Indian Journal of Chemistry

 

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

 

VOLUME 46A

NUMBER 1

January 2007

 

CONTENTS

 

 

9

 

A computational study of the interaction of
[7]-helicene with alkali cations and benzene

 

 

 

 

 

 

 

 

 

 

 

Sangeeta Saini & B M Deb*

 

 

 

Ab initio calculations, using restricted Hartree-Fock, density-functional and Moeller-Plesset perturbation theories have been performed to study the cation-π interactions between alkali cations and [7]-helicene as well as the interaction between
[7]-helicene and benzene.

 

16

 

Influence of amorphicity on properties of Ce-Ti mixed oxide films for electrochromic devices

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Amita Verma*, S K Shukla, A K Bakhshi &
S A Agnihotry

 

 

 

Alcohol based sols of cerium chloride and titanium propoxide mixed in 1:1 and 1:3 mole ratios have yielded mixed oxide films with excellent chemical as well as mechanical stability on densification at 500°C. SEM micrographs show the presence of CeO2 and TiO2 agglomerates respectively in the 1:1 and 1:3 films. The faster coloration-bleaching kinetics for the primary electrochromic electrode working in combination with Ce/Ti (1:1) electrode indicates the better utility of latter in electrochromic windows. Appreciable optical modulation of the electrochromic devices comprising both the Ce/Ti compositions of the counter electrodes over the visible spectral region displays their potential as the ion storage layer for the electrochromic windows.

 

 

24

 

Thermal conductivity prediction for nitrogen and carbon monoxide at the zero density regime via semi-empirically based assessment

 

 

 

 

Behzad Haghighi*, Dariush Shahidi &
Mohammad Mehdi Papari

 

 

 

Thermal conductivity coefficients for gaseous states of N2 and CO are calculated by the inversion technique in conjunction with Wang Chang-Uhlenbeck-de Boer   approach of the kinetic theory of gases for considering the various contributions of the molecular degrees of freedom to the thermal conductivity. The values of calculated thermal conductivity coefficients are commensurate with best experimental values.

 

 

33

 

Force constant calculations for Hg[Co(CO)4]2 from the CO-factored force field

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Cemal Kaya* & Duran Karakaş

 

 

 

An analytical approach to solve the CO-factored force fields of Hg[Co(CO)4]2 belonging to D3d point group is described. The approach leads to relationships, which allow direct calculation of carbonyl stretching force constants and CO-CO interaction constants from C-O stretching frequencies of an all 12C16O molecule.

 

 

39

 

Absorption spectral study of mixed ligand complexes of some biochemically important polyamine polycarboxylic acids with Nd(III) and Pr(III)

 

 

 

 

 

 

Prashant N Bhatt*, Trupti V Pathak,
Pankaj J Bhadani & Sudhindra N Misra

 

 

 

Absorption spectroscopy has been used as a tool to understand the coordination of mixed ligand complexes of Nd(III) and Pr(III) with polyamino carboxylic acids in presence of acetyl acetone in aquo-organic medium (DMF/H2O). The spectral characteristics like oscillator strengths, Tλ and Judd-Ofelt intensity parameters of the 4f-4f transitions have been evaluated in order to investigate the formation and the type of bonding in the lanthanide-ligand complexes in DMF.

 

 

48

 

Aggregation of malonic acid dihydrazide with thymine and 2,6-diaminopyridine in the presence of copper(II) and zinc(II) chlorides: Synthesis, characterization and molecular conducting properties

 

 

 

 

 

L Mishra*, B Pathak & S K Dubey

 

 

 

Malonic acid dihydrazide has been complexed with thymine and 2,6-diaminopyridine separately in presence of Cu(II) and Zn(II) chlorides. Hydrogen bonded networks thus obtained, have been characterized by physicochemical and spectroscopic studies and their solid-state electrical conductances have been measured at different temperatures. Microstructures of the resulting systems have been compared with their optical micrographs.

