uninversity of Mumbai, Matunga,
Mumbai-400 019 India
(Received 5 November 2002, revised 27 January 2003)
Abstract: The neutral extractant, Cyanes-923 has been used for the extraction and separation of
gallium(III), indium(III) and thallium(III) from acidic solution. These metal ions were found to be
quantitatively extracted with Cyanex-923 in toluene in the pH range 4.5–5.5, 5.0–6.5 and 1.5–3.0,
respectively, and from the organic phase they can be stripped with 2.0 mol dm-3 HNO3, 3.0 mol dm-3
HNO3 and 3.0 mol dm-3 HCl, respectively. The effect of pH equilibration period, diluents, diverse ions
and stripping agents on the extraction of Ga(III), In(III) and Tl(III) has been studied. The stroichiometry of
the extracted species of these metal ions was determined on the basis of the slope analysis method. The
reaction proceed by solvation and the probable extracted species found were [MCl3. 3Cyanex-923] [where
M = Ga(III) or In(III) ] and [HTlCl4. 3Cyanex-923]. Based on these results a sequential procedure for the
separation of Ga(III), In(III) and Tl(III) from each other was developed.
Keywords: solvent extraction, Cyanex-923, Ga(III), In(III), Tl(III), stripping, separation.
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J.Serb.Chem.Soc. 68(7)593–598(2003)
UDC 628.665.664+66.092.085:543.632.43
JSCS – 3076
Short communication
SHORT COMMUNICATION
Radiolytic splitting of water molecules in the presence of some supramolecular compounds
ALEXANDRU CECAL1,, ANDREI PARASCHIVESCU1, KARIN POPA1, DAN COLISNIC1,
GRIGORE TIMCO2 and LIDIA SINGEREAN2
1Faculty of Chemistry, “Al. I. Cuza” University, 11, B-dul Carol I, 6600 Iasi, Romania and 2Institute of
Chemistry, Academy of Science, Kishinew, Republic of Moldova
(Received 5 June 2002)
Abstract: This paper deals with the study of the hydrogen output during the catalyzed radiolysis of water in
the presence of the supramolecular compounds Fe2NiO(TMAc)6.3HTMAc, FeCoO (TMAc)6 . 3HTMAc,
[Cr3O(C6H5COO)6] · ClO4, Fe3Ni2O(OH)(TMAc)7(Aacet)3, Ni2(H2O) (TMAc)4(HTMAc)4,
[Cr3O(TMAc).3H2O](TMAc), and Cr8F8(TMAc)16. A 60Co g-source of 5.1´1014 Bq activity at a rate
dose of 8.038 kGy h-1 was used. The radiolysis products were determined by mass spectrometry. For a
given irradiation time, it was found that quantity of hydrogen obtained by water radiolysis is 6 – 18 times
greater in the presence of the supramolecular compounds as catalysts than in their absence from the
irradiated system.
Keywords: hydrogen evolution, radiolysis, supramolecular catalysts, radioactive waste.
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