Indian Journal of Chemistry

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

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

VOLUME 54A

NUMBER 9

SEPTEMBER 2015

 

CONTENTS

 

 

1069

 

Computational modeling of novel donor-acceptor ternary copolymers: Some interesting results

 

 

 

 

 

 

 

 

Priyanka Thakral & A K Bakhshi*

 

 

 

 

 

 

1076

 

Enhanced photocatalytic Fe3+ reduction with H2O2 generation by TiO2 anatase/rutile blend

 

 

 

 

 

 

 

 

 

 

 

C Karunakaran*, D Vasumathi &
P Vinayagamoorthy

 

 

 

Photocatalytic reduction of Fe3+ ion with formation of H2O2 is higher by rutile blended anatase TiO2 than by anatase TiO2 nanocrystals.

 

 

 

 

1085

 

Oxidation of amoxicillin by hexacyanoferrate(III) in aqueous alkaline medium¾A kinetic and mechanistic approach

 

 

 

 

 

 

 

 

 

 

 

 

Amar K Durgannavar, Manjanath B Patgar & Shivamurti A Chimatadar*

 

 

 

 

 

Notes

 

1092

 

On the structural, morphological and gas sensing properties of nanocrystalline SnO2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A Muthuvinayagam & B Viswanathan*

 

 

 

The gas response of crystalline SnO2 nanoparticles synthesized by an oleic acid assisted solvothermal process increases nearly linear as the concentration of LPG increases from 500 ppm to 2000 ppm and is maximum at 250 °C.

 

 

 

 

1098

 

Two novel coordination polymers based on multicarboxylate derivatives and flexible dipyridyl ligand: Synthesis, structures and photoluminescent properties

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xiao-Ling Li, Liu*, Ling-Yun Xin,
Gui-Lian Li, Lu-Fang Ma & Jing-Wen Li

 

 

 

The reactions of 1,2-bi(4-pyridyl)ethane (bpa) and
4-hydroxyphthalic acid
(H2hpc) with Zn/Cd(II) salts yield two novel 2D layer structures. [Zn(hpc)(bpa)]n comprises hpc anion-bridged mononuclear Zn(II) chains that are joined further by flexible trans-bpa ligands into a 2D layer. Different from the Zn(II) complex, the 2D layer structure of [Cd(hpc)(bpa)(H2O)]n features hpc-bridged binuclear Cd(II) motifs cross-linked by flexible trans-bpa ligands along different directions. These complexes show slightly different fluorescent properties, probably due to different metal ions and coordination environments.

 

 

 

 

1104

 

Reaction of electron-deficient triosmium cluster Os3(CO)83-Ph2PCH(CH3)P(Ph)C6H4}(μ-H) with HCl: X-ray structure of two isomers of Os3(CO)8{μ-Ph2P-CH(CH3)PPh2}(μ-Cl)(μ-H)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Md Miaz Uddin, Subas Rajbangshi, Shishir Ghosh, Tasneem A Siddiquee & Shariff E Kabir*

 

 

 

Reaction of electron-deficient Os3(CO)83-Ph2PCH(CH3)-P(Ph)C6H4}(μ-H) with HCl yields two new triosmium clusters with the formula, Os3(CO)8{μ-Ph2PCH(CH3)PPh2}(μ-Cl)(μ-H).

 

 

 

 

1109

 

Chlorine dioxide-iodine-acetylacetone oscillation reaction investigated by UV-vis spectrophotometry

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Laishun Shi*, Demei Li, Jingjing Chen & Jian Gao

 

 

 

A new chlorine dioxide-iodine-acetylacetone chemical oscillatory reaction is studied by UV-vis spectrophotometry. Equations for the starch-triiodide complex reaction rate are obtained, and a plausible reaction mechanism is proposed for the oscillation reaction.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1069-1075

 

 

Computational modeling of novel donor-acceptor ternary copolymers:
Some interesting results

Priyanka Thakral & A K Bakhshi*

Department of Chemistry, University of Delhi, Delhi 110 007, India

Email: akbakhshi2000@yahoo.com

Received 8 July 2015; revised and accepted 27 August 2015

In this study, donor-acceptor (D-A) polymerization has been combined with copolymerization for blueprinting low band gap ternary D-A copolymers based on first two members of Groups XIV and XVI of periodic table using a computational modeling approach. The first members of Groups XIV and XVI alter and modulate the electronic structures and properties of copolymers more in comparison with the respective second members. However, the presence of second members of the respective groups provides electronic flexibility to the overall copolymer backbone.

