Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

 

VOLUME 47A

NUMBER 7

July 2008

CONTENTS

979

A comparative study between the effective pair potential parameters obtained from different equations of states

 

 

 

 

F Kermanpour* & N Farzi

 

Internal energy of liquid methane has been obtained based on the pair-wise additive approximation for the effective pair potential of dense fluids using (12,6) Lennard-Jones model for the intermolecular potential function. This internal energy has been compared with the internal pressure via the equation of state  expressions. The effective pair potential parameters have been calculated using these values. Applying the pair-wise additive approximation, total energy and other thermodynamic functions have been calculated.

 

986

Synthesis, crystal structure, electronic spectra and density functional studies on 1N-phenyl-3-(3,4-dichlorophenyl)-5-phenyl-2-pyrazoline

 

 

 

 

 

 

 

 

 

 

Pu Su Zhao*, Hong Yan Wang, Rong Qing Li &

Huan Mei Guo

 

1N-Phenyl-3-(3,4-dichlorophenyl)-5-phenyl-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-vis and X-ray single crystal diffraction studies.

 

992

Double aromatic amine addition across ruthenium(III) coordinated bis-nitrile function

 

 

 

 

 

 

 

 

 

 

Sudipta Chatterjee, M Nethaji &
Sreebrata Goswami*

 

Double aromatic amine addition reaction at a bisacetonitrile complex of ruthenium(III) is reported.

 

 

996

Microwave assisted synthesis, characterization and antimicrobial studies of unsymmetric imine complexes of organotitanium(IV) and organozirconium(IV)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Kavita Poonia, Monika Swami, Ashu Chaudhary &
R V Singh*

 

A new class of unsymmetrical organotitanium(IV) and organozirconium(IV) complexes of biologically potent ligands derived from heterocyclic ketones and semicarbazide hydrochloride and 2-hydroxy-N-phenyl benzamide have been prepared by the microwave irradiations.

 

 

1004

Synthesis and characterization of hydrotalcites: Potential thermal stabilizers for PVC

 

 

 

 

 

 

Savita Gupta*, D D Agarwal & Susanta Banerjee

 

A new series of Ca-Al-X (X=NO3-, CO32-, Cl-, SO42-, PO43-) hydrotalcites have been prepared by hydrothermal process.

 

 

 

Notes

 

1009

Synthesis and characterization of dioxouranium(VI), thorium(IV), oxozirconium(IV) and oxovana-dium(IV) complexes with 1,11-dihydroxy-
1,4,5,7,8,11-hexaaza-2,3, 9, 10-tetramethyl-1, 3, 8, 10-decatetraene-6-thione and their derivatives with chloroacetic acid

 

 

 

D C Dash*, A Mahapatra, R K Mohapatra,
S Ghosh & P Naik

 

A series of complexes of the type [M(DHTMDT)(NO3)n].2H2O and [VO(DHTMDT)(SO4)].2H2O, has been synthesized. Reactions of the complexes with monochloroacetic acid yield another series of complexes of the type, [M(HDBIT)(NO3)n].2H2O and [VO(HDBIT)(SO4)].2H2O.

 

1014

Molecular interactions of polyvinylpyrrolidone and cellulose acetate butyrate solutions in dimethyl-formamide

 

 

M Selvakumar, D Krishna Bhat* &
N G Renganathanb

 

The ultrasonic velocity, density and viscosities of the polyvinylpyrrolidone and cellulose acetate butyrate solutions in dimethylformamide have been measured. Using these data, free energy of mixing, solvation number and different polymer-solvent interaction parameters for the solution systems have been calculated to know the presence of molecular interactions in the system. The trends in the variation of the solution property parameters indicate the existence of positive molecular interactions between the polymer and the solvent in solutions.