 

 

54

 

Ultrasonic investigations in amino acids with aqueous dimethyl formamide

 

 

 

 

 

A N Kannappan & R Palani*

 

 

 

Ultrasonic velocity, density and viscosity have been measured for three amino acids, viz., glycine, l-alanine and l-serine in dimethyl formamide + water mixtures. Derived parameters like adiabatic compressibility, apparent molal compressibility, apparent molal volume, viscosity B-coefficient, etc., have been calculated for all the ternary systems. The results have been interpreted in the light of intermolecular interactions in terms of the structure-making or structure-breaking effects of these amino acids in the mixtures.

 

 

60

 

Densities, viscosities and thermodynamic excess properties of ternary liquid mixtures of aniline and methyl alcohol as common components and
non-polar solvents at 298.15 K

 

 

 

 

 

 

 

 

 

Arti Goyal & Mukhtar Singh*

 

 

 

Densities and viscosities of the ternary liquid mixtures, aniline
+ methyl alcohol + (benzene;+ toluene;+ carbon tetrachloride;
+ 1,4-dioxane) are reported. The viscosity deviations and thermodynamic excess properties, viz. , excess molar volume and excess Gibbs free energy of activation of viscous flow for the ternary mixtures have also been determined and fitted to Cibulka’s equation. The experimental values of these parameters are found to be in close agreement with those predicted by Cibulka’s equation. The types of interactions taking place between the molecules of mixing components of ternary liquid mixtures are also discussed.

 

Notes

 

70

 

Structural and optical characterization on solution grown methyl p-hydroxybenzoate single crystals

 

 

 

 

 

 

 

 

 

 

 

N Vijayan, G Bhagavannarayana*,
R Gopalakrishnan & P Ramasamy

 

 

 

The optical quality single crystals of methyl
p-hydroxybenzoate have been grown by slow evaporation solution growth technique and characterized using different instrumentation methods. Their structural perfection has been analysed by using high resolution X-ray diffractometry. The crystal system is monoclinic. The presence of carbon molecules has been identified by 13C NMR technique. The laser damage threshold and second harmonic generation efficiency have been studied. The second harmonic generation conversion efficiency ratio of p-MHB to KDP is around 1.29:1.

 

74

 

Effect of valence band and conduction band discontinuities on the electronic structures and conduction properties of copolymers of Type-I

 

 

 

Amit Kumar & A K Bakhshi*

 

 

 

The effect of change in the ratio of conduction band discontinuity to the valence band discontinuity (∆Ec/∆Ev) on the electronic structures and conduction properties of model copolymers (AmBn)x, belonging to the class of Type-I quasi-one-dimensional superlattices are reported. For each of these systems of copolymers, the electronic density of states of the various periodic and aperiodic copolymer chains have been determined on the basis of negative factor counting method in tight binding approximation.

 

 

80

 

Copper(I) complexes of  2-thiouracil

 

 

 

 

 

 

 

 

Sülin Taşcıoğlu

 

 

 

Reaction of 2-thiouracil and cupric hydroxide in different solvents gives mononuclear or polynuclear complexes of Cu(I) depending on the reaction conditions. Hydroxo complexes of copper(I) have been obtained at pH ~3.5. Oligomeric structures of polynuclear complexes are suggested to be via the bridging of copper atoms through electron donating atoms of bidentate thiouracil.

 

 

86

 

Synthesis and characterization of AlPO4-zeolites using alanine and glycine as templates

 

 

 

 

 

 

 

 

 

 

 

B V Suresh Kumar*, K Byrappa,
K M Lokanatha Rai, M K Devaraju,
M S Vijaya Kumar & C Ranganathaiah

 

 

 

Microporous AlPO4-zeolites have been synthesized in the presence of glycine and alanine under mild hydrothermal conditions.

 

 

 

91

 

Role of surfactant in the studies of solar energy conversion and storage: CTAB-Rhodamine 6G – oxalic acid system

 

 

 

 

 

 

 

 

 

K R Genwa* & Mahaveer

 

 

 

The photogalvanic effect, studied in a photogalvanic cell containing cetyltrimethylammonium bromide as surfactant, Rhodamine 6G as photosensitizer and oxalic acid as reductant, is reported. The observed photopotential and photocurrent are
414.0 mV and 90.0 µA, respectively. The observed conversion efficiency is 0.55%, and fill factor is 0.45 while the maximum power output of cell is 25.22 µW.

