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Indian Journal of Chemistry
Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical
VOLUME 41A
NUMBER 8
August 2002
CONTENTS
Papers
1551
Determination of bond phase in HOMO/
LUMO of fully-benzenoid hydrocarbons
Tetsuo Morikawa*, Susumu Narita &
Tai-ichi Shibuya
1554
Oxidation and decomposition of NH3 over
combustion synthesized Al2O3 and CeO2
supported Pt, Pd and Ag catalysts
The catalytic oxidation and decomposition of NH3 have
been carried out over combustion synthesized Al2O3 and
CeO2 supported Pt, Pd and Ag catalysts. It is observed that
NH3 decomposition over all the catalysts occurs above
450oC.
Parthasarathi Bera & M S Hegde*
1562
In situ preparation of polyaniline/silica
composites and study of their adsorption
characteristics
Polyaniline/silica, poly-o-toluidine/silica and poly-2chloroaniline/silica composites have been prepared under a
variety of synthetic conditions. The observed BET surface
area of the composites are found to be nearly ten times
higher than that of the bulk polymer.
Al-Nakib Chowdhury*, M A Yousuf,
M Muhibur Rahman &
A Q M Quamrul Hassan
1569
Thermal decomposition of Gd-Mg oxalate and
the effect of -irradiation
Gd0.9 Mg1.12 (C2O4)2.48 2H2O, which decomposes in two
stages (TGA) upon γ-irradiation, shows a decrease in the
reaction rate at lower doses and subsequent increase at
higher doses.
S C Moharana, J Praharaj & D Bhatta*
1575
Solvent effect on reactivity trends for base
hydrolysis of 2-oxo-, 2-thio- benzopyran-3thiocarboxamide, and 2-iminobenzopyran-3carbonitrile
Rafat M El-Khatib
Kinetics of base-catalysed hydrolyses of 2-oxobenzopyron3-carboxamide, 2-thiobenzopyron-3-carboxamide, and 2iminobenzopyran-3-carbonitrile are studied in aqueous
methanol mixture and the effect of solvent on change in
the activation barrier is measured. It is observed that the
substituents O, S or N in position two and thiocarboxamide
or carbonitrile in position three affect the rate constant and
change the activation barrier.
1580
Studies on solvation interaction: Solubility of a
betaine
dye
and
a
ketocyanine
dye in homogeneous and heterogeneous media
Ramkrishna Pramanik & Sanjib
Bagchi*
1588
Viscometric studies of molecular interactions
in ternary liquid mixtures of ethane-1,2-diol
with some polar and non-polar solvents
Surabhi Singh & Mukhtar Singh*
1593
Excess volumes and viscosities of N–methyl–2–
pyrrolidinone with branched alcohols at
298.15 K
Solubility of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1yl) phenolate, and a ketocyanine dye has been determined
in binary solvent mixtures and in cationic and anionic
micellar media. The results have been explained in terms
of solute-solvent and solvent-solvent interaction. Study in
micellar media provides information regarding the location
of the dye in the heterogeneous media.
Densities and viscosities of ternary liquid mixtures of
ethane-1,2-diol with some polar and non-polar solvents
have been measured as a function of the composition at a
constant temperature. The results have been discussed in
regard to the nature and strength of molecular interactions
between the mixing components.
Excess volumes (VmE) and viscosities () of binary liquid
mixtures of N–methyl-2–pyrrolidinone with branched
alcohols have been measured as a function of composition.
The VmE for each of the mixtures studied are negative over
the entire composition range.
Amalendu Pal*, Anil Kumar
B R Arbad & A B Tekale
1600
Ternary complexes of iron(III) with 1,2-bis(2hydroxybenzamido)ethane, thiocyanate and
sulphur(IV): A kinetic study.
