Indian Journal of Chemistry
Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical
VOLUME 41A
NUMBER 6
June 2002
CONTENTS
Papers
1107
Strengthening of the intramolecular O….H…N
hydrogen bond in 2-(N-benzyl--iminoethyl)naphthol as a result of steric repulsion
A new ortho-hydroxy schiff base 2-(N-benzyl-iminoethyl)-naphthol in which the hydrogen atom in the CC(H)=N group is replaced by a methyl substituent, is
synthesized. The O...N distance found in the O….H…N
hydrogen bond is quite short and this is due to the steric
repulsion of methyl substituent.
A Mandal, A Koll, A Filarowski &
S Mukherjee*
1112
The solvent activity-composition correlation
for systems continuously miscible from molten
salt to dilute solution
A new equation has been proposed to correlate the solvent
activity-composition data for a variety of systems
containing fused salts. The proposed equation comprising
the contributions due to long-range and short-range
interaction forces is capable of correlating the solvent
activities for several systems, including mixtures showing
strong negative, positive and weak deviations from
Rauolt’s law.
Pramod D Sonawane & Anil Kumar*
1120
Ion association and solvent interaction–
conductance of 1-ethyl-4-cyanopyridinium
iodide in aqueous-binary mixtures containing
acetone and 1,4-dioxane at different
temperatures
Conductance of 1-ethyl-4-cyanopyridinium iodide has
been measured in binary solvent mixtures of water and
aprotic cosolvents at different temperatures. In the waterrich region, water molecules become less available for
solvation owing to self association through H-bonding.
The preferential solvation of the solute in water + acetone
mixture is governed by both specific and nonspecific
interaction.
Ajay Mukhopadhyay & Mohan Pal*
1126
Thermodynamics of interaction between
L-cystine and sodium/magnesium chloride in
aqueous solution
Interactions of L-cystine with sodium chloride and
magnesium chloride have been studied by determining the
solubility of cystine in aqueous salt solutions of different
concentration at varying temperatures. The results show
that both NaCl and MgCl2 in water is beneficial to
dissolution of L-cystine.
Dacheng Li, Qingjiang Yu, Yong Wang &
Dezhi Sun*
1131
Partial molar volumes of transfer of some
disaccharides from water to aqueous guanidine
hydrochloride solutions at 298.15 K
T S Banipal*, Damanjit Kaur,
Gagandeep Singh, B S Lark & P K Banipal
Apparent molar volumes of D(+)-maltose monohydrate,
D(+)-cellobiose, D(+)-lactose monohydrate and D(+)trehalose dihydrate have been determined in water and
aqueous guanidine hydrochloride solutions from density
measurements. The results show that hydration behaviour
of saccharides do not depend only on constituting subunits
but also on the linkage between them.
1139
Viscometric studies for some 1:1 electrolytes in
water + tert-butyl alcohol and water + tertbutylamine mixtures at 298.15 K
Viscosity and density measurements for NaI, KI, Bu4NI,
LiCl and KCl in various mixtures of water with tert-butyl
alcohol and tert-butylamine have been carried out. The
values of B coefficient for KCl exhibit a minimum in the
water-rich region for both systems. For NaI and KI, they
are significantly reduced in tert-butylamine-rich mixtures
while in tert-butyl alcohol-rich mixtures they increase
profoundly compared to water-rich mixtures.
Pius K Kipkemboi* & Allan J Easteal
1146
Synthesis and characterization of some
lanthanoid complexes of salicylaldehyde
salicyloyl hydrazone
T R Rao*, Sabita Shrestha, & K K Narang
1152
Synthesis and spectroscopic studies on
platinum(II) complexes of thiosemicarbazone
derivatives of p-anisaldehyde, p-tolualdehyde
and p-vanillin
Narayan T Akinchan* & Richa Akinchan
1157
Heterobimetallic chemistry: Heterobimetallic
complexes
derived
from
monometallic
copper(II) complex of bis(2-hydroxy-1naphthaldehyde) malonoyldihydrazone
R A Lal*, J Chakraborty, S Bhaumik &
A Kumar
Notes
1163
QSAR study on antiviral activity of ester
prodrugs of 6-methoxypurine arabinosides
Vijay K Agrawal, Ruchi Sharma &
P V Khadikar*
The varicella-zoaster antiviral activity of 6-methoxy purine
arabinosides has been modelled using simple as well as
multi-variate regression analysis. The predictive potential of
the model is discussed on the basis of cross-validation
parameters.
