Indian Journal of Chemistry

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

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

 

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VOLUME 51A

NUMBER 4

APRIL 2012

 

CONTENTS

 

 

549

 

Facile synthesis of SnO2-Pt/carbon nanotubes nanocatalyst with high electrocatalytic performance for methanol oxidation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yunsong Zhang, Li Zhang, Weiguo Liu, Maojun Zhao & Hui Chen*

 

 

 

SnO2-Pt/CNTs nanocomposite with SnO2-around-Pt has been synthesized by in situ spontaneous reduction of PtCl62- with Sn2+ on the CNT surface. SnO2-Pt/CNTs catalyst has higher electrocatalytic mass activity and better electrochemical stability than commercial Pt/C for methanol oxidation.

 

 

 

 

 

 

554

 

Pd(II) catalyzed transformation of Schiff bases
in complexes of the type trans-[PdCl2(NH2Ar-X)2]
(X = H, CH3, Cl): Reactivity with aldehydes and
Heck coupling reaction

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Niraj Kumari, Vinod Kumar Yadav, Stanislav Záliš & Lallan Mishra*

 

 

 

Aniline-Pd complexes of the type trans-[PdCl2 (NH2Ar-X)2] have been synthesized and characterized. These complexes efficiently catalyze the Heck reaction of bromobenzene with acrylonitrile and ethyl acrylate.

 

 

 
564
 

Synthesis and structural characterization of
bis(μ2-aqua)tetrakis(aqua)dilithium(I) bis(4-nitrobenzoate)

 
 
 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bikshandarkoil R Srinivasan*, Santosh Y Shetgaonkar, Kiran T Dhavskar, Jeyaperumal Kalyana Sundar &
Subramanian Natarajan

 

 

 

The structure of [(H2O)4Li2(μ-H2O)2](4-nba)2 exhibits a supramolecular chain of [(H2O)4Li2(μ-H2O)2]2+ cations flanked on either side by 4-nba anions.

 

 

 

 

 

 

571

 

Model chemistries of hydrazides. III: SEMO computations of isonicotinic acid hydrazide, its valence isomers and their isopropyl derivatives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

K Rama Krishna, Ch V Kameswara Rao, V Ananta Ramam, R Sambasiva Rao* &  M Venkata Subba Rao

 

 

 

Quantum chemical studies of isonicotinic acid hydrazide and its isomers at semiemperical level are reported. The bond parameters of INH at SEMO level agree with X-ray crystallographic data. Based on electronic energy, BAH is less stable as compared to INH and PAH, while the iso-propyl group increases the polarity of the hydrazides.

 

 

 

 

 

 

Notes

 

580

 

Mineralization of genotoxic Acid Violet 7 by AgBr-ZnO under alkaline conditions using direct sunlight

 

 

 

 

 

 

 

 

 

 

B Krishnakumar, R Velmurugan, B Subash &
M Swaminathan
*

 

 

 

 

 

586

 

Synthesis of nanocrystalline NiO by sol-gel and homogeneous precipitation methods

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Jeevanandam* & V Ranga Rao Pulimi

 

 

 

The nanocrystalline NiO obtained by calcination of precursor prepared by homogenous precipitation has smaller crystallite size and higher net magnetization value as compared to that obtained from precursor prepared by sol-gel process.

 

                                      

 

 

591

 

Density estimation of normal alkanes from the statistical-thermodynamic perturbation theory based equation of state

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ali Reza Zabeti, Behzad Haghighi*,
Mohammad Mehdi Papari & Ebrahim Ghiamati

 

 

 

An analytical equation of state proposed by Ihm-Song-Mason is employed to calculate the density of normal alkanes (C1 – C10). The method uses the scaling parameters of the potential energy function instead of the thermodynamic properties at critical point as input in the equation of state.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 


Electronic Supplementary Data

 

 

Authors are encouraged to take advantage of the recently started facility to submit supplementary data in the electronic form. These data will be made available along with the online version of the article, with a URL reference in the print version. Supplementary data should be submitted along with the main article and shall be peer reviewed. All supplementary data are considered to be part of the submitted article and should not be included in any other publication.