Harapriya Rath & Anadi C. Dash*
k1
Fe(L)(OH2)2+ +HSO3
Fe(L)(OH2)(SO3) + H+
Kd↓↑
H+
+
Q
k2
Fe(L)(OH2)2++SO32
{Fe(L)(OH2)2+,SO32}
Fe(L)(OH2)(SO3)
Notes
1604
Enumeration of non-equivalent carbon atoms
in finitely large triangulenes, rhombulenes and
related structures
Tapanendu Ghosh, Sujit Sankar Panja &
Asok K Mukherjee*
1607
Hydrodechlorination of
dichlorodifluoromethane over novel CrF3 supported palladium
catalysts
Yu Cai Cao & Xuan Zhen Jiang*
Novel CrF3 supported palladium catalysts have been
prepared through two different precursors These catalysts
exhibit improved catalytic activities in hydrodechlorination
of CFC-12 as compared with conventional Pd/-Al2O3.
1612
Kinetics and mechanism of oxidation of lower
oxyacids of phosphorus by tetrabutylammonium tribromide
Pradeep K Sharma
1616
Synthesis, characterization and ion exchange
properties of a new inorganic ion exchange
material: Zirconium(IV) iodooxalate

slow
R PH (O) OH + Br3 
R
P
(O) OH + HBr
+ 2 Br
R

P
fast
(O) OH + H2O  RP(O)(OH)2 + H+
A new three component inorganic ion exchange material
zirconium (IV) iodooxalate (ZIO) has been synthesized.
The ion exchange capacity varies and is found to be depend
upon the crystal ionic radius of exchanging cations.
J P Rawat*, Premvir Singh & Nafisur
Rahman
1619
Synthesis and characterization of complex
[Mn(1-pyS)(dien)(CO)3] by the reaction of
[Mn2(-pyS)2(CO)6] (pySH=pyridine-2-thiol)
and diethylenetriamine (dien)
1621
CO
Mn
N
H2
Gulsan Ara, Shariff E Kabir &
Kalipada Kundu*
O
C
H2
N
CO
S
N
N
3
Synthesis and characterisation of saccharide
complexes of La(III) ion
Anindita Mukhopadhyay,
Erkki Kolehmainen & Chebrolu Pulla Rao*
1625
Metal-pyridylcarboxypropanamide (PCPAH)
and
metal-pyridylcarboxy-benzamide
(PCBAH) interactions : Stability constant,
chemical
speciation
and
molecular
modelling studies
B S Garg*, R K Sharma*, R Shrestha,
Sachin Mittal & M Sarbhai
1629
Synthesis and spectral studies on copper(II)
and cobalt(II) complexes of macrocyclic ligand
containing thiosemicarbazone moiety
Sulekh Chandra* & Sangeetika
New copper(II) and cobalt(II) complexes of macrocyclic
Schiff base ligand containing thiosemicarbazone moiety
have been synthesized and characterized.
1634
Synthesis of N,N-dialkyl dithiocarbamate
triphenyltin(IV) and crystal structures of
Ph3SnS2CN(C2H5)2 and Ph3SnS2CN(C5H10)
Dezhong Zhu, Rufen Zhang, Chunlin Ma* &
Handong Yin
1639
Synthesis and characterisation of some
phthalanilic and maleanilic acid derivatives of
arsenic(III)
H P S Chauhan*, R K Singh, B Porwal &
Kavita Kori
1643
Simultaneous
second
derivative
spectrophotometric determination of nickel(II)
and copper(II) using diacetylmonoxime
isonicotinoyl hydrazone
K B Chandrasekhar & K Hussain Reddy*
1646
Differential pulse polarographic determination
of lead(II) in complex materials after
adsorption of its trifluoroethylxanthate-cetyltrimethylammonium ion-associated complex
on microcrystalline naphthalene or on trifluoroethylxanthatecetyltrimethylammonium-naphthalene adsorbent
Lead(II) is adsorbed as lead trifluoroethylxanthatecetyltrimethylammonium
ion
pair
complex
on
microcrystalline naphthalene quantitatively. In the absence
of cetyltrimethylammonium as the counter ion, the
adsorption is only 80%.
