Indian Journal of Chemistry

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

 

VOLUME 47A

NUMBER 9

September 2008

CONTENTS

1317

Partial oxidation of methanol on Au-Pd/ceria

 

 

 

 

 

 

 

Qing-bo Chen, Lai-tao Luo* & Xiaomao Yang

 

Partial oxidation of methanol over Au/CeO2 and Au-Pd/CeO2 catalysts is reported. The Au-Pd alloy particles are formed, and Au dispersion on CeO2 support is promoted due to the addition of Pd to the Au-Pd/CeO2 bimetallic catalyst. Compared with Au/CeO2 catalyst, the Au-Pd-/CeO2 catalyst has larger active surface area and stronger interaction between Au-Pd and support. The desorption temperature of methanol is low. The Au-Pd/CeO2 catalyst reduced by H2 before the reaction shows higher methanol conversion and hydrogen selectivity, which suggests that the metallic states of Au, Pd and Au-Pd play an important role in the partial oxidation of methanol.

 

1323

Physicochemical studies on some 4-methyl piperazine-1-carbodithioate complexes of zinc(II), cadmium(II) and mercury(II)

 

 

 

 

 

 

 

S B Kalia*, G Kaushal, M Kumar, S Kumar &
K L Khanduja

 

New 4-methylpiperazine-1-carbodithioate complexes with the general formula [M(4-MPipzcdtX)2](Y)2
(M = Zn(II), X = H and Y = ClO4, Cl; M = Cd(II), Hg(II), X = H and Y = Cl; M = Zn(II), Cd(II), Hg(II) when X and
Y = nil) and mixed-ligand complexes, viz. [M(4-MPipzcdtX)a(L)b]Y (L = 1,10-phenanthroline and 2,2-bipyridyl; M = Zn(II), Cd(II), Hg(II), X = H when Y = Cl2, a = 2, b = 1; M = Zn(II), X = nil where Y = Cl when a = 1, b = 2 and Y = nil when a = 2, b = 1) have been prepared and characterized. Two of these complexes, viz. Zn(4-MPipzcdt)2 and [Hg(4-MPipzcdtH)2](Cl)2 have been screened for their in vitro antimicrobial activity against the pathogenic fungi using the agar dilution method. Two complexes, viz. M(4-MPipzcdt)2 (M = Zn(II), Cd(II)) have also been screened for their antileukemic activity.

 

1333

Synthesis, characterization, antibacterial activity and 3D-molecular modeling of some oxoperoxo molybdenum(VI) chelates in mixed (O,O) coordination environment involving 2-hydroxy-1-
naphthaldehyde and
b-diketoenolates

 

 

 

 

 

 

 

 

R C Maurya*, S Sahu & P Bohre

 

A new series of four mixed-ligand complexes of oxoperoxomolybdenum(VI) is reported.

 

 

 

1343

Synthesis, crystal structure and thermal behavior of {4,4',6,6'-tetra(tert-butyl)-2,2'-[ethylenedioxybis-(nitrilomethylidyne)]diphenolato}Cu(II)

 

 

 

 

 

 

 

 

 

 

 

 

Wen-Kui Dong* Jian-Hua Feng, Li Xu, Jin-Kui Zhong, Yin-Xia Sun & Xiao-Qing Yang

 

The title complex has been synthesized by the reaction of 4,4',6,6'-tetra(tert-butyl)-2,2'-[ethylenedioxybis(nitrilomethyli-dyne)]diphenol with copper(II) acetate monohydrate in ethanol.