1167
Thermodynamics of molecular interactions in
mixtures containing ether
V K Sharma* & Romi
1173
Surface tension studies of ternary system:
Copper soap plus benzene plus methanol at
313K
Molar excess volumes, VE and molar excess enthalpies, HE,
have been determined for 1,3-dioxolane + benzene or
toluene or + o, or + p or + m  xylene binary mixtures at
298.15K. The observed data have been analysed in terms of
the Graph-theoretical approach, Flory’s approach and
Sanchez and Lacombe’s theory.
Colloidal behaviour of copper soap solution in benzene plus
methanol mixture from the surface tension studies confirm
that cmc values depend upon the composition of the solvent
mixture and are found to decrease with increase in chain
length of the soap anion.
V P Mehta, P R Talesara, Rashmi Sharma*,
Antima Gangwal & Renu Bhutra
1177
Oxidative dehydrogenation of ethylbenzene
over La and Dy supported vanadia
S Sugunan* & N K Renuka
1184
Determination of osmotic coefficients of
aqueous
solutions
of
polyhydroxylated
compounds at various temperatures
Zuo-Ning Gao* , Jin-Fu Li & Xiao-Lin Wen
1188
A series of supported vanadia systems have been prepared
by excess solvent technique using La2O3 and Dy2O3 as
supports. The oxidative dehydrogenation of ethylbenzene
has been employed as a chemical probe reaction to examine
the catalytic activity. The active species correspond to
amorphous and crystalline tetrahedral vanadyl units in the
supported system.
Osmotic coefficients of aqueous solutions of glycol,
glycerol, sucrose and glucose at various temperatures have
been determined. The relation between the experimental
results of the molal osmotic coefficients and the molal
concentration of the solution are in agreement with that
from the polynomial fitting at various temperatures. The
molar osmotic coefficients increase with increase in
concentration of solutes.
Kinetics and mechanism of the interaction of
thiosemicarbazide
with
di--hydroxo
bis(bipyridyl)dipalladium(II) ion
Sankar Chandra Moi, G S De & A K Ghosh*
1191
Kinetics and mechanism of the reaction of
hydroxopentaaquarhodium(III)
ion
with
L-aspartic acid in aqueous media
HL +[Rh (OH2)5OH]2+
[Rh(OH2)5OH]2+ .HL
Kobs
[Rh(OH2)5OH]2+ , HL.
kan
[Rh(OH2)4(OH)HL]+ + H2O
slow
fast
[Rh (OH2) 4(OH) HL]+
S Mohanty, S Anand & P Mohanty*
1195
Kinetic and mechanistic investigation of the
[Rh (OH2) 3(OH) L] +H2O
Chelation
reaction of cis-diaqua-bis(ethylenediamine)
cobalt(III)
with
glycylglycine
in
aqueous solution
Debabrata Chatterjee* & Biswajit Ruj
1199
The crystal structure and spectroscopic studies
of
iron(III)tris(8-quinolinolato-N,O)
[Fe(C9H6NO)3]C2H5OH complex
Shusheng Zhang, Jingbo Xue &
Fangfang Jian*
1202
Cation- interactions: Synthesis and crystal
structure of complex [K(DB18C6)]I3
Qingjiang Yu, Tong Wang, Jianmin Dou*,
Dacheng Li & Daqi Wang
1205
Spectral
and
thermal
studies
of
homodinuclear
and
heterodinuclear
glutathione complexes
Bhagwan S Garg*, Deo Nandan Kumar &
B K Singh
1208
A study of the under potential deposited
hydrogen on the nickel deposited electrode in
alkaline media
The complexes of the types [M2LSO4.2H2O] where
L=GSH, M = Co(II), Cu(II), Zn(II), Cd(II) and
[MM'LSO4.2H2O] where L = GSH, M = Cu(II), M' = Zn(II)
& M = Co(II), M' = Cd(II)] have been synthesized and
characterized.
Hydrogen evolution reaction has been studied on the nickel
deposited electrode. The sodium ion has no effect on the
hydrogen evolution reaction. The diffusion coefficient of
hydrogen is calculated to be D=2.88x10-10 cm2s-1 using
impedance technique.