 

1020

Intermolecular free length and free volume of pure liquids at varying temperatures and pressures

 

 

J D Pandey*, Vinay Sanguri,  M K Yadava&
Aruna Singh

 

Intermolecular free length and free volume of four cyclic alkanes, viz., cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane, have been calculated at different temperatures and varying pressures. The values of intermolecular free length have been computed from thermoacoustical method and compared with the values obtained from the well-established thermodynamic method.

 

1026

Densities, viscosities and speeds of sound of binary mixtures of phenylacetonitrile with some aliphatic alcohols at 308.15 K

 

Ranjith Kumar Bachu, Murali Krishna Patwari, Sathyanarayana Boodida,  Savitha Jyostna Tangeda & Satyanarayana Nallani*

 

Excess molar volumes, deviation in viscosity and isentropic compressibilities of binary mixtures formed by phenylacetonitrile with aliphatic alcohols (1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2-propanol) have been evaluated from experimental measurements of density, viscosity and speed of sound at T = 308.15 K. The properties have been fitted to the Redlich-Kister polynomial using multiparametric non-linear regression analysis to estimate the binary coefficients and standard errors. The values of these parameters have been discussed in terms of molecular interactions.

 

1032

Brij-35 micellar catalysed chloramine-T oxidation of vitamins: A kinetic study

 

 

 

 

 

 

 

 

 

 

 

 

 

Varuna Shukla & Santosh K Upadhyay*

 

The kinetics of oxidation of the vitamins (B1 and B6) by sodium salt of p-toluene sulfonamide (chloramine-T) have been studied in presence of the non-ionic surfactant, Brij-35, in perchloric acid medium.

 

1037

Kinetics of oxidation of non-ionic surfactants
(Triton X-100 and Brij-35) by KMnO4 in H2SO4 medium

 

 

 

 

 

 

 

 

 

 

 

 

 

Pragya Shukla & Santosh K Upadhyay*

 

 

The kinetics of oxidation of non-ionic surfactants, Triton X-100  and Brij-35, by potassium permangnate in aqueous H2SO4 medium have been investigated in the temperature range 35-45°C. The reactions show first order dependence of rate with respect to [MnO4]. The order of reaction in surfactant and H2SO4 decreases from unity at higher [surfactant] and [H2SO4], respectively.

 

1041

Extraction chromatographic separation of Ga(III) with the high molecular mass liquid cation exchanger SRS-100

 

 

 

Bhabatosh Mandal* & Niladri Ghosh

 

A selective method has been developed for the extraction chromatographic separation of Ga(III) with SRS-100 coated on silanised silica gel and shows quantitative recovery (>99%) with a preconcentration of ~53 and relative error within ±1.0%. The method effectively permits sequential separation of Ga(III) from synthetic quaternary mixtures containing its congeners Al(III), In(III) and Tl(III). A plausible mechanism for the extraction of Ga(III) is also suggested.

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 979-985

 

A comparative study between the effective pair potential parameters obtained from different equations of states

 

F Kermanpour* & N Farzi

Received 8 January 2008; revised 4 June 2008

Internal energy of liquid methane has been obtained based on the pair-wise additive approximation for the effective pair potential of dense fluids using (12,6) Lennard-Jones model for the intermolecular potential function. This internal energy has been compared with the internal pressure via the equation of state (EoS) expression. Thus, the effective pair potential parameters (EPPP) through some given EoSs for dense fluids have been calculated. A relation between the potential parameters with EoS parameters has been obtained. Using the obtained EPPPs and applying the pair-wise additive approximation, one could calculate accurately the thermodynamics functions such as total energy. The results of such calculations for the total energy of the liquid methane obtained via the EPPPs from different EoSs indicate a good agreement with the experimental data. Physical interpretation for the state dependencies of the obtained EPPPs from given EoSs is also presented.