 

 

97

 

Studies on multielemental uptake of amide incorporated Amberlite IRC-50 using tracer packet techniques

 

 

 

 

 

 

 

 

Samir Maji, Sukalyan Basu & Susanta Lahiri*

 

 

 

A chelating resin has been synthesized by incorporating amide group into Amberlite IRC-50. Tracer packet technique has been used to study the multielemental uptake on amide incorporated Amberlite IRC-50 ion exchanger. It has been found that the resin has high adsorption affinity for Cu, Zn, Hg, Pb and Tl, and for the lanthanides, Tb, Dy and Er.

 

 

Authors for correspondence are indicated by (*)


Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 9-15

 

A computational study of the interaction of [7]-helicene with
alkali cations and benzene

Sangeeta Saini & B M Deb*

Received 17 August 2006; revised 4 December 2006

Ab initio calculations, using restricted Hartree-Fock, density-functional (DFT) and Moeller-Plesset perturbation theories, have been performed to study the cation-π interactions between alkali cations and [7]-helicene as well as the interaction between [7]-helicene and benzene. The helical molecule’s two terminal benzene rings give the profile of ‘crocodile’s jaws’ which open up to receive the cations, exhibiting the stability of the complexes increasing in the order Na+>K+>Cs+. The binding energies in these cation-π complexes comprise mainly electrostatic, polarization (including dispersion) and charge transfer contributions. According to DFT, the electrostatic contribution alone is 43% for Na+, 60% for K+ and 75% for Cs+. However, even DFT shows very little stabilization for the helicene-benzene complex so that this interaction between a helical and a neutral molecule cannot serve as a model for DNA-drug interactions due to very little overlap between the π clouds of the two molecules.

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 16-23

 

Influence of amorphicity on properties of Ce-Ti mixed oxide films for electrochromic devices

Amita Verma*, S K Shukla, A K Bakhshi & S A Agnihotry

Received 22 August 2006; revised 7 December 2006

Alcohol based sols of cerium chloride and titanium propoxide mixed in 1:1 and 1:3 mole ratios have yielded mixed oxide films with excellent chemical as well as mechanical stability on densification at 500°C. The 1:1 films are more transparent due to their highly porous structure. Electrochemical studies have revealed the significant role of TiO2 in controlling the ion storage capacity of the films, as it induces amorphicity in them. Although both the films are found to be amorphous to X-rays, the 1:1 composition however, is characterized by the presence of CeO2 nanocrystallites of about 5 nm dimension. XPS studies have shown the presence of both Ce3+ and Ce4+ states in the films. Scanning electron microscopic study has shown the presence of CeO2 and TiO2 agglomerates respectively in the 1:1 and 1:3 films. The faster coloration-bleaching kinetics for the primary electrochromic electrode working in combination with Ce/Ti (1:1) electrode indicates the better utility of the latter in electrochromic windows. Appreciable optical modulation of the electrochromic devices comprising both the Ce/Ti compositions of the counter electrodes over the visible spectral region displays their potential as the ion storage layer for the electrochromic windows.

IPC Code: Int. Cl.8 C01F17/00; C01G23/02; H01M4/88

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 24-32

 

Thermal conductivity prediction for nitrogen and carbon monoxide at the zero density regime via semi-empirically based assessment

 

Behzad Haghighi*, Dariush Shahidi & Mohammad Mehdi Papari

Received 22 June 2006; revised 29 October 2006

Thermal conductivity coefficients for gaseous states of N2 and CO have been calculated by the inversion technique in conjunction with Wang Chang-Uhlenbeck-de Boer (WCUB) approach of the kinetic theory of gases for considering the various contributions of the molecular degrees of freedom to the thermal conductivity. The values of calculated thermal conductivity coefficients are commensurate with best experimental values.