 

 

1348

Kinetics of the reaction between methyl 2,4-dichloro-3,5-dinitro-benzoate and piperidine Solvent effect

 

 

 

 

Magda F Fathalla*, Taher S Kassem &
Ezzat A Hamed

 

 

 

The rate constant for the reaction of methyl 2,4-dichloro-3,5-dinitrobenzoate with different piperidine concentrations have been measured in nine pure solvents. The kinetic results postulate three solvation models: (a) alkanol extensively solvating the amine and weakening the intramolecular hydrogen bonding in the intermediate; (b) the non-polar solvents enhance the intramolecular hydrogen bonding in the intermediate increasing the nucleophilicity of amine; (c) the dipolar aprotic solvents solvate the amine and timely solvating the intermediate by intermolecular hydrogen bond. The solvent parameters have been correlated with the rate constant for the reaction through linear free energy relationships.

 

1355

Partial molar adiabatic compressibilities and viscosities of some amino acids in aqueous glycerol solutions at 298.15 K

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Gagandeep Singh & T S Banipal *

 

Apparent molar adiabatic compressibilities and viscosities of glycine, DL-a-alanine, L-valine, L-leucine and L-phenylalanine have been determined in water and in mixed aqueous solutions of glycerol at 298.15 K. These data have been used to calculate partial molar adiabatic compressibilities at infinite dilution, and viscosity B-coefficients, and their corresponding transfer functions. The positive partial molar adiabatic compressibilities of transfer at infinite dilution have been observed for the studied amino acids. B-coefficient of transfer values are positive for these amino acids, which after passing through maxima decrease at higher concentration of glycerol. The activation energy for viscous flow in aqueous and mixed aqueous glycerol solutions has been calculated from B-coefficient and partial molar volume data. Hydration numbers, interaction coefficients and side chain contributions have also been calculated. The results have been discussed in terms of solute-cosolute interactions, and an attempt has also been made to correlate these parameters with the stability of protein in aqueous glycerol solutions.

 

Notes

 

1365

Synthesis of nano-BaTiO3 by liquid-state methods

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Wang Jing*, Ding Shi-Wen & Lv Shu-Fang

 

Nano-BaTiO3 powder has been synthesized with TiCl4 and Ba(OH)2 by different liquid-state (atmospheric, hydrothermal and microwave) methods. The powder synthesized by microwave method has the least grain size, the lowest sintering temperature, and the best dielectric capacity. Microwave method requires less reaction time, small grain size, and narrow grain size distribution.

 

 

 

1369

Hydrothermal synthesis, crystal structure and strong photoluminescence of [Er(C6NO2H5)2(H2O)4(NO3)]2NO3

 

 

 

 

 

 

 

Wen-Tong Chen*, Xin-Fa Li, Qiu-Yan Luo, Ya-Ping Xu & Dong-Sheng Liu

 

The hydrothermal reaction of erbium nitrate with
isonicotinic acid affords the erbium complex [Er(C6NO2H5)2(H2O)4(NO3)]2NO3, which has been structurally characterized by X-ray diffraction.

 

1373

 

Kinetics and mechanism of oxidation of some thioacids by morpholinium chlorochromate

 

 

 

 

 

N Malani, S Pohani , M Baghmar & Pradeep K Sharma*

 

Oxidation of thioglycollic, thiolactic and thiomalic acids by morpholinium chlorochromate (MCC) is first order both in MCC and thioacids. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence takes the form kobs = a + b [H+].

2 R S H + O2CrClOMH
R S S R + H2O + OCrClOMH

 

1377

Sorption behaviour of D 155 resin for Ce(III)

 

 

Chunhua Xiong

 

The sorption of Ce(III) by D155 resin is reported here. The effect of pH on the sorption of Ce(III), the sorption capacity of the resin, the isotherms, kinetics and thermodynamics have been investigated by the sorption-desorption method. The sorption mechanism is also proposed. The sorption is spontaneous and endothermic under the examined conditions.