B K Puri*, Atamjyot, Keemti Lal &
Himanshu Bansal
1652
Sodium anthraquinone-2-sulphonate sensitized
photoreduction of methylene violet
W R Bansal* & Kulvir Singh
Authors for correspondence are indicated by (*)
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1551-1553
Determination of bond phase in HOMO/LUMO of fully-benzenoid
hydrocarbons
Tetsuo Morikawa*, Susumu Narita & Tai-ichi Shibuya
Classical valence theory suggests the existence of 'quasi-single' bonds in a class of benzenoid hydrocarbons,
called fully-benzenoid hydrocarbons such a bond connects one aromatic sextet with another. The phase of a bond is
defined as the sign either plus for bonding or minus for antibonding. We conclude by use of perturbation molecular
orbital theory that the bond phase of quasi-single bonds has always the minus sign in HOMO of fully-benzenoid
hydrocarbons; the bond phase alters in HOMO and LUMO.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1554-1561
Oxidation and decomposition of NH3 over combustion synthesized Al2O3 and
CeO2 supported Pt, Pd and Ag catalysts
Parthasarathi Bera & M. S. Hegde
The catalytic oxidation and decomposition of NH3 have been carried out over combustion synthesized Al2O3
and CeO2 supported Pt, Pd and Ag catalysts using temperature programmed reaction (TPR) technique in a packed
bed tubular reactor. Metals are ionically dispersed over CeO2 and fine metal particles are found on Al2O3. NH3
oxidation occurs over 1% Pt/Al2O3, 1% Pd/Al2O3 and 1% Ag/Al2O3 at 175, 270 and 350 oC respectively producing
N2, NO, N2O and H2O, whereas 1% Pt/CeO2, 1% Pd/CeO2 and 1% Ag/CeO2 give N2 along with NO, N2O and H2O
at 200, 225 and 250 oC respectively. N2 predominates over other N-containing products during the reaction on all
catalysts. At less O2 concentration, N2 and H2O are the only products obtained during NH3 oxidation. NH3
decomposition over all the catalysts occurs above 450 oC.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1562-1568
In situ preparation of polyaniline/silica composites and study of their
adsorption characteristics
Al-Nakib Chowdhury*, M. A. Yousuf, M Muhibur Rahman & A. Q. M. Quamrul Hassan
Polyaniline/silica, poly-o-toluidine/silica and poly-2-chloroaniline/silica composites have been prepared under
a variety of synthetic conditions by polymerizing the respective monomers in the presence of silica prepared in situ
from an aqueous sodium silicate solution. The composites, thus synthesized, have been characterized by a wide
range of experimental techniques including elemental analysis for silica content, density, infrared spectroscopy and
sedimentometry for particle size determination. When used as column material in the IGC experiments, synthesized
composites have been found to be capable of separating the alkanes (C5C9) from their mixture. The composites
have been further examined for their surface free energy and specific surface area. The observed BET surface area
of the composites were found to be nearly ten times higher than that of the bulk polymer.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1569-1574
Thermal decomposition of Gd-Mg oxalate and the effect of -irradiation
S.C. Moharana, J. Praharaj & D. Bhatta
Decomposition of Mg and Gd oxalates, mechanical mixture and co-precipitated (unirrad. and irrad.) Gd-Mg
oxalate has been studied by adopting rising temperature technique. The kinetics of the decomposition are
investigated using thermogravimetry. The TG-DTA data exhibit two different stages of weight loss and endotherms,
corresponding to individual components in the co-precipitate. Kinetic parameters for different stages are obtained
by applying best fit models of solid state reactions in the Coats-Redfern’s equation. Effects of irradiation and coprecipitation technique on the mechanism of decomposition of Gd-Mg ox have been studied.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1575-1579
Solvent effect on reactivity trends for base hydrolysis of 2-oxo-,
2-thio- benzopyran-3-thiocarboxamide, and 2-iminobenzopyran-3carbonitrile
Rafat M. El-Khatib
Kinetics of base-catalysed hydrolyses of 2-oxobenzopyron-3-carboxamide, 2-thiobenzopyron-3-carboxamide,
and 2-iminobenzopyran-3-carbonitrile are studied in aqueous methanol mixture and the effect of solvent on change
in the activation barrier (δmΔG≠) is measured. Solvent effects on reactivity trends for base hydrolysis of these
compounds have been analysed into initial state and transition state components which are determined from transfer
chemical potentials and kinetic data. It is observed that the substituents O, S or N in position two and
thiocarboxamide or carbonitrile in position three affect the rate constant and change the activation barrier
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1580-1587
Studies on solvation interaction. Solubility of a betaine dye and a ketocyanine
dye in homogeneous and heterogeneous media.