For further information, contributors may consult the Instructions to Authors at the journal home page.

 

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 549-553

 

Facile synthesis of SnO2-Pt/carbon nanotubes nanocatalyst with high electrocatalytic performance for methanol oxidation

Yunsong Zhanga, Li Zhanga, Weiguo Liub, Maojun Zhaoa & Hui Chena, *

aCollege of Life and Science, Sichuan Agricultural University, Yaan, 625014, China

Email: yaanyunsong@yahoo.com.cn

bAgronomy College, Sichuan Agricultural University, Wenjiang 611130, PR China

Received 25 November 2011; revised and accepted 13 March 2012

A green, low-cost and facile strategy for synthesis of SnO2-Pt/carbon nanotubes nanocomposites with SnO2-around-Pt structure by in situ spontaneous reduction of PtCl62- with Sn2+ on the CNT surface is reported. The morphology and structure of the prepared SnO2-Pt/CNTs nanocatalyst are characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. In addition, energy dispersive
X-ray spectroscopy and inductively coupled plasma-atom emission spectroscopy results prove the presence of Pt and SnO2 nanoparticles on CNTs surface with the molar ratio of Pt:SnO2 in SnO2-Pt/CNTs as 0.48. In comparison with the commercial Pt/C, SnO2-Pt/CNTs nanocatalyst exhibits higher electrocatalytic mass activity and better long-term cycle stability for methanol oxidation.

Keywords: Carbon nanotubes, Nanocatalysts, Electrooxidation, Methanol, Tin dioxide, Platinum

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 554-563

 

Pd(II) catalyzed transformation of Schiff bases in complexes of the type
trans-[PdCl2(NH2Ar-X)2] (X = H, CH3, Cl): Reactivity with aldehydes and
Heck coupling reaction

 

Niraj Kumaria, Vinod Kumar Yadava, Stanislav Záliš b & Lallan Mishraa, *

aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221 005, India

Email: lmishrabhu@yahoo.co.in

bJ Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic,
Dolejškova 3, CZ-18223 Prague, Czech Republic

Received 2 September 2011; revised and accepted 1 March 2012

Schiff bases of type (R-Ph-N=CH-Ph-CH=N-Ph-R), where, R = H (L1), CH3 (L2) and Cl (L3), in presence of cis-[Pd(en)Cl2] or [Pd(DMSO)2Cl2] (en = 1,2-diaminoethane, DMSO = dimethylsulphoxide) give
trans-[PdCl2(NH2Ph)2] (1), trans-[PdCl2(NH2PhCH3)2] (2) and trans-[PdCl2(NH2PhCl)2] (3). The complexes are characterized using spectroscopic (IR, UV-vis and NMR) and X-diffraction techniques. The H-bonding interaction generates multinuclear supramolecular structure in complex (2) and (3). Complex (1) on reaction with benzaldehyde, salicylaldehyde and 4-carboxybenzaldehyde yields complexes of the type [PdCl2(PhN=CHPh)2] (4), [Pd(PhN=CHPhO)2] (5) and [PdCl2(PhN=CHPhCOOH)2] (6) respectively. The structures have been optimized using density functional theory at B3LYP level. Heck coupling reactions of bromobenzene with acrylonitrile and bromobenzene with ethyl acrylate in the presence of complexes (1), (2) and (3) have been carried out separately.

Keywords: Schiff base, Palladium, Crystal structure, DFT calculations, C-C Heck coupling

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 564-570

 

Synthesis and structural characterization of

bis(μ2-aqua)tetrakis(aqua)dilithium(I) bis(4-nitrobenzoate)

Bikshandarkoil R Srinivasana, *, Santosh Y Shetgaonkara, Kiran T Dhavskara, Jeyaperumal Kalyana Sundarb & Subramanian Natarajanb

aDepartment of Chemistry, Goa University, Goa 403 206, India

Email: srini@unigoa.ac.in

bSchool of Physics, Madurai Kamaraj University,
Madurai 625 021, Tamil Nadu, India