 

1381

2-Hydroxy-1-naphthaldehyde-p-hydroxybenzoic hydrazone as a spectrophotometric reagent for the determination of lanthanum (III)

 

P Govinda Chowdary, K P P R Mohan Reddy,
V Krishna Reddy* & P Raveendra Reddy

 

A new chromophore, 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoic hydrazone has been used for the determination of lanthanum (III). A brownish yellow coloured 2:3 (M:L) soluble complex is formed having lmax at 415 nm. The colour intensity further increases in the cetyl trimethyl ammonium bromide micellar medium. Beers law is obeyed in the range 0.277-8.334 μg mL-1 and 0.008-2.639 μg mL-1 of La(III) in direct and derivative methods, respectively.

 

1384

Micellar effects on dye sensitized photooxidation of phenothiazine

 

 

 

 

 

 

 

 

 

 

Shipra Kathuria, P K Gupta & N R Dhamiwal*

 

Methylene blue sensitized photooxidation of phenothiazine in sodium dodecylsulphate, cetyl trimethylammonium bromide and brij-35 in methanol-water, ethanol-water and acetonitrile-water gives phenothiazine-3-one and phenothiazine sulphoxide as the products at low conversion. An inverse relationship between log Φ and 1/Є0 supports the participation of singlet oxygen (1O2) at low [PTH].

 

 

Authors for correspondence are indicated by (*)

 

 

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1317-1322

 

 

Partial oxidation of methanol on Au-Pd/ceria

Qing-bo Chen, Lai-tao Luo* & Xiaomao Yang

Received 29 May 2007; revised 21 July 2008

Partial oxidation of methanol over Au/CeO2 and Au-Pd/CeO2 catalysts is reported here. The catalysts have been characterized by using X-ray diffraction, temperature programmed reduction and temperature-programmed desorption of methanol. The studies show that the Au-Pd alloy particles are formed, and Au dispersion on CeO2 support is promoted owing to the addition of Pd to the Au-Pd/CeO2 bimetallic catalyst. Compared with Au/CeO2 catalyst, the Au-Pd-/CeO2 catalyst has larger active surface area and stronger interaction between Au-Pd and support. The desorption temperature of methanol is low. The Au-Pd/CeO2 catalyst reduced by H2 before the reaction shows higher methanol conversion and hydrogen selectivity, which suggests that the metallic states of Au, Pd and Au-Pd play an important role in the partial oxidation of methanol.

IPC Code: Int. Cl.8 C07B33/00

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1323-1332

 

Physicochemical studies on some 4-methylpiperazine-1-carbodithioate complexes of zinc(II), cadmium(II) and mercury(II)

 

S B Kalia *, G Kaushal, M Kumar, S Kumar & K L Khanduja

Received 6 November 2007; revised 9 July 2008

New 4-methylpiperazine-1-carbodithioate (4-MPipzcdt) complexes of the general formula [M(4-MPipzcdtX)2](Y)2
(M = Zn(II), X = H and Y = ClO4, Cl; M = Cd(II), Hg(II), X = H and Y = Cl; M = Zn(II), Cd(II), Hg(II) when X and
Y = nil) and mixed-ligand complexes, viz. [M(4-MPipzcdtX)a(L)b]Y (L = 1,10-phenanthroline (phen) and 2,2
-bipyridyl (bipy); M = Zn(II), Cd(II), Hg(II), X = H when Y = Cl2, a = 2, b = 1; M = Zn(II), X = nil where Y = Cl when a = 1, b = 2 and Y = nil when a = 2, b = 1) have been prepared and characterized by elemental analyses, conductance measurements, proton nuclear magnetic resonance, infrared and electronic absorption spectral, and room-temperature magnetic susceptibility measurements. Two of these complexes, viz. Zn(4-MPipzcdt)2 and [Hg(4-MPipzcdtH)2](Cl)2 have been screened for their in vitro antimicrobial activity against the pathogenic fungus Candida albicans and pathogenic gram-negative Escherichia coli, Pseudomonas aeruginosa and gram-positive Staphylococcus aureus, Enterococcus faecalis using the agar dilution method. Two complexes, viz. M(4-MPipzcdt)2 (M = Zn(II), Cd(II)) have also been screened for their antileukemic activity.