Ramkrishna Pramanik & Sanjib Bagchi*
Solubility of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate, commonly known as Reichardt’s
betaine dye and a ketocyanine dye has been determined in binary solvent mixtures and in cationic and anionic
micellar media. In all the binary mixtures the standard molar free energy of solution, as given by log s12 where s12 is
the solubility in the binary mixture, cannot be represented by the average of log s values in pure solvents weighted
with respect to mole fraction of the components. The deviation from the mole fraction average value, as given by 
(log s)=log s12(x1log s1x2log s2), has been calculated and compared with the similar parameter as obtained from
the electronic spectroscopic transition energy. The results have been explained in terms of solute-solvent and
solvent-solvent interaction. Study in micellar media provides information regarding the location of the dye in the
heterogeneous media.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1588-1592
Viscometric studies of molecular interactions in ternary liquid
mixtures of ethane-1,2-diol with some polar and non-polar solvents
(Ms.) Surabhi Singh & Mukhtar Singh*
Densities and viscosities of ternary liquid mixtures of ethane-1,2-diol with some polar (acetone and
methyl ethyl ketone) and non-polar(benzene, toluene, carbon tetrachloride) solvents have been measured as a
function of the composition at a constant temperature 298.15 K. From the density and viscosity data the
excess thermodynamic properties, viz., the excess molar volume (VE), the excess viscosity(E) and the excess
Gibbs free energy of activation of flow (G#E), have been calculated. On the basis of the values of excess
thermodynamic properties and that of the parameter d (in Grunberg and Nissan equation) the results have
been discussed in regard to the nature and strength of molecular interactions between the mixing
components.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1593-1599
Excess volumes and viscosities of N–methyl–2–pyrrolidinone with branched
alcohols at 298.15 K
Amalendu Pal* , Anil Kumar, B R Arbad & A B Tekale
Excess volumes (VmE) and viscosities () of binary liquid mixtures of N–methyl-2–pyrrolidinone with
branched alcohols have been measured as a function of composition at 298.15 K. The branched alcohol includes 2–
propanol, 2-methyl-1-propanol, 3-methyl-1-butanol, and 2-methyl-2-propanol. The VmE for each of the mixtures
studied are negative over the whole composition range. From the experimental data, the deviation in viscosities ()
and excess energies of activation (G*E) for viscous flow have been calculated. These values are negative over the
entire range of composition. The results for VmE, , and G*E are discussed in terms of interaction between
components. The viscosity data have been correlated with the equations of McAllister, Heric, and Auslaender.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1600-1603
Ternary complexes of iron(III) with 1,2-bis(2-hydroxybenzamido)ethane,
thiocyanate and sulphur(IV): A kinetic study.
Harapriya Rath & Anadi C. Dash*
The kinetics of anation of (diaqua)(1,2-bis(2-hydroxybenzamido)iron(III) by NCS- and SIV (HSO3- and SO32-) are
reported at 25oC, I = 0.5 mol dm-3 in 20%(v/v) MeOH
+ H2O medium. The formation of the monothiocyanato
complex, Fe(L)(OH2)(NCS), is reversible. The monosulphito complex, Fe(L)(OH2)(SO3)- is formed via the reaction
of the diaqua complex with HSO3- and SO32-; dissociation of the sulphito complex to the reactants has not been
observed. Ion-pairing of the diaqua complex with SO32- (but not with HSO3-) has been identified kinetically and
resulted in the reduced reactivity of SO32- in comparison to HSO3-. The results are consistent with the dissociative
mode of activation for the aqua ligand substitution of Fe(L)(OH2)2+. It has been found that there is no significant
labilising action of the coordinated phenoxide and amide functions of the primary ligand (L 2-) on the aqua ligand
replacement reaction at iron(III) center.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1604-1606
Enumeration of non-equivalent carbon atoms in finitely large
triangulenes, rhombulenes and related structures
Tapanendu Ghosh , Sujit Sankar Panja & Asok K Mukherjee*
Simple analytic expressions for the number of non-equivalent carbon atoms (NEC) which is important in counting 13C NMR
signals in some classes of polynuclear aromatic hydrocarbons, viz., linear polyacenes, flanked pyrenes, triangulenes and
rhombulenes have been deduced using Pólya’s enumeration theorem (PET) and Balasubramanian’s method of reduced cycle
indices. Given only a very obvious structural feature of the molecular graph, these analytical expressions directly yield the NEC
value and construction of the cycle index and reduced cycle index can be avoided. Moreover, in case of triangulenes NEC has
been shown to be obtainable from a flow-chart which is easy to construct and for rhombulenes NEC has been shown to be
obtainable from Pascal’s triangle.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1607-1611
Hydrodechlorination of dichlorodifluoromethane over novel CrF3
supported palladium catalysts
Yu Cai Cao & Xuan Zhen Jiang*
Novel CrF3 supported palladium catalysts have been prepared through two different precursors i.e.