Received 19 May 2011; revised and accepted 15 March 2012

Reaction of alkali metal carbonates M2CO3 (M = Li or Na) with 4-nitrobenzoic acid (4-nbaH) results in the formation of [(H2O)4Li2(μ-H2O)2](4-nba)2 (4-nba = 4-nitrobenzoate) (1) and [Na(4-nba)(H2O)3] (2). Compounds (1) and (2) have been characterized by analytical, spectral and thermal data. The structure of (1) consists of bis(μ2-aqua)tetrakis(aqua)dilithium(I) dication situated on an inversion centre and a free 4-nba anion. In compound (2), one of the two independent 4-nba functions as a μ2-bridging bidentate ligand, bridging the two unique Na(I) ions via the oxygen atoms of the nitro functionality. Hydrogen bonding of coordinated water ligands in a dinuclear lithium cation with coordinated water molecules in an adjacent unit leads to the formation of a supramolecular chain of [(H2O)4Li2(μ-H2O)2]2+ cations. The cationic chain is further H-bonded to 4-nba anions resulting in alternating layers of [(H2O)4Li2(μ-H2O)2]2+ cations and 4-nba anions. Compounds (1) and (2) exhibit enhanced fluorescence emission. A study of the known s-block metal compounds containing 4-nba and coordinated water ligands reveals that the coordination number of the central metal varies from four in Li to nine in Ba.

Keywords: Coordination chemistry, Lithium, Sodium, Nitrobenzoates, Supramolecular chains

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 571-579

 

Model chemistries of hydrazides. III: SEMO computations of isonicotinic acid hydrazide, its valence isomers and their isopropyl derivatives

K Rama Krishnaa, Ch V Kameswara Raob, V Ananta Ramama , R Sambasiva Raob, * & M Venkata Subba Raoc

aDepartment of Chemistry, Gitam Institue of Science, Gitam University, Visakhapatnam, 530 017, India

bSchool of Chemistry, Andhra University, Visakhapatnam 530 003, India

Email: rsr_chem@yahoo.com

cDepartment of Chemistry, GMR Institute of Technology, Rajam 532 127, India

Received 11 March 2011; re-revised and accepted 27 February 2012

The computational quantum chemistry of isonicotinic acid hydrazide (INH), an antitubercular drug, is studied at SEMO level of theory. AMPAC 6.7 package is employed to invoke six hamiltonians, viz., MNDO, MNDO3, MNDO/C, AM1, PM3 and SAM1, to arrive at the optimized geometries in the gaseous phase. Picolinic acid hydrazide (PAH), a valence isomer of INH, and benzoic acid hydrazide (BAH) without a hetero atom in the aromatic ring and their isopropyl derivatives are also investigated. PAH and INH are found to be more stable as compared to BAH, based on electronic and total energies. However, heat of formation is positive (endothermic) and increases in the order: BAH < INH < PAH. The HOMO concentrates on the hydrazide fragment, while LUMO extends over the ring. The orbital-based interactions are more probable with isopropyl derivatives as FMOs spread on either side. Isopropyl derivatives have higher. (ELUMO - EHOMO) and electron affinity values, while ionization potential and hardness have lower values compared to parent compounds. The static dipole moment of INH (1.13 Debye) is substantially increased to 1.87 Debye in  isop-INH and to
4.46 Debye in PAH. For INH, the second order hyperpolarizability is higher than that of PAH. The electrophilic centers are the terminal nitrogens of hydrazide fragment and the pyridine nitrogen in INH and PAH. The isopropyl analogues have higher electrophilic character. The 3D-surface and 2-D contours of total electron density (TED) on TED, electrostatic potential (ESP) on TED and ESP on ESP along with Mullikan and ESP charges are analysed. The quantum chemical computed bond characteristics of INH are in agreement with the X-ray crystallographic data.