M Jafarian* , M G Mahjani , M Hoseni &
F Gobal
1212
Silica enriched faujasitic zeolite-Y from flyash
S U Meshram, S S Rayalu*, K N Munshi &
M Z Hasan
Various process modifications to enrich silica on zeolite-Y
have been carried out by increasing substantially the
SiO2/Al2O3 ratio from 1.8-2.0 to 2.5-3.0 with consequent
increase in thermal stability.
Authors for correspondence are indicated by (*)
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1107-1111
Strengthening of the intramolecular OH…N hydrogen bond in
2-(N-benzyl--iminoethyl)-naphthol as a result of steric repulsion
A Mandal, A Koll, A Filarowski & S Mukherjee*
One new ortho-hydroxy Schiff base, 2-(N-benzyl--iminoethyl)-naphthol (BEIN) in which the hydrogen atom
in the C-C(H)=N group is replaced by a methyl substituent, is synthesized. The crystal structure is determined and
ab initio calculations with B3LYP/6-31G** basis sets are performed. The O…N distance found in the O-H…N
hydrogen bond turns out to be quite short and is equal to 2.499 Å. This shortening is due to the steric repulsion of
methyl substituent group and results in strengthening of the hydrogen bond.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1112-1119
The solvent activity-composition correlation for systems continuously
miscible from molten salt to dilute solution
Pramod D Sonawane & Anil Kumar*
The systems, which are continuously miscible from pure fused ionic solute to dilute solutions in aqueous or
non-aqueous phase, exhibit some interesting physical properties. The composition dependence of solvent activity in
these systems resembles that of non-electrolyte mixtures. A new equation has been proposed to correlate the solvent
activity-composition (a1x1) data for a variety of systems containing fused salts. The proposed equation comprises
the contributions due to long-range (a modified Debye-Huckel term) and short-range (an empirical expression)
interaction forces. The equation is capable to correlate the solvent activities, a1 for the systems showing strong
negative, positive and weak deviations from Rauolt’s law. The correlative power of the proposed equation has been
tested against 13 systems showing negative deviations, 4 systems showing positive deviations from Rauolt’s law
and 7 mixtures. These systems are continuously miscible from pure fused salt to dilute solutions. The performance
of our equation has been compared to some existing models available in literature.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1120-1125
Ion association and solvent interaction–conductance of 1-ethyl-4-cyano
pyridinium iodide in aqueous-binary mixtures containing acetone and
1,4-dioxane at different temperatures
Ajay Mukhopadhyay & Mohan Pal*
Conductance of 1-ethyl-4-cyanopyridinium iodide has been measured in the concentration range (7.8-19.1) 
104 mol dm3 in binary solvent mixtures of water and aprotic cosolvents (acetone and 1,4-dioxane) at different
temperatures (293-308 K). The conductance data in all cases have been analysed by the Shedlovsky equation to
obtain 0 and KA. Based on the composition dependence of Walden product, the influence of the mixed solvent
composition on the solvation of ions has been discussed. The association constants, KA, are used to get information
about the influence of solvent composition on the various equilibria present in the solution. Thermodynamic
parameter, H0, as a function of solvent composition has also been determined.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1126-1130
Thermodynamics of interaction between L-cystine and
sodium/magnesium chloride in aqueous solution
Dacheng Li, Qingjiang Yu, Yong Wang & Dezhi Sun*
Interactions of L-cystine with sodium chloride and magnesium chloride have been studied by determining the
solubility of cystine in aqueous salt solutions of different concentration at varying temperatures. The interaction
thermodynamic parameters have been estimated with the solubility data. The results show that both NaCl and
MgCl2 in water is beneficial to dissolution of L-cystine. Enthalpy or entropy of interaction between L-cystine and
NaCl is negative while that between L-cystine and MgCl2 is positive. These interesting results are discussed in the