dichlorobistriphenyl-phosphine palladium (DCTPPP) and PdCl2 for the hydrodechlorination of CFC-12. These
catalysts exhibited improved catalytic activities in hydrodechlorination of CFC-12 as compared with conventional
Pd/-Al2O3. Particularly, high selectivities (~81%) of CH2F2 formation have been achieved over DCTPPP/CrF3. The
improved catalytic performance may be attributed to the nature of support CrF 3 and the formation of fine palladium
particles in the catalysts.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1612-1615
Kinetics and mechanism of oxidation of lower oxyacids of phosphorus
by tetrabutylammonium tribromide
Pradeep K Sharma
Oxidation of lower oxyacids of phosphorus by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid
leads to the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibits
1:1 stoichiometry. The reaction is first order each in [TBATB] and [oxyacids]. The reaction does not induce
polymerization of acrylonitrile. There is no effect of tetrabutylammonium chloride on the reaction rate. The
proposed reactive oxidizing species is tribromide ion. It has been shown that the pentacoordinated tautomer of the
phosphorus oxyacid is the reactive reductant. The oxidation of deuteriated oxyacids exhibits a substantial primary
kinetic isotope effect. The effect of solvent composition indicates that the rate increases with an increase in the
polarity of the solvent. A mechanism involving transfer of a hydride ion in the rate-determining step has been
proposed.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1616-1618
Synthesis, characterization and ion exchange properties of a new
inorganic ion exchange material: Zirconium(IV) iodooxalate
J P Rawat*, Premvir Singh & Nafisur Rahman
A new three component inorganic ion exchange material zirconium (IV) iodooxalate (ZIO) has been
synthesized by adding a mixture of 0.1M potassium iodate and 0.1M oxalic acid to 0.1M zirconium oxychloride in
different volume ratios at pH 1. Among several samples synthesized, ZIO-6 is selected for detailed studies owing to
its highest ion exchange capacity and chemical stability. The material has been characterized on the basis of
chemical composition, pH-titration, FTIR and thermogravimetric studies. The ion exchange capacity of the material
for Na+ ion has been found to be 2.70 meq g1 dry exchanger. The ion exchange capacity varies and is found to be
depend upon the crystal ionic radius of exchanging cations. The chemical stability of the material has been tested in
acidic, neutral and basic media. The sorption studies of some metal ions have been made in distilled water and nitric
acid.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1619-1620
Synthesis and characterization of complex [Mn(1-pyS)(dien)(CO)3] by the
reaction of [Mn2(-pyS)2(CO)6] (pySH=pyridine-2-thiol) and
diethylenetriamine (dien)
Gulsan Ara, Shariff E Kabir & Kalipada Kundu*
The dimeric complex [Mn2(-pyS)2(CO)6] (1) reacts with 2 molar equivalents of diethylenetriamine (dien) to
give the monomeric complex [Mn(1-pyS)(dien)(CO)3] (2) in which the pyridine-2-thiolato group coordinates to
manganese through the S-atom as a two-electron donor ligand. The complex has been characterized by elemental
analysis and IR, PMR and mass spectroscopy.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1621-1624
Synthesis and characterisation of saccharide complexes of La(III) ion
Anindita Mukhopadhyay, Erkki Kolehmainena,
Chebrolu Pulla Rao*
A series of ten La(III)-saccharide complexes have been synthesised with eight different monosaccharides ( Dglucose, D-fructose, D-galactose, D-mannose, L-sorbose, D-arabinose, D-ribose and D-xylose) and two disaccharides
(D-maltose and D-lactose), and characterised by analytical, spectral and electrochemical techniques. 13C NMR
spectra reveal interesting binding modes of saccharide molecules towards La(III).
