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 55A

NUMBER 1

JANUARY 2016

 

CONTENTS

 

 

9

 

Photocatalytic degradation of methylene blue and methyl violet using cation doped (Sn2+ and Ag+) barium tellurite phosphate, Ba2TeO(PO4)2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

CH Sudhakar Reddy, Sreenu K, J R Reddy, G Ravi, Ravinder Guje, M Malathi & M Vithal*

 

 

 

Ag+ and Sn2+ doped BTOP are isomorphous with the parent compound and crystallize in the triclinic lattice with the P1 space group. Ag+ and Sn2+ substitution for Ba2+ in BTOP is effective in decreasing the band gap energy and increasing the photocatalytic activity. Photocatalytic studies in the presence of radical quenchers confirm that O2, OH, and h+ are the main reactive species in the photocatalytic degradation under visible light irradiation. All the photocatalysts are chemically stable and can be used up to at least four cycles.

 

 

 

 

16

 

Photocatalytic degradation of ciprofloxacin·HCl using Aeroxide® P-25 TiO2 photocatalyst: Comparative evaluation of solar and artificial radiation

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rohit Shetty, Gaurav Kothari, Amruta S Tambe, Bhaskar D Kulkarni & Sanjay P Kamble*

 

 

 

In presence of both solar as well as artificial radiation, ciprofloxacin·HCl (CFX) is degraded from aqueous solutions using Aeroxide® P-25 TiO2 photocatalyst, with maximum degradation at pH 9. Rate of degradation of CFX using solar radiation is about 1.7 times higher than that under artificial radiation. Sodium carbonate has a substantial detrimental effect, while on a comparative basis, ammonium sulfate and sodium chloride do not show any significant effect on the photocatalytic degradation of CFX.

 

 

 

 

23

 

Internal pressure, free volume and excess thermodynamic properties of methyl acrylate+1-alkanols (C4-C10) binary mixtures from ultrasonic speed and density

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A K Nain* & P Droliya

 

 

 

Excess thermodynamic parameters of methyl acrylate+1-alkanol (C4–C10) binary mixtures indicate weak interactions in the order:
1-butanol > 1-hexanol > 1-octanol > 1-decanol. The results indicate the applicability of scaled particle theory in estimating their ultrasonic speeds reasonably well.

 

 

 

 

34

 

Influence of organic solvents, head-groups and temperature on the micellization behavior of some cationic surfactants

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A K Sood, Rupinderjit Kaur & T S Banipal*

 

 

 

The CMC of tetradecyltrimethyl ammonium bromide, tetradecyl-dimethylbenzyl ammonium chloride and their dimeric homologue, dimethylene-1,2-bis(tetradecyldimethyl ammonium bromide) increases in the presence of ethylene glycol, dioxane and dimethyl formamide as these are better solvents than pure water. The increment in CMC in presence of ethylene glycol is the least among the studied solvents. Both CMC and α values increase with temperature and concentration of the solvents.

 

 

 

Notes

 

44

 

Pyridoxal derived chemosensor: Its application in anion sensing and molecular logic gate building

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Suban K Sahoo*, Darshna Sharma, Shilpa Bothra, Sutapa Mondal Roy, Rajender Kumar,
Ashok Kumar SK, Jitendra P Nandre,
Umesh D Patil & John F Callan

 

 

 

A new, simple and easy-to-prepare colorimetric anion sensor has been developed using Schiff base reaction of pyridoxal with hydrazine. The color of the sensor changes from colorless to red on introduction of F and AcO anions due to partial deprotonation of aromatic-OH protons. It is also selective for F and AcO anions in a competitive environment, with a detection limit in the micromolar range. The sensor also displays INHIBIT type molecular logic gate with the inputs of F- and Ca2+.