light of static electricity theory as well as hydration of ions.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1131-1138
Partial molar volumes of transfer of some disaccharides from water
to aqueous guanidine hydrochloride solutions at 298.15 K
T S Banipal*, Damanjit Kaur, Gagandeep Singh, B S Lark & P K Banipal
Apparent molar volumes (v) of some disaccharides [D(+)-maltose monohydrate, D(+)-cellobiose, D(+)-lactose
monohydrate and D(+)-trehalose dihydrate] have been determined in water and in aqueous guanidine hydrochloride
solutions (0.5, 1.0, 4.0, 6.0 and 8.0 m) at 298.15 K from density measurements using a vibrating-tube digital
densitometer. Partial molar volumes at infinite dilution (Vo2) determined from v values have been utilised to
estimate partial molar volumes of transfer (Vo2,tr) for various disaccharides from water to aqueous guanidine
hydrochloride solutions. The Vo2,tr values have been found to be positive for all the disaccharides and increase with
the increase in the concentration of the co-solute which suggest that overall structural order is enhanced in aqueous
guanidine hydrochloride solutions. The Vo2,tr values have been rationalized in terms of solute-co-solute interactions
using co-sphere overlap hydration model. Pair, triplet and quartet interaction coefficients have also been calculated
using McMillan-Mayer approach and their sign and magnitude have also been discussed
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1139-1145
Viscometric studies for some 1:1 electrolytes in water + tert-butyl
alcohol and water + tert-butylamine mixtures at 298.15 K
Pius K Kipkemboi* & Allan J Easteal
Viscosity and density measurements for NaI, KI, Bu4NI, LiCl and KCl in various mixtures of water with tertbutyl alcohol and tert-butylamine were carried out at 298.15 K. The viscosity data have been analysed on the basis
of the Jones-Dole equation and viscosity B-coefficients have been evaluated. The small and positive values of B
coefficients for LiCl in mixed liquid solvents as observed in both systems lead to the conclusion that ion-solvent
interaction is not strong. The B coefficients for hydrophobic Bu 4NI are large, positive and fairly constant for both
systems probably due to the absence of specific hydration and solvation effects. The values of B coefficient for KCl
exhibit a minimum in the water-rich region for both systems. However, the solvent composition dependence of B
coefficients for both NaI and KI electrolytes are drastically different in the two solvent systems. The viscosity B
coefficients for NaI and KI are significantly reduced in tert-butylamine-rich mixtures while in tert-butyl alcohol-
rich mixtures they increase profoundly compared to water-rich mixtures. Values of the partial molar volumes of the
electrolytes at infinite dilution in the various solvent mixtures have been evaluated from the density measurements.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1146-1151
Synthesis and characterization of some lanthanoid complexes of
salicylaldehyde salicyloyl hydrazone
T R Rao* , Sabita Shrestha & K K Narang
Some Lanthanoid complexes of the types, [Ln(ssh)(H2O)n].H2O and [Ln'(Hssh)(X)(H2O)3].H2O, where Ln = Y,
La, Nd, Gd, Tb and Dy; Ln' = Pr/Sm for X = NO3/Cl and H3ssh = salicylaldehyde salicyloyl hydrazone, have been
synthesized and characterized by elemental analyses, molar conductance, magnetic susceptibility, infrared, electronic
and 1H NMR spectral data. Selected complexes have also been studied on the basis of their solid state electrical
conductivity, band gap, and powder X-ray diffraction data. The complexes, except those of the Pr and Sm, are
polymeric in nature showing high decomposition points. Dehydration study indicates the presence of water
molecules both in the lattice and coordination sphere of the complex metal ions. IR and 1H NMR spectral data
suggest trinegative tetradentate and dinegative tridentate coordination of H3ssh in the complexes. The chloro and
nitrato groups were found to coordinate to the metal ion as monodentate and bidentate-chelating species respectively.
Solid state electrical conductivity data at various frequencies show semi-conducting nature of the complexes.