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1625-1628
Metal-pyridylcarboxypropanamide (PCPAH) and metal-pyridylcarboxybenzamide (PCBAH) interactions : Stability constant, chemical
speciation and molecular modelling studies
B S Garg*, R K Sharma*, R Shrestha, Sachin Mittal & M Sarbhai
Chemical speciation and molecular modeling studies have been carried out for accessing the interactions of metal
ion with some amide containing ligands. Chemical speciation has been carried out using the program BEST and SPE
and method of Bjerrum and Calvin, as modified by Irving and Rassotti has been used to find out the values of
stabilityconstants. The order of stability constants is found to be fairly in agreement to Irving-Williams order.
Molecular modeling studies have been carried out to determine the ideal site for metal binding to the ligands PCPAH
and PCBAH.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1629-1633
Synthesis and spectral studies on copper(II) and cobalt(II) complexes of
macrocyclic ligand containing thiosemicarbazone moiety
Sulekh Chandra* & Sangeetika
New copper(II) and cobalt(II) complexes of macrocyclic Schiff base ligand containing thiosemicarbazone moiety
have been prepared with a general composition [M(H2L2)X2] [where M = Cu(II) or Co(II); H2L2 = 3,4,9,10tetraphenyl-1,2,5,6,8,11-hexaazacycldodeca-7,12-dithione-2,4,8,10-tetraene; X = Cl-, NO3-, ½ SO42-, and ML2
[where salt used is copper acetate and cobalt thiocyanate]. When the mesocycle 6-ethoxy-1,6-diphenyl-4-thio-2,3,5triazine (H2L1) in ethanol react with metal salt (chromium chloride) acting as template using high dilution technique,
the macrocyclic ligand H2L2 was formed. The complexes have been characterized on the basis of elemental analysis,
molar conductance, magnetic susceptibility, IR, electronic 1H NMR, Mass and EPR spectral studies. The complexes
from H2L2 show different characteristics stoichiometry ratio with a variable grade of deprotonation in the ligand,
depending upon the salt used [Cl-, NO3-, ½SO42-, CH3COO- or SCN-] and working conditions.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1634-1638
Synthesis of N,N-dialkyl dithiocarbamate triphenyltin(IV) and
crystal structures of Ph3SnS2CN(C2H5)2 and Ph3SnS2CN(C5H10)
Dezhong Zhu, Rufen Zhang, Chunlin Ma* & Handong Yin
Eleven triphenyltin(IV) complexes with N,N-dialkyl dithiocar-bamate ligands have been synthesized by the
reaction of triphenyltin chloride with N,N-dialkyl dithiocarbamates and characterized by elemental analysis, UV, IR
and 1H NMR. The crystal structures of Ph3SnS2CN(C2H5)2 and Ph3SnS2CN(C5H10) have been determined by X-ray
single crystal diffraction, their structures show a distorted tigonal bipyramidal configuration with five-coordination
for the central tin atoms.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1639-1642
Synthesis and characterization of some phthalanilic and maleanilic acid derivatives
of arsenic(III)
H P S Chauhan* , R K Singh , B Porwal & Kavita Kori
Replacement reaction of arsenic trichloride and 2-chloro-1,3-dithia-2-arsacyclopentane with sodium
salts of phthalanilic and maleanilic acids (prepared in situ by the reaction of corresponding anilic acids with sodium
isopropoxide in the mixture benzene and isopropanol ) in the 1:3 and 1:1 molar ratios respectively, in benzene and
isopropanol mixture , yield the arsenic derivatives of the type [L] 3 As and
[L] AsSCH2CH2S (where L =
phthalanilate and maleanilate anions). These derivatives have been characterized by elemental analysis as well as IR
and 1H NMR spectral studies.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1643-1645
Simultaneous second derivative spectrophotometric determination of nickel(II) and
copper(II) using diacetylmonoxime isonicotinoyl hydrazone