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 986-991

 

Synthesis, crystal structure, electronic spectra and density functional studies on 1N-phenyl-3-(3,4-dichlorophenyl)-5-phenyl-2-pyrazoline

Pu Su Zhao*,  Hong Yan Wang, Rong Qing Li & Huan Mei Guo

Received 20 March 2008; revised 16 May 2008

1N-Phenyl-3-(3,4-dichlorophenyl)-5-phenyl-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-vis and X-ray single crystal diffraction studies. Density functional calculations have been carried out for the compound by using B3LYP method at 6-311G** basis set. The calculated results show that the predicted geometry resembles the structural parameters. The electronic absorption spectra calculated in gas phase are better than those calculated in EtOH solvent to model the experimental electronic spectra and the Natural Bond Orbital (NBO) analyses suggest that the above electronic transitions are mainly assigned to π π* transitions. On the basis of vibrational analyses, the thermodynamic properties of the compound at different temperature have been calculated, revealing the correlations between C0p, m, S0m and temperature.

 

 

Indian Journal of Chemistry

Vol.  47A, July 2008, pp. 992-995

 

Double aromatic amine addition across ruthenium(III) coordinated
bis-nitrile function

Sudipta Chatterjee,   M Nethaji  & Sreebrata Goswami*

Received 11 April 2008; revised 22 May 2008

Double aromatic amine addition reaction at a bisacetonitrile complex of ruthenium(III) is reported here. The cationic complex, cis-[(acac)2Ru(CH3CN)2](ClO4) (1) [acac = acetylacetonate] reacts with aniline in neat to produce an orange bis-amidine complex, [RuIII(acac)2{HN=C(Me)NHPh}2](ClO4), [2]ClO4 in 60% yield. X-ray structure of the complex is also reported. The reaction occurs with addition of two equivalents of PhNH2 across the two coordinated acetonitrile ligands. Optical spectra and redox properties of the complex have been discussed. It shows a reversible Ru(III)/Ru(II) response at -0.6 V and its visible spectrum is dominated by a broad ligand to metal charge transfer at 505 nm.

IPC Code: Int Cl.8 C07F15/00

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 996-1003

 

Microwave assisted synthesis, characterization and antimicrobial studies of unsymmetric imine complexes of organotitanium(IV) and organozirconium(IV)

Kavita Poonia, Monika Swami ,  Ashu Chaudhary  & R V Singh*

Received 3 May 2007; revised 19 May 2008

A new class of unsymmetrical organotitanium(IV) and organozirconium(IV) complexes of biologically potent ligands derived from heterocyclic ketones and semicarbazide hydrochloride and 2-hydroxy-N-phenyl benzamide have been prepared by the microwave irradiations. The ligands act in monobasic bidentate manner with NÇOH and OÇOH as donor systems. The ligands and the resulting complexes of the type Cp2M(OÇO) (NÇO) (where M represents titanium or zirconium) are characterized by the elemental analysis, conductance measurements, molecular weight determinations and spectral studies. On the basis of the electronic, IR, 1H NMR and 13C NMR spectral studies, octahedral geometry has been proposed for the resulting complexes. The isolated products are coloured solids, soluble in methanol, DMF, DMSO and THF. A comparative study has been made between microwave assisted synthesis and the thermal synthesis. All the complexes and their parent ligands have been screened against a number of microbes and discussed with positive findings.

IPC Code: Int. Cl.8 C07F7/00

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1004-1008

 

Synthesis and characterization of hydrotalcites: Potential thermal stabilizers for PVC

Savita Gupta*,  D D Agarwal  & Susanta Banerjee

                                Received 9 January 2008; revised 2 July 2008 

Layered double hydroxides (LDH) are considered as a new emerging class of PVC stabilizers to replace toxic and environmentally hazardous class of heavy metals. A new series of Ca-Al-X (X=NO3-, CO32-, Cl-, SO42-, PO43-) hydrotalcites have been prepared by hydrothermal process. The hydrotalcite particles are nanosized and have been characterized by EDX, XRD, FTIR and TGA techniques. A comparative study has been carried out to evaluate the effect of anions on PVC stabilization mechanism. A clear anionic effect is observed when they are subjected to HCl evolution studies. Color stability and UV-Vis spectroscopic studies of stabilized and unstabilized polymeric sheets support the long-term stability behavior of LDHs. A mechanistic approach indicates the role of adsorption process along with ion-exchange.

