Indian Journal of Chemistry

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

http://www.niscair.res.in; http://nopr.niscair.res.in

Total visitors: 1982 since 11-12-2014

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

 

 

 

 

 

 

VOLUME 53A

NUMBER 12

DECEMBER 2014

 

CONTENTS

 

 

1485

 

Synthesis of isoamyl acetate using polyoxometalate-based sulfonated ionic liquid as catalyst

 

 

 

 

 

 

 

 

 

Miaoli Fang, Keke Chen, Jiawen Zhang, Wei Yan, Xiujuan Tang & Xiaoxiang Han*

 

 

 

Synthesis of isoamyl acetate is optimized by response surface methodology using organic TPA salts, [MIM-PSH]xH3-xPW12O40 (x = 1.0–3.0) as catalyst. The coefficient of determination of the proposed model is 0.9849. Under the optimized conditions, the yield of isoamyl acetate reaches 98.2%. [MIM-PSH]1.5H1.5PW12O40 shows the high activity and stability on esterification.

 

GA image

 

 

1493

 

Sulphated Fe2O3-TiO2 catalysed transesterification of soybean oil to biodiesel

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Anuradha, K Joseph Antony Raj,
V R Vijayaraghavan & B Viswanathan
*

 

 

Transesterification of soybean oil over sulphated Fe2O3-TiO2 catalysts has been carried out at 100 °C for 2 h. The catalysts, characterised to have both Bronsted and Lewis acidity, show 98% conversion with high biodiesel yield.

 

 

 

1500

 

Catalytic oxyfunctionalization of alkanes and alkenes by hetero-metal Mn-Cu and Mn-Ni clusters

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Akshay Mehta, Shino Stephen & Gopal Tembe*

 

 

 

Novel Mn-Cu and Mn-Ni clusters have been used as catalysts for oxidation and epoxidation of alkane and alkenes respectively under mild conditions in presence of tert-butyl hydroperoxide as an oxidant. The hexanuclear cluster (2) containing μ-oxo linkages shows high activity for C-H activation.

 

 

 

1505

 

Electrical conductivity of polyazomethine nanocomposites

 

 

 

 

 

 

 

 

Sandeep M Tripathi, Devendra Tiwari &
Arabinda Ray
*

 

 

 

image description

 

 

1513

 

Effect of thermal treatment on the phase structure and electrical properties of CexGd1-xO2-d electrolytes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ping Fang*, Shiping Li, Jiqing Lu, Yueqing Lu & Mengfei Luo

 

 

 

The Ce0.6Gd0.4O2-d-N and Ce0.6Gd0.4O2-d-A electrolytes present
the best electrical conductivity among the studied CexGd1-xO2-
d electrolytes. The oxygen vacancy increases with increasing Gd3+ doping. However when the dopant concentration is higher than 40%, the formation of {GdʹCe VÖ} lacuna cluster decreases the conductivity.

 

 

Notes

 

1520

 

Co(II), Ni(II), Cu(I) and Pd(II) complexes of
p-anisaldene-thiosemicarbazone

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Geetika Borah*, Jayantajit Baruah & Devid Kardong

 

 

 

Synthesis and characterization of Co(II), Ni(II), Cu(I) and Pd(II) complexes with anisaldene-thiosemicarbazone are reported. The copper(I) complex exhibits good antifungal activity and also possesses better antiproliferative activity against cancer cells than the ligand.

 

 

 

1526

 

Na+ affinity of a series of substituted acetophenones in their low-lying excited triplet state: A DFT based computational study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

U Senapati, D De & B R De*

 

 

 

The gas phase sodium ion affinity of acetophenones and its
para-substituted counterparts in the lowest excited triplet state is spontaneous irrespective of their electron releasing or withdrawing nature. The electronic properties of the complexes indicate that the interaction is predominantly an ion-dipole attraction and ion-induced dipole interaction rather than a covalent interaction.