 

Presentation1

 

 

 

51

 

Design and construction of ion-selective electrode based on a new Schiff base and its application in determination of copper(II) ions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Z Valilue, M T Vardin* & E Ghorbani Kalhor

 

 

 

A Cu(II) selective sensor has been made from polyvinyl chloride matrix membrane based on the carrier, 2-(5-bromo-2-hyroxybenzylidineamino)pyridine-3-ol as the ionophore,
ortho-nitrophenyl octyl ether (o-NPOE) as mediator solvent and sodium tetraphenylborate (NaTPB) as additive. The best performance is presented by membrane composition 3:33:63:1 (ionophore:PVC:o-NPOE:NaTPB; by wt). The sensor shows a detection limit of 7.4×10-8 M with a linear response in the
concentration range of 1.0×10-7 to 1.0×10-2 M with Nernstian slope of 29.5±0.5 mV per decade of Cu2+. The sensor can be used in the pH range of 4–7. The sensor shows a response time of less than 10 s and can be used for at least eight weeks without any difference in potential.

 

 

 

 

57

 

Effect of flocculating agents on solubility behavior of calcium sulfate dihydrate (gypsum) in aqueous sodium chloride system and solution properties at 35 °C

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jignesh Shukla, Tushar J Trivedi,
Pankaj Bharmoria & Arvind Kumar
*

 

 

 

The effect of addition of flocculating agents, viz., alum (KAl(SO4)2·12H2O) (up to 10 wt%) and polyaluminum chloride ([Al(OH)aClb]n, a >1.05; n~15) (up to 6 wt%) on the solubility behavior of CaSO4·2H2O) in aqueous NaCl solutions has been examined at 35 °C. The solubility of CaSO4·2H2O decreases on addition of alum, while it increases on addition of polyaluminum chloride without any significant shift in solubility maximum.

 

 

 

 

64

 

Guide to Authors

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 9-15

 

Photocatalytic degradation of methylene blue and methyl violet using
cation doped (Sn2+ and Ag+) barium tellurite phosphate, Ba2TeO(PO4)2

CH Sudhakar Reddy, Sreenu K, J R Reddy, G Ravi, Ravinder Guje, M Malathi & M Vithal*

Department of Chemistry, University College of Science, Osmania University, Hyderabad 500 007, India
Email: mugavithal@gmail.com

Received 14 October 2015; accepted 16 December 2015

One-dimensional barium tellurite phosphate of composition, Ba2TeO(PO4)2, is prepared by solid state method. Tin (Sn2+) and silver (Ag+) doped Ba2TeO(PO4)2 materials are prepared via a facile room temperature ion-exchange method. Structural, morphological, and optical properties of all the materials are characterized by powder X-ray diffraction, FT-IR, SEM-EDS, and UV-visible diffuse reflectance spectroscopy techniques. The band gap energy (Eg) of all the phosphates is deduced from their Kubelka–Munk (KM) plot. The synthesized phosphates are used as photocatalyst for the degradation of methylene blue and methyl violet dyes under the visible light irradiation. The systematic degradation pathways of the dyes are studied in the presence of all the photocatalysts and scavengers. The stability and reusability of all the photocatalyst are assessed by the cycling runs in the photodegradation experiment.

Keywords: Photocatalysts, Doping, Photodegradation, Dye degradation, Barium tellurite phosphate, Methylene blue, Methyl violet, Tin, Silver

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 16-22

 

Photocatalytic degradation of ciprofloxacin·HCl using Aeroxide® P-25 TiO2 photocatalyst: Comparative evaluation of solar and artificial radiation

Rohit Shetty, Gaurav Kothari, Amruta S Tambe, Bhaskar D Kulkarni & Sanjay P Kamble*

Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory,

Dr. Homi Bhabha Road, Pune 411 008, India

Email: sp.kamble@ncl.res.in

Received 20 October 2015; revised and accepted 22 December 2015

The photocatalytic degradation of ciprofloxacin (CFX) has been investigated using Aeroxide® P-25 TiO2 photocatalyst in the presence of solar as well as artificial radiation. The effects of different operating parameters like initial concentration of CFX, catalyst loading, pH of solution and effect of co-existing ions on photocatalytic degradation of CFX have been investigated with a view to establish the optimum operating conditions. It is observed that as the initial concentration of CFX increases, the rate of photocatalytic degradation decreases. Optimum catalyst loading is observed at 1 g L-1 for CFX concentration of 100 mg L-1. Over the pH range 3-11, maximum degradation rate occurs at pH 9. The mechanism and intermediates formed during the photocatalytic degradation of CFX are discussed based on UPLC-MS/MS analysis. From kinetic studies, it is found that the photocatalytic degradation obeys pseudo-first order kinetics. The degradation rate constant using solar radiation is about 1.7 times higher than that under artificial radiation.

