Solvent-Free Green Synthesis of Azines and Their Conversion to 2,5-Disubstituted-1,3,4-thiadiazoles

A solvent-free, clean, and efficient method has been developed for the synthesis of 2,5-disubstituted-1,3,4-thiadiazoles via azines. This approach exploits the synthetic potential of clean reactions and offers many advantages such as excellent product yields, easy isolation of products, and ecofriendly benign reaction conditions. The newly synthesized compounds were analyzed by infrared, ¹H NMR, ¹³C NMR, and elemental analysis.     

Speciation of 30 % tri-n-butyl phosphate solvent during extraction of nitric acid

Several solutions of 30 % TBP/n-dodecane were equilibrated with different concentrations of aqueous nitric acid solutions at 298.15 K at a phase ratio of unity. The resultant equilibrated aqueous and organic solutions were analyzed for acidity. A three-solvate model with molecular HNO₃ based mechanism was assumed for nitric acid extraction by TBP. With nonlinear chemometric methods, the coefficients were evaluated. With the set of optimized coefficients, derived on the basis of experiments reported in this work, the estimated solvate species and free-TBP species in the TBP containing organic phase were found to be in good agreement with the reported concentrations in the literature.     

Sedimentation rate in the Sungai Linggi estuary using excess 210Pb and 137Cs

The purpose of this study was to estimate the sedimentation rate in the Sungai Linggi estuary using the constant initial concentration of unsupported or excess ²¹⁰Pb model and verified with ¹³⁷Cs method. Five sediment cores were collected on 25 January 2011 using gravity corer with the inner tube of 50 cm length and 7.5 cm diameter. The total ²¹⁰Pb activities in the sediment cores profile at all sampling stations were varied and upper than those obtained for supported ²¹⁰Pb i.e. ²²⁶Ra, indicated disequilibrium among ²¹⁰Pb and its grandparents in the ²³⁸U decay series. Meanwhile, the lower ¹³⁷Cs activities were observed at all sampling stations due to no significant sources of ¹³⁷Cs releases were transferred into Malaysian marine. The estimation of sedimentation rate indicated the agreement of ²¹⁰Pb and ¹³⁷Cs method with a general presence of deep mixing in the Sungai Linggi estuary. Therefore, the apparent sedimentation rates calculated from ²¹⁰Pb profiles generally reflect the true value with the range from 0.70 to 1.97 cmyr^?1. High sedimentation rate was observed at some sampling stations which are located in river channel, estuary and closer to mainland. This suggested that land-use development, agriculture activities, channelization etc. introduced a large amount of sediment loaded into those areas.     

Direct spectrophotometric determination of ruthenium in aqueous streams of nuclear reprocessing

A fiber optic aided spectrophotometric technique has been developed for determination of ruthenium in nitric acid medium. The developed method is simple, accurate and applicable to aqueous streams of nuclear reprocessing. The system obeys Lambert–Beer’s law at 468 nm in the concentration range of 30–360 μg/mL of ruthenium. The molar absorption coefficient, detection limit and Sandell’s sensitivity are 68.477 L Mol^?1 cm^?1, 31 μg/mL and 0.0124 μg/cm² respectively. Relative standard deviation was less than 2 % and correlation coefficient was 0.9998. The results obtained by the developed procedure are in good agreement with those obtained by the standard ICP-OES method. Fission products like zirconium and strontium are not interfering. Uranium is interfering and needs prior separation by solvent extraction method. The developed method is adaptable for remote operation and on-line monitoring.     

Effect of tri-n-butyl phosphate on physical properties of dodecane–nitric acid system

Extraction power of solvent depends upon the physical properties of the system. Tri-n-butyl phosphate (TBP) in dodecane is a versatile solvent used in the nuclear fuel reprocessing like PUREX process. The study of physical properties like density, viscosity, interfacial tension and solubility for TBP–nitric acid–dodecane system will be helpful in carrying out different extraction studies during PUREX process. Thus, physical properties like density, viscosity, interfacial tension and solubility have been measured for TBP–nitric acid–dodecane system using pycnometer, viscometer, pendant drop method and high performance liquid chromatography respectively. It has been observed that density and viscosity increases but interfacial tension and solubility decreases with the concentration of TBP in dodecane–nitric acid system. Physical properties of 30 % TBP–nitric acid–dodecane system have also been studied in detail. All these studies will also be useful in stripping out dissolved TBP from the nuclear waste.     