 

 

 

 

 

1531

 

Announcement

 

 

 

 

 

1532

 

Annual Index

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 


Online Submission for IJCA Articles

 

 

From 1 January 2015 onwards, articles submitted for consideration of publication in the Indian J Chem, Sec A, should be uploaded through our Online Submission portal, http://op.niscair.res.in.

Authors are requested to register at http://op.niscair.res.in. The articles (in MS Word) appended with the certificate of originality, illustrations (jpeg/tiff) and supplementary data,
if any, may be uploaded through the User Home page. Further information is available
at http://www.niscair.res.in/jinfo/author_guidelines_online_submission.pdf.

It may be noted that from 1 January 2015 onwards, articles submitted by email or postal services shall not be processed.

For technical support and assistance for online submission, Shri Sanjay Burde may be contacted (sanjayburde@niscair.res.in); Tel.: 91-11-25846301.

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1485-1492

 

Synthesis of isoamyl acetate using polyoxometalate-based
sulfonated ionic liquid as catalyst

Miaoli Fanga, c, Keke Chena, Jiawen Zhanga, Wei Yana, Xiujuan Tangb & Xiaoxiang Hana, *

aDepartment of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, China

Email: hxx74@126.com/han-xx74@163.com

bCollege of environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China

cZhejiang Medical College, Hangzhou 310053, P R China

Received 11 June 2014; revised and accepted 24 November 2014

Response surface methodology is successfully applied to optimize esterification of isoamyl alcohol with acetic acid by [MIM-PSH]1.5H1.5PW12O40 catalyst prepared by incorporating tungstophosphoric acid with
3-(1-methylimidazolium-3-yl) propane-1-sulfonate zwitterionic precursor. The effects of various reaction conditions, including reaction time, amount of catalyst, alcohol/acid molar ratio and amount of water-carrying agent are investigated. A Box–Behnken experimental design has been employed to search for the optimal yield of isoamyl acetate. The catalytic system invoking homogeneous reaction over the polyoxometalate-based sulfonated ionic liquid catalyst is also unique due to its “self-separation” characteristics, which facilitates high yield of product, product separation and catalyst recycling. The optimum reaction conditions are established and for validating. Under the optimum conditions, the yield of isoamyl acetate reaches 98.2%. The ionic liquid can be reused five times without noticeable drop in activity.

Keywords: Catalysts, Heteropolyacids, Ionic liquids, Polyoxometalates, Esterification, Isoamyl acetate, Response surface methodology

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1493-1499

 

Sulphated Fe2O3-TiO2 catalysed transesterification of
soybean oil to biodiesel

S Anuradhaa, b, K Joseph Antony Rajb, V R Vijayaraghavanc & B Viswanathanb, *

aPSNA College of Engineering and Technology, Kothandaraman Nagar, Dindigul 624 622, India

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

Email: bvnathan@iitm.ac.in

cDepartment of Physical Chemistry, University of Madras, Chennai 600 0025, India

Received 18 June 2014; revised and accepted 19 November 2014

Sulphated Fe2O3-TiO2 has been synthesized from ilmenite ore and calcined over 300-900 °C. The catalyst samples have been examined for acidity by adsorption of pyridine. The spectral studies reveal the presence of sulphate groups and both Brønsted and Lewis acid sites. The transesterification of soybean oil with methanol is studied over unsulphated and sulphated Fe2O3-TiO2 catalysts with varying sulphate contents and the results are evaluated on the basis of acidity. The catalyst samples calcined below 500 °C show higher conversion of vegetable oil with significant yield of biodiesel which could be due to the greater affinity of hydroxyl groups of methanol on Fe2O3-TiO2. The sulphated Fe2O3-TiO2 samples calcined above 500 °C show lower conversion of biodiesel and this is proposed to be due to the removal of sulphate groups during calcination.