K B Chandrasekhar & K Hussain Reddy*
A derivative spectrophotometric method, based on the use of second-derivative absorption spectra, has been
developed for the simultaneous determination of nickel(II) and copper(II) in aqueous medium using
diacetylmonoxime isonicotionyl hydrazone (DMIH). The reagent gives intense colour reaction with nickel(II) and
copper(II) in basic medium. The zero-order spectrophotometric method for the determination of these metal ions has
been developed in aqueous medium. The molar absorptivity and Sandell’s sensitivity for nickel(II) and coppers(II)
are 1.75  104; 1.12  104 lit. mol-1 cm-1 and 0.00335, 0.00565 µg of metal/cm2 respectively. Beer’s law is obeyed in
the range 0.235-2.35 and 0.25-2.54 µg/ml for Ni(II) and Cu(II) respectively. The proposed simultaneous method
involves the use of peak-to- base line measurement techniques.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1646-1651
Differential pulse polarographic determination of lead (II) in complex
materials after adsorption of its trifluoroethylxanthate-cetyltrimethylammonium ion-associated complex on microcrystalline naphthalene
or on trifluoroethylxanthate-cetyltrimethylammonium– naphthalene adsorbent
B K Puri*, Atamjyot, Keemti Lal & Himanshu Bansal
Lead(II) is adsorbed as lead trifluoroethylxanthate (TFEX)-cetyltrimethylammonium (CTMA) ion pair complex
on microcrystalline naphthalene quantitatively in the pH range 4.50-10.50. In the absence of
cetyltrimethylammonium as the counter ion, the adsorption is only 80%. Lead(II) is desorbed with HCl and
determined with a differential pulse polarograph. Dissolved oxygen is removed by adding 3 ml of 4% NaBH 4
solution. Alternatively, lead (II) can be quantitatively adsorbed on TFEX-CTMA-naphthalene adsorbent packed in a
column at a flow rate of 1-2 ml min-1 . Well defined peak has been obtained in this medium at –0.40 V versus S.C.E.
Cyclic voltammetric, differential polarographic and D.C. polarographic studies indicate that lead(II) has been
reduced reversibly in a two-electron reduction under these conditions. The detection limit is 0.20 g ml-1 at the
minimum instrumental settings (signal-to-noise ratio = 2). Linearity is maintained in the concentration range 0.516.40 g ml-1 with correlation factor of 0.9997 and a relative standard deviation of 1.07%. Various parameters such
as the effect of pH, volume of aqueous phase, flow rate and the interference of a large number of metal ions and
anions on the determination of lead(II) have been studied in detail to optimize the conditions for its trace
determination in various standard alloys, standard biological materials and environmental samples.
Indian Journal of Chemistry
Vol. 41A, August 2002, pp. 1652-1656
Sodium anthraquinone-2-sulphonate sensitized photoreduction of
methylene violet
W R Bansal* & Kulvir Singh
Department of Chemistry, Punjabi University,
Patiala 147002, India
Received 8 August 2000; revised 24 January 2002
Sodium anthraquinone-2-sulphonate sensitizes the photoreduction of methylene violet in aqueous medium in the presence of
hydrogen donors, isopropyl alcohol and benzhydrol, to give leuco methylene violet. Reduction takes place by reducing sodium
anthraquinone-2-sulphonate produced through hydrogen abstraction by excited triplet state of sodium anthraquinone-2sulphonate from the hydrogen donors. Effect of viscosity and role of electron transfer have been examined by adding ethylene
glycol and triethylamine respectively. LMV reaches a plateau at 4.0 and 1.7102 mol dm3 of IPA and BPH2 concentrations
where LMV =1.7 and 1.0 respectively. Difference in maximum quantum yields in the case of IPA and BPH2 has been explained.
LMV is not afected by viscosity change.