Research Journal of Chemistry and Environment

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Vol. 14(2) June 2010

Study on Copolymerization of CO/Styrene with [CH3C4Py]+PF6- as Novel Reaction Medium

Jintang Guo, Shan Gao, Yakai Feng* and Jing Wang

In this paper, pyridine (N-methylimidazole),bromoalkane, potassium hexafluorophosphate (sodium fluoborate） were used to prepare eleven ionic liquids, which were further applied to the copolymerization of CO and styrene as reaction medium. NMR, IR, XPS, TEM were employed to prove the prepared poly(1-oxo-2- phenyltrimethylene) was high crystal and strictly alternating copolymer. Effect of various ionic liquids on the copolymerization was studied to identify that the optimal ionic liquid to the copolymerization was 1-butyl-4-methylpyridine hexafluorophosphate which was then used as solvent of the CO/Styrene reaction. Moreover, effect of volume of ionic liquid, reaction temperature, reaction time, consumption of p-benzoquinone and ligands were also studied in detail. Results showed that the highest catalytic activity reached 723.34gSTCO/ (gPd•h) with the reaction conditions as follows: volume of ionic liquid=3ml, temperature of reaction temperature =600, reaction time=2h, molar ratio of pbenzoquinone/acetate palladium=80 and 0.0225 mmol, [Pd(N(CH3)-N(CH3))2][PF6]2 as composite catalyst; polyketones could still be obtained after 4times recycles of the catalyst. The application of ionic liquids instead of traditional solvents in the copolymerization of CO/Styrene supplied a feasible approach to reuse the catalyst and reduce the reaction cost.

Photocatalytic Decomposition of Methylene Blue over Titanium Dioxides Doped With Yttrium Ions Prepared Using Low Temperature Combustion Method

Jung Won Young1, Park Seong Soo1, Lee Gun Dae1, Lee Man Sig2, Lee Gang-Woo3 and Hong Seong-Soo1*

Nanosized TiO2 and yttrium ions doped TiO2 particles have been prepared using low temperature combustion method. The physical properties were investigated and we have also examined the activity of TiO2 particles as photocatalysts for the decomposition of methylene blue. From XRD results, the major phase of all TiO2 particles was an anatase structure regardless of doping of yttrium ions. It can be seen that no peak from yttrium oxide were observed and a rutile peak was observed above 7000C. The photocatalytic activity for the decomposition of methylene blue is proportional to the intensity of the PL peaks of the yttrium doped TiO2 particles. The doping of 1.0 mole% yttrium oxide on the TiO2 enhanced the photocatalytic activity and showed the higher activity than P-25 used as a commercial catalyst. In addition, the titania particles calcined at 600oC showed the highest photocatalytic activity.

Physico-chemical and Heavy Metals Evaluation of Polluted Urban Wetlands of Bangalore

Jumbe Aboud S. and Nandini N*.

The urban aquatic ecosystems are strongly influenced by long term discharge of untreated domestic and industrial wastewaters, storm water runoff, accidental spills and direct solid waste dumping. All these released pollutants have a great ecological impact on the water quality of the urban wetlands. In carrying out the present study, a total of seventeen (17) lake systems located in three major valleys of Bangalore City – Vrishabavarthy, Koramangla- Challagatta, and Hebbal with five (5) of its total six (6) lake series within these valley systems were selected. The chemical quality was compared with a series of local and international standards pertaining to drinking water as well as tolerance limits for wetlands. Several physicochemical and heavy metal parameters were evaluated along with the irrigation, corrosion and productivity indices. Overall, the mean ionic concentrations showed the following pattern: Na > Ca > Mg > K > Fe > Co >Pb > Cr > Ni > Cu > Zn > Mn > Cd. Sodium (188.85 mg/L) and Potassium exceeded the ground water guidelines limit of 175 and 12 mg/L respectively. K also exceeded the EU limit of 10 mg/L. Mg (37.6 mg/L) exceeded the BIS limits. Cu (0.33 ppm), Zn (0.28 ppm) and Mn (0.24 ppm) were within the BIS maximum limit of 1.5, 5 and 0.3 ppm respectively. Although Cd (0.16 ppm) and Ni (1.01 ppm) exceeded the drinking water limits of 0.01 and 0.1 ppm (EPA) respectively, both metals were within the tolerance limits of inland surface water subject to pollution (2.0 and 3.0 ppm as prescribed in CPCB effluent discharge limits). However, Cr, Pb, and Fe exceeded discharge limits (2.0, 0.1, and 3.0 ppm respectively). Anionic evaluation produced the following pattern: Cl > HCO3 > SO4 > NO3 > PO4 > CO3 > F. Chlorides exceeded the BIS limit of 250 mg/L while Nitrates exceeded the ICMR highest desirable level of 20 mg/L. These findings underline the increasing environmental pollution impact on these fragile urban wetlands and necessitate for a major policy shift in restoration and rejuvenation programs.