Keywords: Photocatalysis, Advanced oxidation process, Pharmaceutical micropollutants, Degradation,
Solar radiation, Artificial radiation, Aeroxide® P-25 TiO2, Ciprofloxacin·HCl

 

 

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 23-33

 

Internal pressure, free volume and excess thermodynamic properties of methyl acrylate+1-alkanols (C4-C10) binary mixtures from ultrasonic speed and density

A K Nain* & P Droliya

Department of Chemistry, Dyal Singh College (University of Delhi), Lodi Road, New Delhi 110 003, India

Email: ak_nain@yahoo.co.in

Received 2 November 2015; revised and accepted 7 December 2015

The experimental values of ultrasonic speeds and densities, of binary mixtures of methyl acrylate with
1-butanol, 1-hexanol, 1-octanol and 1-decanol have been used to calculate the internal pressures, free volumes, excess internal pressures, excess free volumes, excess free energy, excess enthalpy and excess entropy of mixing over the entire composition range at 298.15 K using regular solution theory. The results have been interpreted in terms of intermolecular interactions between the component molecules in the mixture. The variations of these excess properties with composition indicate that the methyl acrylate-alkanol interaction in these mixtures follows the order: 1-butanol > 1-hexanol > 1-octanol > 1-decanol. It is observed that the order of interactions in these mixtures depends upon the length of alkyl chain in the studied 1-alkanol molecules. In addition, the values of ultrasonic speeds have also been calculated theoretically for these mixtures using scaled particle theory and found to be in good agreement with experimental findings.

Keywords: Solution chemistry, Thermodynamics, Excess properties, Methyl acrylate, Alkanols,
Molecular interactions, Regular solution theory, Scaled particle theory

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 34-43

 

Influence of organic solvents, head-groups and temperature on the
micellization behavior of some cationic surfactants

A K Sood, Rupinderjit Kaur & T S Banipal*

*Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005, Punjab, India

Email: tsbanipal@yahoo.com (TSB)/ aksoodchem@yahoo.co.in (AKS)/
rupinderrandhawa55@yahoo.com (RK)

Received 19 May 2015; revised and accepted 29 December 2015

The effect of organic solvents, viz., dioxane, dimethylformamide and ethylene glycol on the micellization behavior of cationic surfactants, i.e., tetradecyltrimethyl ammonium bromide (TTAB), tetradecyldimethylbenzyl ammonium chloride (C14BCl) and their dimeric homologue, dimethylene-1,2-bis(tetradecyldimethyl ammonium bromide) (14-2-14) is studied in aqueous solutions using conductometric and viscometric techniques at different temperatures (288.15–318.15 K). It is observed that the critical micelle concentration and degree of counterion dissociation values increase with the increase in volume percentage and the temperature. Studies on the the temperature dependence of the CMC values show that the standard Gibbs free energy of micellization values increase with the concentration of organic solvents and temperature whereas the opposite trend is observed for enthalpy. The randomness of the system decreases in presence of solvents.
The relative viscosity of the surfactants was found to be more in presence of ethylene glycol among the studied systems. The effect of temperature on relative viscosity for these systems has also been discussed.

Keywords: Solution chemistry, Micellization, Surfactants, Cationic surfactants, Organic solvents, Conductivity, Relative viscosity

 

 

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 44-50

 

Pyridoxal derived chemosensor: Its application in anion sensing and
molecular logic gate building

Suban K Sahooa, *, Darshna Sharmaa, Shilpa Bothraa, Sutapa Mondal Roya, Rajender Kumara,
Ashok Kumar SKb, Jitendra P Nandrec, Umesh D Patilc & John F Calland

aDepartment of Applied Chemistry, SV National Institute of Technology (SVNIT), Surat, Gujarat, India

Email: suban_sahoo@rediffmail.com

bSchool of Advanced Sciences, VIT University, Vellore, Tamilnadu, India

cSchool of Chemical Sciences, North Maharashtra University, Jalgaon, Maharashtra, India

dSchool of Pharmacy and Pharmaceutical Sciences, The University of Ulster,
Northern Ireland, BT52 1SA