 

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 33-38

 

Force constant calculations for Hg[Co(CO)4]2 from the CO-factored force field

Cemal Kaya* & Duran Karakaş

Received 12 June 2006; revised 23 November 2006

An analytical approach to solve the CO-factored force fields of Hg[Co(CO)4]2 belonging to D3d point group is described here. The approach leads to relationships which allow direct calculation of carbonyl stretching force constants and CO-CO interaction constants from C-O stretching frequencies of an all 12C16O molecule. The force constants calculated by these relationships have been found to be in excellent agreement with those obtained from the Cosb parameter method. In addition, carbonyl stretching frequencies of the mono 13CO substituted derivatives of Hg[Co(CO)4]2 have been estimated. The results exhibit agreement between calculated and observed frequencies, showing thereby that the analytical approach presented here gives a valid solution to the CO-factored force field of the molecule under study.

Indian Journal of Chemistry

Vol. 46A, January 2007, pp 39-47

Absorption spectral study of mixed ligand complexes of some biochemically important polyamine polycarboxylic acids with Nd(III) and Pr(III)

Prashant N Bhatt*, Trupti V Pathak, Pankaj J Bhadani & Sudhindra N Misra

 

Received 26 April 2006; revised 29 November 2006

Absorption spectroscopy has been used as a tool to understand the coordination of a mixed ligand complexes of neodymium (III) and praseodymium (III) with the polyamino carboxylic acids, viz., nitrilotriacetic acid,
10-(2-hydroxypropyl)-1,4,7-10 tetraazacyclo dodacane 1,4,7-triacetic acid, ethylene diamine-N,N,N
¢,N¢-tetraacetic acid, cyclohexylene diamine tetraacetic acid, and diethylene triamine-N,N,N¢,N¢-pentaacetic acid (NTA, HEDTA, EDTA, CDTA and DTPA) in presence of acetyl acetone in aquo-organic medium (DMF/H2O). The spectral characteristics like oscillator strengths, Tl, and Judd-Ofelt intensity parameters of the 4f-4f transitions have been evaluated in order to investigate the formation and the type of bonding in lanthanide-ligand complexes in DMF. The values have been computed for energy interaction Slater Condon (Fk'), nephelauxetic effect (b), bonding (b1/2) and %covalency (d) parameters.

IPC Code: Int. Cl.8 C07F5/00

 

Indian Journal of Chemistry

Vol. 46A, January 2007, pp.48-53

 

Aggregation of malonic acid dihydrazide with thymine and 2,6-diaminopyridine in the presence of copper(II) and zinc(II) chlorides: Synthesis, characterization and molecular conducting properties

L Mishra*, B Pathak & S K Dubey

Received 20 April 2006; revised 22 November 2006

Malonic acid dihydrazide (MADH) earlier condensed with thymine (Thy) and 2,6-diaminopyridine (DAP) separately has been complexed with CuCl2.2H2O and ZnCl2. Resulting solids have been assigned the compositions Cu(MADH)2Cl2.2Thy.5H2O, (1); Cu(MADH)2Cl2.2DAP.8H2O, (2); Zn(MADH)2Cl2.2Thy.2H2O, (3); and
Zn(MADH)2 Cl2.2DAP.10H2O, (4) on the basis of elemental analysis and FAB mass data, and further characterized by the IR, NMR, UV-vis and EPR spectra together with their powder X-ray diffraction and microstructures. Peak widths in almost all complexes have been found to be higher than those introduced by instrumental broadening in their XRD data which clearly indicates size restriction on the coherently scattering domain, thus characterizing the complexes with larger motifs. Significant differences in solid-state electrical conductances between Thy-based complexes and DAP-based complexes are noted as closer linear fit of log
s versus 1000/T curve is observed for the former whereas polynomial relationship is being followed by the latter. In optical micrographs, MADH.DAP consists of lamellae and connected network of granules in local regions. However, the addition of Zn(II) chloride in this system leads to the formation of fine colonies which totally disappear in the Cu(II) complex. Presence of H-donors in DAP and both the H-donor and H-acceptors in Thy-based complexes have been observed as a variable parameter in their structural networking.