Water quality of Dhulikhel area, Nepal

Shrestha R. A. 1,2 , Kafle B. K. 1 and Sillanpää M. 2*

This study consisted of the determination of the physiochemical properties of different types of untreated water in Dhulikhel area of Nepal. The aim was to ascertain the quality of river water, ground water and pond water. Only the concentration of chloride exceeded the permissible limits of the World Health Organization drinking water quality guidelines. The four out of five ponds had very low dissolved oxygen content. On an average, the water in this area was slightly polluted. A simple pre-treatment is enough to make the water potable.

Effect of earthworms on nutrients dynamics in soil and growth of crop

Mayilswami Srinithi and Reid Brian*

Effects of earthworms especially with Lumbricus terrestris on nutrients dynamics and on plant growth were studied in the laboratory. Soil was amended with varied levels of compost and earthworms were introduced: 60.9 g soil alone, 60.9 g soil + 20.78 g compost (60:40), 60.9 g soil + 41.57 g compost alone (80:20) and 41.57 g compost alone. The ion chromatography data showed there was significant variation in the nutrient status mainly nitrite, nitrate, ammonium and phosphate between the treatments (with worms) and control (devoid of worms). The significant variation in nitrite concentration was observed in treatment containing 60.9 g soil+ 20.78 g compost which was around 6.32(mg/kg ). Phosphate concentration was predominant in treatment having 41.57 g compost alone with 23.855 mg/kg concentration. The amount of ammonium varied slightly, though major concentration around 6.90 mg/kg was observed in treatment with 41.57 g compost alone. The difference in nutrient status appeared to be due to the variations in nutrient cycling probably ascribable to the earthworm’s activities. Pot experiment showed that the mustard plant growth was stimulated by earthworms digging capacity. The germination percentage, shoot length, root length and fresh biomass were determined. The variations between treatments and controls were measured. The average germination percentage in treatment containing 60.9 g soil + 20.78 g compost was 75.83 which was more significant. The total fresh biomass was measured to be 1.96 g more suggestive compared to controls. These modifications emerged due to the active participation of earthworms in stirring of soil.

Computer Augmented Modeling Studies on Complexes of Lanthanone ions with Creatinine in Dioxane-Water Mixtures

Sharma Sangita,* Patel Ashish, Bhalodia Jasmin, Ramani Jayesh and Vora J. J.

Chemical speciation of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III) and Dy(III) complexes of creatinine was studied at 30ºC in 10%, 20%, 30%, 40%, 50%, 60% v/v dioxane-water mixtures and ionic strength was maintained as 0.2M (NaClO4). Titration data were obtained on the basis of Irving-Rossotti technique and data were pruned with computer program PKAS & BEST. The active forms of ligand are LH+ & L which were obtained with SPEPLOT. The dominant species of complexation are ML, ML2 and ML(OH)3. The stability of complexes that formed has increased with increasing dioxane content. The change in stability constants with change in dielectric constant of medium is explained on the basis of cation solvating nature of cosolvent, specific solvent-water interaction, specific interaction of cosolvent with solute, electrostatic and non-electrostatic effects. The effects of systematic errors on stability constants are also studied. The order for these effects is dissolved carbon dioxide > alkali > acid > ligand > metal. The trends of transportation and the availability of lanthanide ion for complexation can be explained on the basis of distribution diagrams and the stability constants of complexes so formed.