IPC Code: Int.Cl.8 C07F3/06; C07F3/08; C07F3/10

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1333-1342

 

Synthesis, characterization, antibacterial activity and 3D-molecular modeling of some oxoperoxomolybdenum(VI) chelates in mixed (O,O) coordination environment involving 2-hydroxy-1-naphthaldehyde and b-diketoenolates

R C Maurya,,* S Sahu & P Bohre

Received 12 May 2008; revised 4 August 2008

A new series of four mixed-ligand complexes of oxoperoxomolybdenum(VI) of the general composition, [MoO(O2)(2-hnd)(L)]H2O, where 2-hndH = 2-hydroxy-1-naphthaldehyde and LH = o-acetoacetanisidide (o-aansH), o-acetoacetotoluidide (o-aatdH), acetylacetone (acacH) or methyl acetoacetate (macacH), has been synthesized by the interaction of [MoO(O2)]2+ (in situ obtained during the interaction of MoO3 and 30% H2O2 on continuous stirring at 50C for 24 h) and the ligands in aquous-ethanol medium. The complexes so obtained have been characterized by elemental analyses, molar conductance, decomposition temperature and magnetic measurements, thermogravimetric studies, 1H-NMR, IR, mass and electronic spectral studies. Antibacterial studies of the ligand and the metal complexes have also been carried out. The complexes have been found to be more potent bactericides than the ligands. The 3D-molecular modeling and analysis for both bond lengths and bond angles have also been carried out for one of the representative compounds, [MoO(O2)(2-hnd)(o-aatd)]H2O (1), to substantiate the proposed structure. Pseudopentagonal bipyramidal structures have been proposed for these complexes.

IPC Code: Int. Cl.8 C07F4/00

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1343-1347

 

Synthesis, crystal structure and thermal behavior of {4,4',6,6'-tetra(tert-butyl)-
2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenolato}Cu(
II)

Wen-Kui Dong*, Jian-Hua Feng, Li Xu, Jin-Kui Zhong, Yin-Xia Sun & Xiao-Qing Yang

Received 8 April 2008; revised 10 July 2008

The title complex, [Cu(L)], has been synthesized by the reaction of 4,4',6,6'-tetra(tert-butyl)-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol (H2L) with copper(II) acetate monohydrate in ethanol and characterized by its elemental analyses, IR spectra, TG-DTA analysis and X-ray crystallography. The complex belongs to monoclinic system with space group C2/c and unit cell parameters a = 27.231(3) , b = 11.196(3) , c = 10.704(2) , b = 101.293(2),
V = 3200.2(11)
3 and Z = 4. X-ray crystal structure of the complex reveals that Cu(II) ion lies in the N2O2 coordination sphere, and forms a mononuclear structure. The dihedral angle between the coordination plane of N1-Cu1-O2 and that of N1#-Cu1-O2# is 32.78(3), indicating that the coordination sphere has a slightly distorted tetrahedral geometry.

IPC Code: Int. Cl.8 C07F1/08

 

Indian Journal of Chemistry

Vol. 47A, September2008, pp. 1348-1354

 

Kinetics of the reaction between methyl 2,4-dichloro-3,5-dinitrobenzoate and piperidine Solvent effect

Magda F Fathalla*, Taher S Kassem & Ezzat A Hamed

Received 12 March 2008; revised 28 July 2008

The rate constant for the reaction of methyl 2,4-dichloro-3,5-dinitrobenzoate (1) with different piperidine concentrations have been measured spectrophotometrically in nine pure solvents, viz. methanol, ethanol, n-propanol, isopropanol, t-butyl alcohol, acetonitrile, dimethysulphoxide, dioxane and benzene at different temperatures to study the effect of the solvents. The kinetic results postulate three solvation models: (a) alkanol extensively solvating the amine and weakening the intramolecular hydrogen bonding in the intermediate; (b) the non-polar solvents enhance the intramolecular hydrogen bonding in the intermediate increasing the nucleophilicity of amine; (c) the dipolar aprotic solvents solvate the amine and timely solvating the intermediate by intermolecular hydrogen bond. The solvent parameters have been correlated with the rate constant for the reaction through linear free energy relationships. The adequacy of the multi-parametric scales as appropriate approaches to describe the solvent features in microscopic environments has also been analyzed.