Received 13 November 2015; accepted 31 December 2015

A new chemosensor L has been synthesized using Schiff base reaction of pyridoxal with hydrazine and characterized by various spectroscopic techniques such as FTIR, 1H NMR and mass spectrometry. The anion recognition ability of the synthesized sensor has been investigated by UV-vis, fluorescence and 1H NMR methods. Among the tested anions, the developed sensor shows a naked-eye detectable color change from colorless to red and spectral changes in the presence of fluoride and acetate ions due to the partial deprotonation of the sensor. With a micromolar detection limit, the developed sensor is highly efficient and may be utilised for the colorimetric detection of fluoride/acetate ions. The developed sensor has been successfully fabricated in to the INHIBIT logic gate at molecular level.

Keywords: Analytical chemistry, Chemosensors, Anion sensors, Fluoride, Acetate, Pyridoxal derivative, Molecular logic gate

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 51-56

 

Design and construction of ion-selective electrode based on a new Schiff base and its application in determination of copper(II) ions

Z Valilue, M T Vardin* & E Ghorbani Kalhor

Department of Chemistry, Tabriz Branch, Islamic Azad University, Tabriz, Iran

Email: mtvardini@iaut.ac.ir

Received 19 March 2015; revised and accepted 21 Nov 2015

A copper(II) selective sensor has been made from polyvinyl chloride matrix membrane based on the carrier, 2-(5-bromo-2-hyroxybenzylidineamino) pyridine 3-ol as an ionophore, ortho-nitrophenyl octyl ether (o-NPOE) as mediator solvent and sodium tetraphenylborate (NaTPB) as additive. The best performance is presented by membrane of composition of ionophore (Schiff base):PVC:o-NPOE:NaTPB of 3:33:63:1 (by weight). The membrane potential response is linear in the concentration range of 1.0×10-7 to 1.0×10-2 M with the Nernstian slope of 29.5±0.5 mV per decade of Cu2+ and a detection limit of 7.4×10-8 M. The response time of the sensor is very short; less than 10 s, and it can be used for at least 8 weeks without any difference in potential. The proposed copper(II) selective electrode displays excellent selectivity towards alkali, alkaline earth and transition metal ions and can be used in the pH range of 4-7. It has been successfully used as an indicator electrode for the determination of Cu(II) in water samples. The electrode has also been employed as an indicator electrode in titration of Cu2+ with EDTA.

Keywords: Electrochemistry, Electroanalytical chemistry, Ion-selective electrodes, Schiff bases, Potentiometry, PVC-membrane, Copper

 

 

Indian Journal of Chemistry

Vol. 55A, January 2016, pp. 57-63

 

Effect of flocculating agents on solubility behavior of calcium sulfate dihydrate (gypsum) in aqueous sodium chloride system
and solution properties at 35 °C

Jignesh Shuklaa, Tushar J Trivedib, Pankaj Bharmoriaa & Arvind Kumara, *

aSalt and Marine Chemicals Division, CSIR-Central Salt and Marine Chemicals Research Institute,
GB Marg, Bhavnagar 364 002, India

Email: arvind@csmcri.org/ mailme_arvind@yahoo.com

bGraduate School of EEWS (Energy Environment Water Sustainability), KAIST, 291 Daehak-ro,
Yuseong Gu, Daejeon 305-701, Republic of Korea

Received 17 September 2015; revised and accepted 01 January 2016

The effect of addition of flocculating agents, viz., alum (KAl(SO4)2·12H2O) (up to 10 wt%) and polyaluminum chloride ([Al(OH)aClb]n, a >1.05; n~15) (up to 6 wt%) on the solubility behavior of calcium sulfate dihydrate (gypsum, CaSO4·2H2O) in aqueous NaCl solutions has been examined at 35 °C. The solubility of CaSO4·2H2O decreases with the addition of alum while it increases with the addition of polyaluminum chloride without any significant shift in solubility maximum. Density (ρ) and speed of sound (u) have also been determined for the quaternary systems (CaSO4·2H2O+NaCl+alum/PAC+H2O) at
35 °C and used to estimate solution isentropic compressibility (κs) and ion-hydration (nh) characteristics. Empirical equations describing the s, ρ, u and κs as a function of solution composition are presented.

Keywords: Solution chemistry, Solubility, Flocculating agents, Gypsum, Density, Speed of sound