IPC Code: Int. Cl. 8 C07F1/08; C07F3/06

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 54-59

 

Ultrasonic investigations in amino acids with aqueous dimethyl formamide

A N Kannappan & R Palani*

Received 19 April 2006; revised 6 December 2006

Ultrasonic velocity (U), density (ρ) and viscosity (h) have been measured for three amino acids, namely, glycine,
l-alanine and l-serine in the mixture of dimethyl formamide (DMF) and water, at different proportions of DMF at 298 K. The adiabatic compressibility (β), change in adiabatic compressibility (
Dβ), relative change in adiabatic compressibility (Dβ/β0), apparent molal compressibility (), apparent molal volume (), limiting apparent molal compressibility (), limiting apparent molal volume (), and their constants (SK, SV), and viscosity B-coefficient have been calculated for all the ternary systems. The results have been interpreted in the light of intermolecular interactions in terms of the structure-making or structure-breaking effects of these amino acids in the mixture.

IPC Code: Int. Cl.8 G01B17/00

 

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 60-69

 

 

Densities, viscosities and thermodynamic excess properties of ternary liquid mixtures of aniline and methyl alcohol as common components and
non-polar solvents at 298.15 K

 

Arti Goyal & Mukhtar Singh*

Received 5 May 2006; revised 9 November 2006

             Densities and viscosities of the ternary liquid mixtures, aniline + methyl alcohol + (benzene;+ toluene;+ carbon tetrachloride; + 1,4-dioxane) at 298.15 K are reported here. From the density and viscosity data, the values of viscosity deviations (Dh) and thermodynamic excess properties, viz., the excess molar volume (VE) and excess Gibbs free energy of activation of viscous flow (DG#E) for the ternary mixtures have been determined and fitted to Cibulka’s equation. The experimental values of Dh, VE and DG#E have been found to be in close agreement with those predicted by Cibulka’s equation. The types of interactions taking place between the molecules of mixing components of ternary liquid mixtures are also discussed.

 

 

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 70-73

Structural and optical characterization on solution grown methyl p-hydroxybenzoate single crystals

N Vijayan, G Bhagavannarayana*, R Gopalakrishnan & P Ramasamy

Received 21 June 2006; revised 17 November 2006

The optical quality single crystals of methyl p-hydroxybenzoate (p-MHB) have been successfully grown by slow evaporation solution growth technique at 33°C. The grown single crystals have been characterized using different instrumentation methods. The structural perfection has been analysed by using high resolution X-ray diffractometry, which shows that the crystalline perfection is reasonably good except with two low angle internal structural boundaries. That may be due to entrapment of impurities and solvent molecules during growth. The crystal system is monoclinic with calculated lattice parameter values: a = 13.977 Å; b = 15.774 Å; c = 12.684 Å; a = g = 90°; b = 131.97°. The presence of carbon molecules has been identified from 13C NMR. The laser damage threshold and second harmonic generation efficiency have been studied. The second harmonic generation conversion efficiency ratio of p-MHB to KDP has been found to be around 1.29:1.

IPC Code: Int. Cl.8 C30B7/02

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 74-79

 

Effect of valence band and conduction band discontinuities on the electronic structures and conduction properties of copolymers of Type-I

Amit Kumar & A K Bakhshi*

Received 27 June 2006; revised 4 December 2006

The effect of change in the ratio of conduction band discontinuity to the valence band discontinuity (∆Ec/∆Ev) on the electronic structures and conduction properties of model copolymers (AmBn)x, belonging to the class of Type-I quasi-one-dimensional superlattices are reported. Six different systems of copolymers (AmBn)x, differing in respect of the ratio ∆Ec/∆Ev, have been modelled using the model band structure of constituent homopolymers (A)x and (B)x. For each of these systems of copolymers the electronic density of states of the various periodic and aperiodic copolymer chains have been determined on the basis of negative factor counting method in tight binding approximation. The trends obtained in the electronic structures and conduction properties of these copolymers as a function of the ratio ∆Ec/∆Ev are useful guidelines for designing copolymers with desired electronic and conduction properties.