 

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1355-1364

 

Partial molar adiabatic compressibilities and viscosities of some amino acids in aqueous glycerol solutions at 298.15 K

Gagandeep Singh & T S Banipal*

Received 7 March 2008; revised 15 July 2008

Apparent molar adiabatic compressibilities, ks,2,f, and viscosities, h, of glycine, DL-a-alanine, L-valine, L-leucine and L-phenylalanine have been determined in water and in mixed aqueous solutions of glycerol (0.5, 1.0, 2.0, 3.5, and 5.0 mB molality of glycerol in water / mol kg-1) at 298.15 K. These data have been used to calculate partial molar adiabatic compressibilities at infinite dilution, and viscosity B-coefficients, and their corresponding transfer functions. The positive partial molar adiabatic compressibilities of transfer at infinite dilution, Dtr, have been observed for the studied amino acids (except at lower concentration up to 0.6 mB in some cases), and their magnitude increases with increase in concentration of glycerol. B-coefficient of transfer, DtrB, values are positive for these amino acids, which after passing through maxima 3.5 mB decrease at higher concentration of glycerol. The activation energy for viscous flow in aqueous and mixed aqueous glycerol solutions has been calculated from B-coefficient and partial molar volume data. Hydration numbers, interaction coefficients and side chain contributions have also been calculated. These results have been discussed in terms of solute-cosolute interactions, and an attempt has also been made to correlate these parameters with the stability of protein in aqueous glycerol solutions.

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1365-1368

 

Synthesis of nano-BaTiO3 by liquid-state methods

Wang Jing*, Ding Shi-Wen & Lv Shu-Fang

Received 22 February 2008; revised 16 July 2008

Nano-BaTiO3 powder has been synthesized with TiCl4 and Ba(OH)2 by different liquid-state (atmospheric, hydrothermal and microwave) methods. Its phase, shape and capacity have been investigated by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, small-angle X-ray scattering and LCR data. XRD pattern of the series of the nanometer powders demonstrates that BaTiO3 has cubic structure. TEM shows that the products have a shape of uniform, substantially spherical particles. Powder synthesized by microwave method has the least grain size, the lowest sintering temperature, and the best dielectric capacity. Microwave method requires less reaction time, little grain size, and narrow grain size distribution.

IPC Code: Int. Cl.8 B82B

 

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1369-1372

 

 

Hydrothermal synthesis, crystal structure and strong photoluminescence of [Er(C6NO2H5)2(H2O)4(NO3)]2NO3

Wen-Tong Chen*, Xin-Fa Li, Qiu-Yan Luo, Ya-Ping Xu & Dong-Sheng Liu

Received 24 January 2008; revised 27 June 2008

The hydrothermal reaction of erbium nitrate with isonicotinic acid affords the erbium complex [Er(C6NO2H5)2(H2O)4(NO3)]2NO3, which has been structurally characterized by X-ray diffraction. The title complex is characteristic of an isolated structure based on one discrete [Er(C6NO2H5)2(H2O)4(NO3)]2+ moiety and two isolated nitrate anions. The [Er(C6NO2H5)2(H2O)4(NO3)]2+ moieties and the nitrate anions are interconnected via hydrogen bonds to form a two-dimensional supramolecular network. Photoluminescent investigation reveals that the title complex displays a greenish yellow emission band and a red emission band. The greenish yellow emission band is stronger than that of the red emission band. The greenish yellow and red emission bands are identified as the Er3+ transitions from the 2H11/2, 4S3/2 and 4F9/2 levels to the 4I15/2 ground state.