 

Keywords: Theoretical chemistry, Hydrazides, Quantum chemical paramaters, Optimized geometries, Isonicotinic acid hydrazide, Electron densities

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 580-585

 

Mineralization of genotoxic Acid Violet 7 by AgBr-ZnO under alkaline conditions using direct sunlight

B Krishnakumar, R Velmurugan, B Subash & M Swaminathan*

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

Email: chemres50@gmail.com

Received 11 January 2012; revised and accepted 22 February 2012

The photocatalytic degradation of a genotoxic azo dye, Acid Violet 7 (AV 7), using AgBr-ZnO in aqueous solution has been investigated under solar irradiation at pH 12. The photocatalytic activity of AgBr-ZnO is higher than that of bare ZnO (prepared ZnO), commercial ZnO, TiO2 and Degussa TiO2-P25 in the degradation of AV 7. Mechanism of degradation by AgBr-ZnO is proposed to explain its higher activity under solar light. The effects of operational parameters such as the amount of photocatalyst, dye concentration, initial pH, cations, anions and oxidants, on photomineralization by AgBr-ZnO have been analyzed. The degradation of AV 7 follows pseudo-first order kinetics according to the Langmuir-Hinshelwood model. Based on the intermediates formed during the photodegradation, a degradation pathway is proposed. The mineralization of AV 7 has also been confirmed by chemical oxygen demand measurements.

Keywords: Photocatalysis, Dye degradation, Solar light, Acid Violet 7, Zinc oxide, Silver bromide

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 586-590

 

Synthesis of nanocrystalline NiO by sol-gel and homogeneous precipitation methods

P Jeevanandam* & V Ranga Rao Pulimi

Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India

Email: jeevafcy@iitr.ernet.in

Received 20 October 2011; revised and accepted 15 March 2012

Nanocrystalline nickel oxide has been prepared via thermal decomposition of precursors obtained using two methods, sol-gel process and homogeneous precipitation. The precursors and the oxide obtained by calcination are characterized by various analytical techniques such as powder X-ray diffraction, thermal gravimetric analysis, FT-IR spectroscopy, surface area measurements, scanning electron microscopy, transmission electron microscopy and magnetic measurements. The crystallite size of nickel oxide prepared from homogeneous precipitation method is ~ 2 nm whereas that of the nickel oxide prepared from sol-gel process is about 19 nm. The nanocrystalline NiO samples obtained by both the methods exhibit superparamagnetic behavior.

Keywords: Nanocrystalline materials, Nickel oxide, Sol-gel process, Homogeneous precipitation

 

Indian Journal of Chemistry

Vol. 51A, April 2012, pp. 591-594

 

Density estimation of normal alkanes from the statistical-thermodynamic perturbation theory based equation of state

 

Ali Reza Zabetia, Behzad Haghighib,*,
Mohammad Mehdi Paparic & Ebrahim Ghiamatid

aR&D Division of Paint Shop, Iran Khodro Khorasan Co, Binalood Industrial Estate, 91775-1734, Binalood, Razavi Khorasan Province, Iran

bDepartment of Physics, Faculty of Science, Neyshabur University, Postal Code 91136, Neyshabur, PO Box 899, Razavi Khorasan Province, Iran

Email: haghighi.behzad@gmail.com

cChemistry Department, Shiraz University of Technology, 71555-313, Shiraz, Fars Province, Iran

dAnalytical Chemistry Research Laboratory, Department of Chemistry, Faculty of Science, Birjand,

South Khorasan Birjand University, 97175-615, Province, Iran

Received 16 August 2011; revised and accepted 27 February 2012

An analytical equation of state (EoS) proposed by Ihm-Song-Mason (ISM) is employed to calculate the density of normal alkanes from methane to decane. The best available values of the Lennard-Jones (12,6) parameters have been used to evaluate the second virial coefficient of the EoS for each compound. The second virial coefficient is not very sensitive to the feature of the intermolecular potential. The remaining parameters in the EoS depend only on the repulsive part of the potential. Consequently, they are insensitive to the details of the interaction potential. The calculated second virial coefficients in conjunction with other temperature-dependent parameters of the EoS are employed to predict the density of all alkanes (C1-C10). There is a good agreement comparison between the experimental values of density and the calculated values from ISM EoS for all of the compounds.

Keywords: Statistical thermodynamics, Density, Perturbation theory, Equations of state, Pair interaction potential, Alkanes