Optical band gap studies show the complex [Gd(ssh)(H2O)3].H2O to be a direct band gap semi-conducting material
with a band gap of 2.64 eV. Powder X-ray diffraction patterns show orthorhombic structure for most of the
complexes. Various polyhedral geometries such as distorted octahedron, pentagonal bipyramid and distorted square
antiprism were tentatively proposed for the complexes.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1152-1156
Synthesis and spectroscopic studies on platinum(II) complexes of
thiosemicarbazone derivatives of p-anisaldehyde, p-tolualdehyde and pvanillin
Narayan T Akinchan* & Richa Akinchan
The platinum(II) complexes of thiosemicarbazone derivatives of p-anisaldehyde (ATSCH), p-tolualdehyde
(TTSCH) and p-vanillin (VTSCH) have been prepared and characterized by analytical, molar conductance, infrared,
electronic, 1H and 13C NMR spectral data. Thiosemicarbazones exist in thione form and coordinate through
thiolato/thione sulphur and azomethine nitrogen. The chloro bridged dinuclear structures for [Pt(ATSC)Cl] 2,
[Pt(TTSC)Cl]2 and [Pt(VTSC)Cl]2 having four coordinate platinum(II) centres and square planar for [Pt
(ATSCH)2]Cl2, [Pt(TTSCH)2]Cl2 and (Pt(VTSCH)2Cl2 are suggested.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1157-1162
Heterobimetallic chemistry : Heterobimetallic complexes derived from
monometallic copper(II) complex of bis(2-hydroxy-1naphthaldehyde)malonoyldihydrazone
R A Lal*, J Chakraborty , S Bhaumik & A Kumar
Monometallic copper(II) complex [Cu(LH2)(H2O)2] ( 1) and heterobimetallic complexes [MCu(L)(H2O)3]
(where M = UO2(2) and Zn(4)) and [MCu(L)(H2O)4] (where M = MoO2(3), Ni(5), Co(6) and Mn(7)) and
homobimetallic copper(II) complex [Cu2(L)(H2O)4].2H2O(8) have been isolated and characterized by analytical,
molecular weight, magnetic moment, electrical conductance, electronic IR and ESR spectral data. IR spectral
evidences indicate that dihydrazone coordinates to the metal centres in enol forms. The monometallic copper(II)
complex (1) and the heterobimetallic complexes UO2Cu (2) and MoO2Cu (3) and Zn-Cu (4) are normal
paramagnetic indicating absence of any metal-metal interaction in the structural unit of the complexes while the
remaining heterobimetallic complexes Ni-Cu(5), Co-Cu (6) and Mn-Cu (7) have much less eff values than those
required for 3, 4 and 6 unpaired electrons indicating considerable metal – metal interactions. Copper has distorted
octahedral geometry in monometallic and heterobimetallic complexes. Uranium has pentagonal bipyramidal
stereochemistry while zinc has square pyramidal stereochemistry. However, copper(II) has square pyramidal
stereochemistry in homobimetallic complex (8).
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1163-1166
QSAR study on antiviral activity of ester prodrugs of
6-methoxypurine arabinosides
Vijay K Agrawal, Ruchi Sharma & P V Khadikar*
The varicella-zoaster antiviral activity of 6-methoxy purine arabinosides has been modelled using simple as
well as multi-variate regression analysis. Excellent results are obtained in curvilinear regression. The predictive
potential of the model is discussed on the basis of cross-validation parameters.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1167-1172
Thermodynamics of molecular interactions in mixtures containing ether
V K Sharma* & Romi
Molar excess volumes, VE and molar excess enthalpies, HE, for 1,3-dioxolane(i) + benzene or toluene or + o, or + p or +m 
xylene(j) binary mixtures have been measured by dilatometer and microflow calorimeter as a function of composition at the
temperature 298.15K. The observed data have been analysed in terms of (i) the Graph-theoretical approach, (ii) Flory’s approach
and (iii) Sanchez and Lacombe’s theory. The analysis of VE data by Graph-theoretical approach suggest that various (i+j)
mixtures are characterized by interactions between delocalised -electron cloud of aromatic ring of aromatic hydrocarbons and 
electrons of oxygen atoms in 1, 3-dioxolane. The IR studies lend further credance to the nature and extent of interactions with
support for the proposed structures in studied mixtures. It has also been observed that VE and HE data calculated by Graph theory
compare well with their experimental values.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1173-1176
Surface tension studies of ternary system: Copper soap plus benzene
plus methanol at 313 K
V P Mehta, P R Talesara, Rashmi Sharma*, Antima Gangwal & Renu Bhutra
Colloidal behaviour of copper soap solution in benzene plus methanol mixture from the surface tension studies confirms that
cmc values depend upon the composition of the solvent mixture and are found to decrease with increase in chain length of the
soap anion. The results of the surface tensions have been explained on the basis of Szyszkowski’s empirical equation and it is
observed that the values X, Y, and (-X ln Y) lead to the confirmation of the fact that the change in the behaviour of the soap takes
place at 50% methanol concentration. The plots of the parachor against the mole fraction of the soap are characterised by an
intersection of two straightlines at the cmc of the soap. Hammic and Andrew’s equation has been successfully applied to explain
the behaviour of soap in benzene-methanol mixture.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1177-1183
Oxidative dehydrogenation of ethylbenzene over La and Dy supported
vanadia
S Sugunan* & N K Renuka
A series of supported vanadia systems have been prepared by excess solvent technique using La 2O3 and Dy2O3 as supports.