Behaviour of Phenoxyacetic Acids During Underground Passage with Different Redox Zones

Abstract

The behaviour of the three phenoxyacetic acid herbicides 2,4-D, 2,4,5-T and MCPA during underground passage and bankfiltration was tested in a model system consisting of laboratory filter columns filled with natural underground materials. Different redox environments were reproduced by operating the filters with natural aerobic and anaerobic groundwater. In the presence of oxygen, biodegradation of the three herbicides started after a lag phase. Under sulfate reducing conditions, no degradation could be observed. To assess the factors that may influence microbial degradation in the anaerobic environment, the concentration of herbicides, the time and the nutrient content were varied, but this did not increase degradation. The maximum retention of the herbicides in the filters was 30%, mainly due to adsorption to the filter material.     

Assessment of the polluting effects of the Iponri-Alaka Canal,Lagos State,Nigeria

ABSTRACT

The polluting effects of Iponri-Alaka Canal in Surulere area of Lagos State on the environment have been studied using six sampling points. The study aimed at assessing the effects of exposure to pollutants on humans and other life forms. The quality of air, wastewater and sediments was assessed between March and August 2017. The concentrations of SO₂ and H₂S were measured using MSA Altair 5X. Temperature, pH and DO were measured in-situ using Thermometer, pH meter and Winkler method, respectively. TSS, TDS, TS, TA, TH, BOD, chloride Cl^?, PO₄^3-, SO₄^2- and NO₃^? were determined using appropriate standard methods in the laboratory. EC and some heavy metals (Cr, Pb, Mn, Cd and Ni) concentrations were determined using conductivity meter and Atomic Absorption Spectroscopy, respectively. The results showed that pH, TS, DO and TH were well within the WHO and FEPA maximum limits. EC, SO₄^2- and TDS were observed to be higher than guideline values only at one sampling point. The TSS, BOD, TA, NO₃^? and PO₄^3- were higher than WHO and FEPA guideline limits at all sampling points. Cr was seen to be within, while Pb and Mn were higher than WHO and FEPA guideline values. Cd was higher than guideline values only at two sampling points. Ni was below detection concentration at all the sampling points.

The concentration of SO₂ was seen to be higher than WHO and NESREA guideline values at two sampling points, while H₂S concentration was higher than WHO limit at all the six sampling points.     

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

A detailed chemical kinetic model for oxidation of CH₃OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for , , , and . The experiments, involving CH₃OH/O₂ mixtures diluted in N₂, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH₃OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the reaction.     

Dielectric and ac impedance studies of nanostructured CaCu3Ti3.90Ce0.10O12 electro-ceramic synthesized by citrate-gel route

Effect of doping at Ti⁴⁺ site by Ce³⁺ has been examined in CaCu₃Ti_3.90Ce_0.10O₁₂ synthesized by citrate-gel route. DTA/TG analysis of dry powder gives pre-information about formation of final product around 850 °C. X ray diffraction analysis confirmed the formation of CaCu₃Ti_3.90Ce_0.10O₁₂ phase of the ceramic sintered at 950 °C for 12 h. Microstructure has been studied using scanning electron microscopy and confirmed the average grain size found in nano range 200–400 nm in system CaCu₃Ti_3.90Ce_0.10O₁₂.The nature of relaxation behavior of ceramic was also rationalized by using the impedance and modulus spectroscopy. The bulk conductivity indicates an Arrhenius-type thermally activated process. The ac conductivity spectrum obeyed the Jonscher power law. The complex impedance diagrams of the ceramic exhibited a significant contribution from the grains, grain boundaries and electrode. The activation energies calculated from the grain-boundary relaxation time constant was found to be 0.49 eV which confirmed the Maxwell–Wagner type of relaxation present in the ceramic.     

One-pot synthesis of 2-(dicyanomethylene)-1,2-dihydropyridine derivatives

The synthesis of 2-(dicyanomethylene)-1,2-dihydropyridine derivatives from the reactions of arylmethylidene derivatives of malononitrile dimers with 1,3-dicarbonyl compounds is described.