Keywords: Catalysts, Transesterification, Metal oxides, Sulphated metal oxides, Iron oxide, Titania, Ilmenite ore, Vegetable oils, Biodiesel

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1500-1504

 

Catalytic oxyfunctionalization of alkanes and alkenes by hetero-metal
Mn-Cu and Mn-Ni clusters

Akshay Mehtaa, Shino Stephenb & Gopal Tembea, *

aReliance Technology Group, Reliance Industries Ltd., Vadodara Manufacturing Division, Vadodara 391 346, India

bTotal Lubricants, Jebel Ali 17001, Dubai, UAE

Email: Gopal.Tembe@ril.com

Received 6 June 2014; revised and accepted 5 November 2014

Novel hetero-metal di-, octa- and tetranuclear Mn-Cu, Mn-Ni clusters such as [MnIIICuII(5-Cl-sap)2Cl(MeOH)](1)  [H25-Cl-sap = 5-chlorosalicylidene-3-aminopropanol], MnIII2MnII2CuII4(3-OMe-sap)4-
(
μ4-O)2(μ2-OMe)2Cl2]Cl2·2MeOH(5Cl2.2MeOH)(2) [H23-OMe-sap = vanillidene-3-aminopropanol)] and [MnIII2NiII2(sap)2(sal)2(μ3-OMe)2(OAc)2] (3) [Hsal = salicylaldehyde; H2sap = salicylidene-3-aminopropanol] have been used as catalysts in the oxidation of alkanes and alkenes in the presence of tert-butyl hydroperoxide as an oxidant. The investigations reveal marked differences in the reactivity of the Mn-Cu and Mn-Ni clusters. The probable mechanism of hydroxylation in these systems is discussed.

Keywords: Catalysts, Hetero-metal clusters, Oxidation, Metal clusters, Alkanes, Manganese, Copper, Nickel

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1505-1512

 

Electrical conductivity of polyazomethine nanocomposites

Sandeep M Tripathia, Devendra Tiwarib & Arabinda Rayc, *

aDepartment of Chemistry, Sardar Patel University, V V Nagar 388 120, Gujarat, India

bDr K C Patel Research and Development Centre, Charotar University of Science & Technology,
Changa 388 421, Gujarat, India

cP D Patel Institute of Applied Sciences, Charotar University of Science & Technology, Changa 388 421, Gujarat, India

Email: arabinda24@yahoo.co.in

Received 2 May 2014; revised and accepted 18 November 2014

Nanocomposites of polyazomethines have been prepared via in situ and ex situ addition of Ag and PbS nanoparticles. Structural characterization of nanocomposites by X-ray diffraction shows formation of pure nanocrystalline Ag and PbS with cubic structure. Transmission electron microscopy gives evidence for spherical nanoparticles distributed homogenously within the polymer matrix. Electrical measurements show a significant increase in conductivity in some of the nanocomposites with respect to the virgin polymers. Infrared spectroscopy reveals strong interaction between the nanoparticles and polymers in these nanocomposites. Finally, a theoretical model based on PM6 molecular orbital calculations to explain the observed changes in the electrical conductivities is suggested. It is concluded that increase in electrical conductivity is governed by strong interaction between the polymer and the inorganic nanoparticles, resulting in considerable decrease of energy difference between the highest occupied molecular orbital and lowest unoccupied molecular orbital.

Keywords: Polymer nanocomposites, Composites, Nanocomposites, Molecular orbital calculations, Vibrational spectroscopy, Electrical conductivity

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1513-1519

 

Effect of thermal treatment on the phase structure and electrical properties of CexGd1-xO2-d electrolytes

Ping Fanga, *, Shiping Lib, Jiqing Lub, Yueqing Lua & Mengfei Luob

aSchool of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China

Email: fangping@usx.edu.cn

bZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry,

Zhejiang Normal University, Jinhua 321004, China

Received 16 May 2014; revised and accepted 3 November 2014

A series of CexGd1-xO2-d electrolytes has been prepared by typical and improved sol-gel methods with different thermal treatment conditions. The CexGd1-xO2-d phase structures have been characterized by XRD and Raman spectroscopy, and the electrolytes properties studied by the AC impedance spectroscopy. It is found that the improved sol-gel method is beneficial for the formation of CeO2-based or Gd2O3-based solid solutions and consequently oxygen vacancies, through which the electrolytes can absorb and desorb oxygen continuously, resulting in improved electrical conductivity. Amongst the studied electrolytes, the Ce0.6Gd0.4O2-d-A electrolyte prepared by typical method and the Ce0.6Gd0.4O2-d-N electrolyte prepared by improved method show the highest electrical conductivity.