Physical characterization has been carried out using XRD, FTIR, TG studies, BET surface area measurement, pore volume
analysis etc. Cyclohexanol decomposition has been used as a test reaction for evaluating the acid base properties of the supported
system. The oxidative dehydrogenation of ethylbenzene has been employed as a chemical probe reaction to examine the catalytic
activity. The active species correspond to amorphous and crystalline tetrahedral vanadyl units in the supported system.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1184-1187
Determination of osmotic coefficients of aqueous solutions of
polyhydroxylated compounds at various temperatures
Zuo-Ning Gao*, Jin-Fu Li & Xiao-Lin Wen
Osmotic coefficients of aqueous solutions of polyhydroxylated compounds such as glycol, glycerol, sucrose and glucose at
various temperatures over the concentration range of 0.0 ~ 2.1 mol kg-1 and 0.0 ~ 2.0 mol kg-1 have been determined,
respectively. Using a linear least-squares fitting routine, the osmotic coefficients have been fitted by a simple polynomial
equation. It is found that the relation between the experimental results of the molal osmotic coefficients  and the molal
concentration of the solution m are in agreement with that from the polynomial fitting at various temperatures. The experimental
results also show that over the studied concentration range and at various temperatures, the molar osmotic coefficients of aqueous
solutions increase with increase in concentration of solutes. The aqueous glycol solution system exhibits the properties of the
ideal solution.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1188-1190
Kinetics and mechanism of the interaction of thiosemicarbazide with di-hydroxo bis(bipyridyl)dipalladium(II) ion
Sankar Chandra Moi, A K Ghosh* & G S De
Kinetics of interaction between thiosemicarbazide with the title complex has been studied spectrophotometrically as a
function of [Pd2(bipy)2(OH)22+], [thiosemicarbazide], pH and temperature. The reaction has been monitored at 280 nm, the max
of the substituted complex, where the spectral difference between the reactant and the product is maximum. The reaction rate
increases linearly with increase in [thiosemicarbazide]. The second order rate constants have been calculated from the slope of
the kobs versus [ligand] plot. From the experimental findings an associative mechanism for the substitution process is suggested.
The activation parameters (H = 50.4  1.9 kJ mol-1, S = -105  6 J K-1 mol-1) also support the proposition.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1191-1194
Kinetics and mechanism of the reaction of
hydroxopentaaquarhodium(III) ion with L-aspartic acid in aqueous
media
S Mohanty, S Anand & P Mohanty*
The kinetics of the reaction of L-aspartic acid (H3L+) with hydroxopentaaquarhodium (III) has been studied over the range
2.58≤103[H3L+] ≤12.90, 3.49 ≤pH≤ 4.3, 50≤ t ≤65C and I=0.1mol dm3(NaClO4).The reaction takes place via an outer sphere
association between RhOH2+ and (H3L+) followed by transformation of the outer into an inner-sphere complex (chelate is
formed) by slow interchange. The anation rate constant RhOH3+ at 25C and I= 0.1mol dm (NaClO4) is found to be 2.2106s–1.