 

IPC Code: Int. Cl.8 C07F5/00

 

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1373-1376

 

 

Kinetics and mechanism of oxidation of some thioacids by morpholinium chlorochromate

 

N Malani, S Pohani, M Baghmar & Pradeep K Sharma*

Received 11 April 2008; revised 20 June 2008

Oxidation of thioglycollic, thiolactic and thiomalic acids by morpholinium chlorochromate is first order both in MCC and thioacids. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence takes the form kobs=a+b [H+]. Oxidation of the thiolactic acid has been studied in nineteen different organic solvents. The solvent effect has been analysed by using Kamlets and Swains multiparametric equations. A mechanism involving the formation of a thioester and its decomposition in slow step is also proposed.

IPC Code: Int. Cl.8 C07B33/00

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1377-1380

 

 

Sorption behaviour of D 155 resin for Ce(III)

Chunhua Xiong

Received 29 October 2007; revised 24 July 2008

The sorption of Ce(III) by D155 resin is reported here. The effect of pH on the sorption of Ce(III), the sorption capacity of the resin, the isotherms, kinetics and thermodynamics have been investigated by the sorption-desorption method. The sorption mechanism is also proposed. The sorption is spontaneous and endothermic under the examined conditions.

IPC Code: Int. Cl.8 B01J39/00

 

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1381-1383

 

 

2-Hydroxy-1-naphthaldehyde-p-hydroxybenzoic hydrazone as a spectrophotometric reagent for the determination of lanthanum (III)

P Govinda Chowdary, K P P R Mohan Reddy, V Krishna Reddy* & P Raveendra Reddy

Received 13 February 2008; revised 20 June 2008

A new chromophore, 2-hydroxy-1-naphthaldehyde-p-hydroxybenzoic hydrazone has been used for the determination of lanthanum (III). The reagent reacts with lanthanum (III) in aqueous dimethyl formamide in wide pH range forming brownish yellow coloured 2:3 (M:L) soluble complex with lmax at 415 nm. The colour intensity further increases in the cetyl trimethyl ammonium bromide micellar medium (0.1%) at room temperature. Beers law is obeyed in the range 0.277-8.334 μg mL-1 and 0.008-2.639 μg mL-1 of La(III) in direct and derivative methods, respectively. The molar absorptivity, Sandells sensitivity, detection limit, determination limit and relative standard deviation are found to be: 2.38104 L mol-1 cm-1, 0.006 μg cm-2, 0.035 μg mL-1, 0.106 μg mL-1 and 0.42%, respectively. The second order derivative spectrophotometric method developed for the determination of lanthanum (III) shows greater sensitivity and selectivity. The proposed direct and derivative methods are applied for the determination of lanthanum in standard lanthanum samples.

IPC Code: Int. Cl.8 G01N21/2

 

Indian Journal of Chemistry

Vol. 47A, September 2008, pp. 1384-1388

 

Micellar effects on dye sensitized photooxidation of phenothiazine

Shipra Kathuria, P K Gupta & N R Dhamiwal*

Received 11 February 2008; revised 5 August 2008

Methylene blue sensitized photooxidation of phenothiazine (PTH) in sodium dodecylsulphate, cetyl trimethylammonium bromide and brij-35 in methanol-water, ethanol-water and acetonitrile-water gives phenothiazine-3-one (PTN) and phenothiazine sulphoxide as the products at low conversion. A small shift in the λmax indicates the formation of an additional product, which is destroyed during the separation. An inverse relationship between log Φ (Φ= quantum yield of PTN formation) and 1/Є0 0 = dielectric constant of the medium) supports the participation of singlet oxygen (1O2) at low [PTH]. A mechanism consistent with the results showing the participation of 1O2 at low [PTH] and electron transfer-exciplex formation at high [PTH] is postulated. The formation of phenothiazine sulphoxide has been suggested to be through the phenothiazinyl radical.