Keywords: Solid electrolytes, Sol-gel method, Oxygen vacancy, Phase structure, Electrical conductivity

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1520-1525

 

Co(II), Ni(II), Cu(I) and Pd(II) complexes of
p-anisaldene-thiosemicarbazone

Geetika Boraha, *, Jayantajit Baruaha & Devid Kardongb

aDepartment of Chemistry, Dibrugarh University, Dibrugarh 786 004, Assam, India

bDepartment of Life Sciences, Dibrugarh University, Dibrugarh 786 004, Assam, India

Email: geetikachem@yahoo.co.in

Received 26 December 2013; re-revised and accepted 25 November 2014

The reaction of anisaldene-thiosemicarbazone (HL) with MCl2.6H2O (where M = Co(II) and Ni(II) ), Cu(CH3COO)2.H2O and [Pd(COD)Cl2] on stirring/refluxing affords six-coordinated [Co(L)2(HL)] (1) and four-coordinated [Ni(L)2] (2), [Cu(L)(HL)] (3) and [Pd(L)(COD)]Cl (4) complexes. All the complexes have been characterized by conductivity measurements, FTIR, UV-vis, ESI(+) mass, 13C and 1H NMR spectroscopy, TGA-DTA analysis, magnetic and cyclic voltammetry studies and screened in vitro for antimicrobial activity by the agar well method. The ligand and the Cu(I) complex have been tested for anticancer activity The Cu(I) complex exhibits quite good antifungal activity against R. solani and F. oxosporum ciceri, and also possesses better antiproliferative activity than the ligand against the cancer cells.

Keywords:  Coordination chemistry, Antibacterial activity, Antifungal activity, Anticancer activity, Anisaldene, Thiosemicarbazone, Cobalt, Nickel, Copper, Palladium

 

 

Indian Journal of Chemistry

Vol. 53A, December 2014, pp. 1526-1530

 

Na+ affinity of a series of substituted acetophenones in their low-lying excited triplet state: A DFT based computational study

U Senapatia, D Deb & B R Deb, *

aDepartment of Chemistry, Santipur College, Nadia 741 404, West Bengal, India

Email: senapatiumasankar@gmail.com

bDepartment of Chemistry and Chemical Technology, Vidyasagar University, Midnapore 721 102, West Bengal, India

Email: brdranjan@yahoo.com

A detailed study of Na+ affinities of a series of para-substituted acetophenones and their O–Na+ counterparts has been carried out using density functional theory by B3LYP method using 6-311G(d,p) basis set with complete geometry optimization in the relevant excited state. The gas phase O–Na+ complex formation is exothermic and the local stereochemical disposition of the Na+ is found to be almost the same in each case. The presence of para-substituent causes very little change in the Na+ affinity relative to the unsubstituted acetophenones. Electron releasing p-substituents are seen to increase the affinity, while electron withdrawing p-substituents have an opposite effect. The computed Na+ affinities are correlated with a number of computed system parameters such as the net charge on the Na+ and the carbonyl oxygen of the Na+ complexes and the net charge on the carbonyl oxygen of the free bases as well as the computed hardness of the free bases. The Na+ ion induced shifts are, in general, red shifts for the low-lying excited triplet state. The energetics, structural and electronic properties of the complexes indicate that in the lowest excited triplet state the interaction between the Na+ ion and a carbonyl base is predominantly an ion-dipole attraction and the ion-induced dipole interaction as well rather than a covalent interaction.

Keywords:  Theoretical chemistry, Density functional calculations, Gas phase ion chemistry, Charge distribution, Acetophenones