Keywords: Computational chemistry, Conducting polymers, Copolymers, Electronic properties, Donor-acceptor polymerization, Particle swarm optimization.

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1076-1084

 

 

Enhanced photocatalytic Fe3+ reduction with H2O2 generation by
TiO2 anatase/rutile blend

C Karunakaran*, D Vasumathi & P Vinayagamoorthy

Department of Chemistry, Annamalai University, Annamalainagar 608 002, Tamilnadu, India

Email: karunakaranc@rediffmail.com

Received 2 March 2015; revised and accepted 25 August 2015

TiO2 P25 Degussa, TiO2 Hombikat, anatase TiO2 and WO3 nanocrystals photocatalyze the reduction of iron(III) ion in aqueous acidic solution with generation of hydrogen peroxide. The photocatalytic activities of TiO2 P25 and TiO2 Hombikat are much higher than those of anatase TiO2 and WO3. The nanomaterials have been characterized by powder X-ray diffraction and solid state impedance, UV-visible diffuse reflectance and photoluminescence spectroscopies. The photoreduction decreases with increase of iron(III) ion concentration because of inner filter effect. While the photoreaction is slow at high acidity the reaction rate increases with increase in photon flux. Molecular oxygen does not play any role in the photoreduction. The Fe(III)-reduction is more effective with UV-C light than with UV-A light. The nanooxides show sustainable photocatalytic activity. Charge separation between anatase and rutile phases is the likely reason for the observed large photocatalytic activities of TiO2 P25 and TiO2 Hombikat.

Keywords: Photooxidation, Photoreduction, Photocatalysis, Interparticle charge transfer, Iron, Titania

 

 

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1085-1091

 

 

Oxidation of amoxicillin by hexacyanoferrate(III) in aqueous alkaline
medium—A kinetic and mechanistic approach

Amar K Durgannavar, Manjanath B Patgar & Shivamurti A Chimatadar*

P. G. Department of Studies in Chemistry, Karnatak University, Pavate Nagar, Dharwad 580 003, India

Email: schimatadar@gmail.com

Received 19 February 2015; revised and accepted 19 August 2015

The kinetics and mechanism of oxidation of amoxicillin by hexacyanoferrate(III) in aqueous alkaline medium at constant ionic strength of 0.10 mol dm-3 is studied spectrophotometrically at 25 °C. The reaction exhibits 2:1 ([Fe(CN)6]3-: amoxicillin) stoichiometry. The reaction products have been identified with the help of TLC and characterized by FT-IR, GCMS and LCMS. The reaction is first order in hexacyanoferrate(III) concentration but fractional order in both amoxicillin and alkali concentrations. The effects of ionic strength and dielectric constant have been investigated. In a composite equilibrium step, amoxicillin binds to hexacyanoferrate(III) to form a complex that subsequently decomposes to the products. Based on investigation of the reaction at different temperatures, computation of the activation parameters with respect to the slow step of the proposed mechanism was evaluated.

Keywords: Kinetics, Reaction mechanism, Oxidation, Amoxicillin, Hexacyanoferrate(III)

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1092-1097

 

 

On the structural, morphological and gas sensing properties of nanocrystalline SnO2

A Muthuvinayagama & B Viswanathanb, *

aDepartment of Physics, Indian Institute of Technology Madras, Chennai 600 036, India

bNational Centre for Catalysis Research, Indian Institute of Technology Madras, Chennai 600 036, India

Email: bvnathan@iitm.ac.in

Received 8 July 2015; revised and accepted 28 August 2015

Tin salt precursor capped by oleic acid under solvothermal conditions gives tetragonal rutile phase of SnO2 with average particle size of 14 nm with a band gap of 4.27 eV. The SnO2 nanoparticles exhibit photoluminescence with an intense purple emission band at 425 nm. The transmission electron micrographs show the growth of nanoparticles in specific orientation. The petroleum gas sensing response of this material decreases with increase of sensing temperature.