Synthesis, Characterisation and Antimicrobial Activities of Copper(II) and Zinc(II) Complexes of Schiff Bases derived from Amino Acids and 1,10-Phenanthroline Mixed Ligands

Peter Ndifon T.*, Agwara Moise O.2, Njapba Julius N., Yufenyi Mbom D.1, Paboudam Awawou G. and Nyamen Lynda D.2

Copper(II) and Zinc(II) complexes of Schiff bases and 1,10-phenanthroline mixed ligands have been synthesized in aqueous/methanolic solution. These complexes were characterised by elemental analyses, infrared and visible electronic spectroscopy. The results suggest a distorted octahedral coordination for Cu(II) and Zn(II) complexes in which the central metal ion is bonded to O-, N- and Odonor sites of the imino-N, phenoxyl-O and carboxyl- O groups respectively. Antimicrobial studies on the ligands and the metal complexes show that the ligands, salicylidene alanine (Sal-Al) and salicylidene histidine(Sal-His) are active against 3 out of the 8 tested organisms while the copper complex Cu(Sal- Ala)phen is active against 4 of the pathogens. The zinc complex Zn(Sal-Ala)phen is active against 7 of the pathogens. None of them is active against the fungus, candida albicans.

Coordination Polymers of N, N’-Di-(8-Hydroxyquinolinolyl-5-methyl)-N, N’Dimethyl-1, 4 But-2-enediamine (QMBD)

Patel Sunil P.1, Prajapati N.K.2, Patel Asha D.2*, and Jain Swanti2

Coodination polymer containing a novel bis- (bidentate) ligand, namely N, N’-di(8- hydroxyquinolinolyl- 5-methyl)-N,N’-dimethyl-1,4-but-2 enediamine(QMBD) was synthesized by condensation of 5-chloromethyl-8-hydroxyquinoline hydrochloride with N,N’-dimethyl-1,4-but-2-ene diamine in the presence of a base catalyst. The coordination polymers of this bis ligand QMBD have been prepared with the metal ions Zn(II), Cu(II), Ni(II), Co(II) and Mn(II). All of these coordination polymers and the parent ligand QMBD were characterized by elemental analyses and IR spectral and diffuse reflectance spectral studies. The number- average molecular weights (Mn) of all the coordination polymers were determined by nonaqueous conductometric titrations. The thermal properties of all coordination polymers were determined by theremogravimetry. In addition, all the coordination polymers have also been characterized by their magnetic susceptibilities.

Synthesis and study of Bimeric Cu(II), Ni(II), Mn(II) and Co(II) Complexes with Schiff base ligands derived from primary aliphatic amines with 3-acetyl-4-hydroxy-6-methyl-5-(phenyldiazenyl)-2H-pyran-2-one

Chandole S.S. 1, Pachling S.P. 2 and Shirodkar S.G. *2

Schiff base ligands derived from 3-acetyl-4-hydroxy-6-methyl-5-(phenyldiazenyl)-2H-pyran-2-one and primary aliphatic amines have been synthesized and characterized by their elemental analysis,UV, IR and NMR studies. These ligands were used to synthesize Cu(II), Ni(II), Mn(II) and Co(II) complexes. The complexes were haracterized by elemental analysis, magnetic moment, molar conductance along with electronic, infrared and XRD spectral analysis. Octahedral geometry around these metal ions have been proposed on the basis of magnetic and spectral studies. The fungicidal activities of the ligands and their metal complexes have been screened in vitro against A. niger and the % inhibition in found to be in the order Cu > Ni > Mn > Co.

Sorption and Separation of Lead(II) using Poly [dibenzo-18-crown-6] in L-valine medium