IPC Code: Int. Cl.8 C08F141/06; C08K3/20

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1009-1013

 

Synthesis and characterization of dioxouranium(VI), thorium(IV), oxozirconium(IV) and oxovanadium(IV) complexes with 1,11-dihydroxy-1,4,5,7,8,11-hexaaza-2,3,9,10-tetramethyl-1,3,8,10-decatetraene-6-thione and their derivatives with chloroacetic acid

D C Dash*, A Mahapatra, R K Mohapatra, S Ghosh & P Naik

Received 4 December 2007; revised 6 June 2008

A series of complexes of the type [M(DHTMDT)(NO3)n].2H2O and [VO(DHTMDT)(SO4)].2H2O, where DHTMDT is the Schiff’s base, 1,11-dihydroxy-1,4,5,7,8,11-hexaaza-2,3,9,10-tetramethyl-1,3,8,10-decatetraene-6-thione derived from thiocarbohydrazide and diacetylmonoxime, have been synthesized. Reactions of the complexes with monochloroacetic acid yield another series of complexes of the type [M(HDBIT)(NO3)n].2H2O and [VO(HDBIT)(SO4)].2H2O, where HDBIT is another Schiff’s base, 3-(1¢-hydroxy-1¢,4¢-diaza-2¢,3¢-dimethyl-1¢,3¢-butene-4¢-yl)-2-(1¢-hydroxy-1¢,4¢-diaza-2¢,3¢-dimethyl-1¢,3¢-butene-4¢-yl)-imino-4-thiazolidinone obtained after cyclization with chloroacetic acid, M= UO2(VI), ZrO(IV) and Th(IV), n=2 for UO2(VI) and ZrO(IV), n=4 for Th(IV). All the complexes are characterized on the basis of elemental analysis, thermal analysis, molar conuctivity, magnetic moment, electronic, infrared, 1H NMR and ESR spectral studies. The results indicate that the VO(IV) ion is penta coordinated yielding paramagnetic complexes; UO2(VI), ZrO(IV) ions are hexa coordinated, whereas Th(IV) ion is octa coordinated yielding diamagnetic complexes of above stoichiometry.

IPC Code: Int. Cl.8 C07F5/00; C07F7/00; C07F9/00

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1014-1019

 

Molecular interactions of polyvinylpyrrolidone and cellulose acetate butyrate solutions in dimethylformamide

M Selvakumar , D Krishna Bhat  * & N G Renganathan

Received 9 January 2008; revised 27 May 2008

The ultrasonic velocity, density, and viscosities of polyvinylpyrrolidone (PVP) and cellulose acetate butyrate (CAB) solutions in dimethylformamide (DMF) have been measured in the temperature range, 303K-323 K. Using these data, free energy of mixing, solvation number and different polymer-solvent interaction parameters for the solution systems have been calculated to know the presence of molecular interactions in the system. The trends in the variation of the solution property parameters indicate the existence of positive molecular interactions between the polymer and the solvent in solutions. The results also show the presence of higher degree of interaction between PVP and DMF in solution compared to CAB and DMF.

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1020-1025

 

Intermolecular free length and free volume of pure liquids at varying temperatures and pressures

J D Pandey, * Vinay Sanguri ,  M K Yadav  & Aruna Singh

Received 29 January 2008; revised 5 June 2008

Intermolecular free length and free volume of four cyclic alkanes, viz. cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane have been calculated at different temperatures and varying pressure. The values of intermolecular free length have been computed from thermoacoustical method and compared with the values obtained from the well-established thermodynamic method.