∆H# and ∆S# for kan path are found to be 62.0±1.2 kJ mol1 and –120.8 ±3.4 JK1mol1 respectively. Anation reaction of RhOH2+
follows an Ia path.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1195-1198
Kinetic and mechanistic investigation of the reaction of cis-diaquabis(ethylenediamine) cobalt(III) with glycylglycine in aqueous solution
Debabrata Chatterjee* & Biswajit Ruj
]3+
The reaction of cis-[Co(en)2(H2O)2 (complex-1) with glycylglycine (gly.gly) resulted in the formation of a mixed-chelate
cis-[Co(en)2(gly.gly)]2+ product (complex-2). The kinetics of the reaction has been studied spectrophotometrically as a function
of [complex-1], [gly.gly], pH, ionic strength (ClO4 and NO3) and temperature (25-55C). Kinetic data and activation
parameters are compared to all available literature information which confirms the proposed conventional dissociative
interchange mechanism involving pre-association of complex-1 ion and gly.gly species in the present reaction.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1199-1201
The crystal structure and spectroscopic studies of iron(III)tris(8quinolinolato-N,O), [Fe(C9H6NO)3]C2H5OH complex
Shusheng Zhang, Jingbo Xue & Fangfang Jian*
The crystal and molecular structure of the complex [Fe(Quin)3]C2H5OH [Quin = 8-hydroxyquinoline-N,O] has been
determined by X-ray crystallography. The complex crystallizes in the monoclinic system, space group Pn, with lattice parameters
a = 11.229(2), b = 13.483(3), c = 16.753(3) Å, =94.35(3)° and Z = 4. The central Fe atom is coordinated octahedrally with the
three N atoms and three O atoms from three 8-quinolinolato ligands. The three Fe-O bonds distances are in the range of
1.963(11)-2.013(9)Å, while the three Fe-N bond distances range from 2.114(11)-2.253(9)Å. In the solid state, the ligand and the
ethanol moiety form one-dimensional hydrogen bonds network through O(1)...H-O(4) intermolecular hydrogen bond.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1202-1204
Cation- interactions: Synthesis and crystal structure of complex
[K(DB18C6)]I3
Qingjiang Yu, Tong Wang , Jianmin Dou*, Dacheng Li & Daqi Wang
A dibenzo-18-crown-6 (DB18C6) complex, [K(DB18C6)]I3 has been isolated and characterized by elemental analysis, IR and
X-ray diffraction analysis. The complex belongs to triclinic, space group P2 1/c with cell dimensions, a = 0.97870(17), b =
1.6909(3), c = 1.5435(3) nm,  = 98.435(3)º, V = 2.5266(7) nm3, Z = 2, Dcalc. = 1.026 Mg/m3, F(000) = 740, R1 = 0.0534 and
wR2 = 0.1666. In the solid state, two [K(DB18C6)] + complex cations form a dimeric structure bridged by K+- interactions.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1205-1207
Spectral and thermal studies of homodinuclear and
heterodinuclearglutathione complexes
Bhagwan S Garg*, Deo Nandan Kumar & B K Singh
The complexes of the types [M2LSO4.2H2O] where L=GSH, M = Co(II), Cu(II), Zn(II), Cd(II) and
[MM'LSO4.2H2O] where L = GSH, M = Cu(II), M' = Zn(II) and M = Co(II), M' = Cd(II)] have been prepared and
characterized by elemental analysis, magnetic susceptibility measurements, IR, EPR, electronic spectral studies and
thermal analysis. Deprotonation and coordination of thiol group occurs and glycine residue binds with the metal
ions in all the complexes. Copper(II) and cobalt(II) complexes show low magnetic moment. EPR spectral data show
that complexes have planar geometry. Ligand to metal charge transfer are observed in all the complexes and d-d
transition are also observed in copper(II) and cobalt(II) complexes. Thermal decomposition of all the complexes
proceeds via first order kinetics.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1208-1211
A study of the underpotential depositedhydrogen on the nickel deposited
electrode in alkaline media
M Jafarian*, M G Mahjani, M Hoseni & F Gobal
Hydrogen evolution reaction has been studied on the nickel deposited electrode. Two reduction peaks at –1V/Ag-AgCl and –
1.3V/Ag-AgCl and one oxidation peak at –1.3V/Ag-AgCl have been observed. Shift due to oxidation peak arises from change of
cathodic limit, attributed to the two competitive reactions on the surface. The peak located on the more anodic side is due to the
oxidation of HUPD and the second peak due to the oxidation of HOPD. The sodium ion has no effect on the hydrogen evolution
reaction. The diffusion coefficient of hydrogen is calculated to be D=2.88×10 -10 cm2s-1using impedance technique.
Indian Journal of Chemistry
Vol. 41A, June 2002, pp. 1212-1216
Silica enriched faujasitic zeolite-Y from flyash
S U Meshram, S S Rayalu*, K N Munshi & M Z Hasan
Various process modifications to enrich silica in zeolite-Y have been carried out by increasing substantially the SiO2 /Al2O3
ratio from 1.8-2.0 to 2.5-3.0 with consequent increase in thermal stability. Some new phases of zeolites have been observed with
improved silica alumina ratio up to 3.0 to 3.5. Crystallinity has been monitored by XRD analysis, ranging from 70-99% for
different samples