Jadhav Deepali V., Sabale Sandip R. and Mohite Baburao S.*

A column chromatographic separation method has been developed for separation of Pb(II) using poly[dibenzo-18-crown-6]. The separation was carried out in L-valine medium. The sorption of Pb(II) was quantitative from 110-6 M to 110-2 M L-valine. The capacity of column of poly[dibenzo 18-crown-6] for Pb(II) was found to be 0.86 0.01 mmol/g of crown polymer. The result showed that 1.0 M to 8.0 M hydrochloric acid, 4.0 M to 7.0 M hydrobromic acid, 1.0 M to 8.0 M sulfuric acid and 4.0 M to 6.0 M acetic acid and 2.0 M to 4.0 M perchloric acid were found to be efficient eluents. Pb(II) was separated from commonly associated metal ions such as Mg(II)/Sb(III), Co(II), Zn(II), Hg(II), Ni(II), Cd(II) and Th(IV) and other associated metal ions in binary as well as in multicomponent mixtures. The sorption of Pb(II) was carried out in presence of various ions to ascertain the tolerance limits of individual. The lead content was determined in type metal alloy. The simple, rapid and selective method having good reproducibility (approximately 2%) was developed.

Inorganics Accumulation in Low-Sludge Wastewater Treatment Technique: Case Study of SBR with Sonication

Zhang Panyue and Zhang Guangming*

Large amount of excess sludge imposes great environmental pollution and high handling cost and hence, excess sludge reduction techniques are of great importance. However, inorganics might accumulate in the activated sludge when less excess sludge was discharged. This paper analyzed in detail the accumulation of inorganics in a subsequent batch reactor (SBR) with sonication cryptic growth method to reduce excess sludge. Results showed that for the treatment of normal urban sewage, sonication cryptic growth effectively reduced the excess sludge by around 50%, inorganics accumulation in sludge was insignificant, sludge bioactivity was stable but the effluent turbidity slightly increased. On the other hand, for the treatment of artificial wastewater with 500 mg/L inorganics addition, the inorganics accumulated significantly in the activated sludge and counted for 72% of sludge dry weight after 20 d. Correspondingly, the sludge bioactivity reduced by 55.6%. As a result, the effluent turbidity reached 42 NTU and the COD removal efficiency dropped from 88% to 67%. Interestingly, sonication could improve the sludge bioactivity, reduce the inorganics accumulation and enhance the effluent quality while reducing the amount of excess sludge by around 20%. Therefore, sonicationcryptic growth method did not cause the accumulation of inorganics in sludge and might even improve the sludge activity when high turbidity wastewater was treated.

Abnormal Levels of Lanthanides in Common Beverages: A Study by ICP-MS

Williams J. R.*, Pillay A. E. and Al-Asmi S. K.

This study found abnormal concentrations of lanthanides in five Indian teas and four coffees (Brazilian, Indian and Turkish) popular currently in the Middle East. This is of concern, because some lanthanides could have adverse health effects in humans. The original aim of this study was to obtain baseline concentrations as reference data, but elevated levels were encountered. Average levels of lanthanides in tea on a dry mass basis across the five brands were 10-100 times literature values and ranged as follows: La 3.78-3.98, Ce 3.49-4.04, Pr 1.81-1.86, Lu 1.17-1.24, Tm 1.02-1.08, Nd 4.72-7.97, Eu 2.33-2.43, Gd 4.83-5.28, Tb 1.29-1.37, Dy 3.67-3.83, Ho 1.20-1.27 and Er 3.48-3.63 g/g. For the four coffee brands, the corresponding concentrations were again 10-100 times higher than literature values and were: La 4.00-4.38, Ce 4.05-11.1, Pr 1.93-2.15, Lu 1.28-1.41, Tm 1.05-1.22, Nd 5.07-5.41, Eu 2.40-2.57, Gd 5.24-7.57, Tb 1.34-1.51, Dy 3.90-4.20, Ho 1.29-1.42 and Er 3.70-3.99 g/g (dry mass). Some of these elements have never been studied in tea and coffee before. Specifically, Lu, Tm, Eu, Tb and Ho in tea and Pr, Nd, Ho and Er in coffee have not appeared in the chemical literature before. The impact of lanthanides on human health is reviewed. Quantitation was achieved by inductively coupled plasma-mass spectrometry.