 

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 80-85

 

Copper (I) complexes of 2-thiouracil

Sülin Taşcıoğlu

Received 26 July 2006; revised 15 November 2006

Copper complexes obtained from the reactions between2-thiouracil and cupric hydroxide in different solvents have been investigated. Mononuclear or polynuclear complexes of Cu(I) have been obtained depending on the reaction conditions. Hydroxo complexes of copper(I) have been obtained at pH around 3.5. 2-Thiouracil acts as mono- or bidentate ligand in complexes. [Cu(H2TU)2 OH], [Cu5(H2TU)6 (OH)5] and [Cu3(H2TU)4-(HTU)(OH)2] have been obtained from the aqueous ethanolic, aqueous and dioxan solutions, respectively. Oligomeric structures of polynuclear complexes are suggested to be via the bridging of copper atoms through electron donating atoms of bidentate thiouracil. The complex, [Cu3(H2TU)4(HTU)(OH)2], reacts with concentrated HCl to give [Cu3(H2TU)4Cl3], in which its trinuclear structure is preserved. The properties and structure of [Cu3(H2TU)4Cl3] are different from those of [Cu(H2TU)2 Cl], which is synthesized from cuprous chloride. Spectral, thermal, magnetic studies and elemental analyses for the complexes have been carried out.

IPC Code: Int. Cl.8 C07F1/08

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 86-90

 

Synthesis and characterization of AlPO4-zeolites using alanine and glycine as templates

B V Suresh Kumar*, K Byrappa, K M Lokanatha Rai, M K Devaraju, M S Vijaya Kumar & C Ranganathaiah

 

Received 30 January 2006; revised 18 November 2006

Microporous AlPO4-zeolites have been synthesized in the presence of glycine and alanine under mild hydrothermal conditions, maintaining temperature at 150°C under autogeneous pressure. Reaction mechanism has been proposed for the crystallization process. The use of amino acids results in tremendous effects on the pore size of AlPO4-zeolites. The cell volume and surface area are increased while the void fraction is decreased. The products have been characterized using XRD, FTIR, Positron annihilation life time techniques and BET surface area analysis. Scanning electron micrographs show the morphological and structural changes when alanine and gylcine are used as structure directing agents or templates.

IPC Code: Int. Cl.8  B01J29/00; C01B39/54

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 91-96

 

Role of surfactant in the studies of solar energy conversion and storage: CTAB-Rhodamine 6G-oxalic acid system

K R Genwa* & Mahaveer

Received 30 November 2005; rerevised 23 November 2006

The photogalvanic effect, studied in a photogalvanic cell containing cetyltrimethylammonium bromide as surfactant, Rhodamine 6G as photosensitizer and oxalic acid as reductant, is reported. The effects of concentrations of surfactant photosensitizer and reductant, pH, diffusion length, electrode area and temperature on electrical output of the cell are reported. The observed photopotential and photocurrent are 414.0 mV and 90.0 µA, respectively. The observed conversion efficiency is 0.55 %, fill factor is 0.45 and the maximum power output of cell is 25.22 µW. The photogalvanic cell can be used for 96 minutes in the dark (the storage capacity of cell in dark). A mechanism has also been proposed for the generation of photocurrent in photogalvanic cell. Dye-surfactant spectra have also been studied.

IPC Code: Int. Cl.8  H01L31/04; H01M14/00

Indian Journal of Chemistry

Vol. 46A, January 2007, pp. 97-100

 

Studies on multielemental uptake of amide incorporated Amberlite IRC-50 using tracer packet techniques

Samir Maji, Sukalyan Basu & Susanta Lahiri*

Received 7 July 2006; revised 2 November 2006

A chelating resin has been synthesized by incorporating amide group into Amberlite IRC-50, a weakly acidic polymer. Tracer packet technique has been used to study the multielemental uptake on amide incorporated Amberlite IRC-50 ion exchanger. It has been found that the resin has high adsorption affinity for Cu, Zn, Hg, Pb and Tl, and for the lanthanides Tb, Dy and Er.

IPC Code: Int. Cl.8  B01D15/04; B01J39/00