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1026-1031

 

Densities, viscosities and speed of sound of binary mixtures of phenylacetonitrile with some aliphatic alcohols at 308.15 K

Ranjith Kumar Bachu, Murali Krishna Patwari, Sathyanarayana Boodida,  Savitha Jyostna Tangeda & Satyanarayana Nallani*

Received 28 January 2008; revised 28 May 2008

Excess molar volumes, deviation in viscosity and isentropic compressibilities of binary mixtures formed by phenylacetonitrile with aliphatic alcohols (1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2-propanol) have been evaluated from experimental measurements of density, viscosity and speed of sound at T = 308.15 K. All the properties have been fitted to the Redlich-Kister polynomial using multiparametric non-linear regression analysis to estimate the binary coefficients and standard errors. The values of these parameters have been discussed in terms of molecular interactions.

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1032-1036

 

Brij-35 micellar catalysed chloramine-T oxidation of vitamins: A kinetic study

Varuna Shukla & Santosh K Upadhyay*

Received 13 September 2007; revised 27 May 2008

The kinetics of oxidation of the vitamins (B1 and B6) by sodium salt of p-toluene sulfonamide (Chloramine-T) have been studied in presence of a non-ionic surfactant, i.e., polyoxyethylene(23)laurylether (Brij-35) in perchloric acid medium. Catalytic effect of Brij-35 micelle has been observed on the rate of oxidation. The reactions show first order, fractional order and zero-order dependence of rate with respect to chloramine-T, vitamins and HClO4, respectively. The mechanism in absence as well as in presence of surfactant has been proposed. The spectrophotometric evidence supports the binding/association between chloramine-T and Brij-35 micelle. The kinetic data have also been rationalised in terms of Menger and Portnoy’s kinetic model and binding parameters have been evaluated.

IPC Code: Int. Cl.8 C07B33/00

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1037-1040

 

Kinetics of oxidation of non-ionic surfactants (Triton X-100 and Brij-35) by KMnO4 in H2SO4 medium

Pragya Shukla & Santosh K Upadhyay*

Received 13 September 2007; revised 27 May 2008

The kinetics of oxidation of non-ionic surfactants, viz. polyoxyethylene(10)octylphenol (Triton X-100) and polyoxyethyleneglycol dodecylether (Brij-35) by potassium permangnate in aqueous H2SO4 medium have been investigated in temperature range 35-45°C. The reactions show first order dependence of rate with respect to [MnO4]. The order of reaction in surfactant and H2SO4 decreases from unity at higher [surfactant] and [H2SO4], respectively. Probable reaction mechanism involving an intermediate between surfactant and active species of the oxidant is proposed and constants involved in the rate law have been evaluated.

IPC Code: Int. Cl.8 C07B33/00

 

 

Indian Journal of Chemistry

Vol. 47A, July 2008, pp. 1041-1046

 

Extraction chromatographic separation of Ga(III) with the high molecular mass liquid cation exchanger SRS-100

Bhabatosh Mandal* & Niladri Ghosh

Received 31 January 2008; revised 29 May 2008

A selective method has been developed for the extraction chromatographic separation of Ga(III) with SRS-100 (liquid cation exchanger) coated on silanised silica gel. Its quantitative extraction has been achieved in 2.5 h from 0.1 M acetate buffer (pH 5.5-6.5). The effects of pH, flow-rate and stripping agents on extraction and elution have been investigated. Exchange capacity of the prepared exchanger at different temperatures with respect to Ga(III) has been determined. Breakthrough capacity and preconcentration factor at different pH values have been investigated. The effect of pH on Rf in ion exchange paper chromatography has also been investigated. Ga(III) has been separated from its synthetic binary and multi-component mixtures containing various metal ions as are found in ores and alloy samples. The method effectively permits sequential separation of Ga(III) from synthetic quaternary mixtures containing its congeners Al(III), In(III) and Tl(III). A plausible mechanism for the extraction of Ga(III) is also suggested.

IPC Code: Int. Cl.8 B01D15/08