Optimized Extraction Protocol for Extracellular Polymeric Substances (EPS) From Two Activated Sludges

Liyun Ge, Huanhuan Deng*, Hongwei Gao and Feng Wu

Extracellular polymeric substances (EPS) are significant components of activated sludge. They are considered important in the removal of pollutants from wastewater, in bioflocculation, in settling and in dewatering of activated sludge. The present paper investigates the extraction efficacies of EPS from two different activated sludges. One chemical method (NaOH), two physical methods (cation exchange resin, heating) and a control method (centrifugation alone) were tested and cation exchange resin was found to be an effective extraction method. We also optimized the cation exchange resin (CER) procedure in extraction time, the dose of CER and the stirring intensity. Results show that CER was most effective in extracting EPS for all sludge samples; only 0.73% and 1.61% of DNA in all sludges were detected within 16 hr of extraction time, suggesting the EPS isolated were not contaminated by intracellular substances. For each gram of volatile solids, CER extracted 74 mg and 80 mg of EPS from the two sludges respectively. Carbohydrate and protein were main components of both EPS. Optimization of CER extraction procedures showed the best extraction time was 8hr and higher total mass of EPS was harvested by CER method with higher stirring intensity and CER dose.

Removal of Pb (II), Zn (II) and Cd (II) from Hydrometallurgical Effluent by Ferrite Formation

Li Dou and Li Dongwei*

The hydrometallurgy industry discharges large numbers of heavy metal wastewater annually in China, especially during the production of Germanium extracted from Lead and Zinc oxide ore. The effluent contains Pb(II), Zn(II) and Cd(II) and the concentration is 7.0, 50.0 and 4.12mg/L respectively. In this research, the XRD was introduced to detect the ferrite generated in chemical coprecipitation. The crystal structure of ferrite may play a important role in parceling heavy metal ions. The hydrometallurgical effluent quality treated by chemical coprecipitation and ferrite combined process was excellent. The extraction toxicity of ferrite was far below the allowed standard concentration. It was also found that the removal efficiency is optimal when the pH is from 8.86 to 9.24 and the temperature is from 40oC to 60oC.

Thermal Explosion Simulation of Hydrogen Peroxide in Three Types of Vessels by Explosion Models

Meng-Lung Lin, Kun-Yue Chen, Sheng-Hung Wu, Yung-Chuan Chu, Sun-Ju Shen and Chi-Min Shu*

Hydrogen peroxide (H2O2), which has highly reactive and exothermically unstable features, has been extensively employed in the chemical industry. It has caused many thermal explosion and runaway reaction accidents during manufacturing processes in the last four decades in Taiwan, Japan, Korea and China. The goal of this study was to simulate upsets by H2O2 for an emergency response. Vent sizing package 2 (VSP2) was used to determine the thermokinetics of 20 mass% H2O2. A numerically simulated model was adopted to simulate thermal explosion development and thermokinetic data of runaway reaction for three types of vessels of 20 mass% H2O2. Important parameters, such as maximum temperature (Tmax), maximum pressure (Pmax), etc. were necessary and useful for investigating the emergency response procedure in terms of industrial applications.

Photodegradation of tetracycline in Water in the presence of Ferric-Oxalate Complex

Thil Thu Anh Vu, Hou Liwei, Beibei Wang and Nansheng Deng *

Photodegradation of tetracycline in aqueous solution was investigated under UV-Vis light (l ≥ 365 nm) in Fe(III)/oxalate system in this work. After 15 min of irradiation with C(Fe(III)) =10.0μM, C(oxalate) =100 μM, 10.0μM tetracycline could totally degrade at pH 4.1. The influence factors of light source, pH value, Fe(III)/oxalate ratio as well as the chemicals adding sequence on tetracycline photodegradation efficiency were studied.

Ion Selective Electrodes for Rare Earth Metal Ions

Kumar Raj, Sharma H.K.*, Dogra Pernita and Kumar Pankaj

This review presents a general overview about the development of ion-selective electrodes for lanthanide ions during the past decade. Ionophore-incorporated binder-membrane sensors are well established analytical tools routinely used for direct measurement of a wide variety of different lanthanide ions in environmental samples. The active ingredient of the membrane is the ionophore, which forms the complex with the cation of interest and dictates the selectivity of the electrode. In the last few years, the development of new ion-selective electrodes for various lanthanide ions has been reported by researchers. This review contains the information about most of the lanthanide (La, Ce, Pr, Dy, Tb, Eu, Lu, Nd, Gd, Sm, Ho, Er and Yb) ion-selective electrodes