Keywords: Nanoparticles, Semiconducting oxides, Quantum dots, Gas sensors, Oxides, Tin oxides, Solvothermal method

 

 

 

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1098-1103

 

 

Two novel coordination polymers based on multicarboxylate
derivatives and flexible dipyridyl ligand:
Synthesis, structures and photoluminescent properties

Xiao-Ling Li, Guang-Zhen Liu*, Ling-Yun Xin, Gui-Lian Li, Lu-Fang Ma & Jing-Wen Li

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, 471022, PR China

Email: gzliuly@126.com

Received 24 March 2015; revised and accepted 28 August 2015

The reactions of 4-hydroxyphthalic acid (H2hpc) and 1,2-bi (4-pyridyl) ethane (bpa) with Zn/Cd (II) salts yield two novel 2D layer structures. [Zn(hpc)(bpa)]n (1) consists of hpc anion-bridged mononuclear ZnII chains that are joined further by flexible trans-bpa ligands into a 2D layer. Different from complex (1), the 2D layer structure of [Cd(hpc)(bpa)(H2O)]n (2) features hpc-bridged binuclear cadmium(II) motifs cross-linked by flexible trans-bpa ligands along different directions. Photoluminescence measurements of (1) and (2) in the solid state at room temperature show that there is a slight difference in their fluorescent properties probably due to the different metal ions and coordination environments, which allows a case study on the structure-property correlation.

Keywords: Coordination chemistry, Coordination polymers, Photoluminescent properties, Cadmium, Zinc, Hydroxyphthalic acid

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1104-1108

 

 

Reaction of electron-deficient triosmium cluster Os3(CO)83-Ph2PCH(CH3)-
P(Ph)C6H4}-(μ-H) with HCl: X-ray structure of two isomers of
Os3(CO)8{μ-Ph2PCH(CH3)PPh2}(μ-Cl)(μ-H)

Md Miaz Uddina, Subas Rajbangshia, Shishir Ghosha, Tasneem A Siddiqueeb & Shariff E Kabira, *

aDepartment of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh

Email: skabir_ju@yahoo.com

bDepartment of Chemistry, Tennessee State University, 3500 John A Merritt Blvd, Nashville TN 37209, USA

Received 11 May 2015; accepted 26 August 2015

Treatment of electron-deficient Os3(CO)83-Ph2PCH(CH3)-P(Ph)C6H4}(μ-H) (1) with HCl at room temperature furnishes the adduct Os3(CO)8{μ-Ph2PCH(CH3)PPh2}(μ-Cl)(μ-H) (2) in almost quantitative yield via oxidative addition of HCl bond. Cluster (2) is electron-precise and contains bridging chloride and hydride ligands which rearranges upon heating at 110 °C to form isomeric (3). Both clusters have been characterized by a combination of elemental analyses, IR and NMR spectroscopic data together with single crystal X-ray diffraction studies.

Keywords: Coordination chemistry, Cluster compounds, Triosmium clusters, Protic acids, Osmium, Carbonyls, 1,1’-Bis(diphenylphosphino)ethane

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, September 2015, pp. 1109-1113

 

 

Chlorine dioxide–iodine–acetylacetone oscillation reaction investigated by
UV-vis spectrophotometry

Laishun Shi*, Demei Li, Jingjing Chen & Jian Gao

School of Chemistry and Chemical Engineering, South Campus, Shandong University,
Jinan 250061, PR China

Email: lshunsh@sdu.edu.cn

Received 4 February 2015; revised and accepted 7 August 2015

A new chlorine dioxide-iodine-acetylacetone chemical oscillatory reaction has been studied by UV-vis spectrophotometric method. The initial concentrations of acetylacetone, chlorine dioxide, iodine, sulfuric acid, and the pH value influence the oscillation observed at wavelength of 575 nm for the starch-triiodide complex. There is a pre-oscillatory or induction stage and the amplitude and the number of oscillations depend on the initial concentration of the reactants. Equations for the starch-triiodide complex reaction rate change with reaction time and the initial concentrations in the oscillation stage have been obtained. The induction time decreases linearly with the initial concentration of acetylacetone. The oscillation reaction can be accelerated by increasing the reaction temperature. The apparent activation energies at the induction stage and the oscillation stage are 24.94 kJ/mol and 7.38 kJ/mol, respectively. Generating the enol isomer by keto-enol tautomerism is an important step to constrain the time of induction period.

Keywords: Oscillation reactions, Chemical oscillations, UV-vis spectrophotometry, Activation energy,
Apparent activation energy,
Chlorine dioxide, Acetylacetone