Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.

Temperature dependence study of chlorine NQR frequency and spin-lattice relaxation time in 2-amino,-3,5-dichloropyridine

Chlorine-35 NQR frequency and spin-lattice relaxation time measurements as a function of temperature in the range 77-300 K were carried out on 2-amino-3,5-dichloropyridine. Two NQR signals were observed and were assigned to the two chlorines present in the molecule using the additive model for substituent effects. The temperature dependence of the NQR frequency was analysed in terms of the torsional oscillations of the molecule and the torsional frequencies and their temperature dependence were calculated numerically using a two-mode approximation. The temperature dependence of the NQR spin-lattice relaxation time was found to be mainly due to the torsional oscillations of the molecule, with anharmonicity effects showing up at higher temperatures. Copyright (C) 1999 John Wiley & Sons, Ltd.

Greenhouse gas inventory estimates for India

This article reports the greenhouse gas emissions of anthropogenic origin by sources and removals by sinks of India for 2007 prepared under the aegis of the Indian Network for Climate Change Assessment (INCCA) (note 1). The emission profile includes carbon dioxide (CO(2)), methane and nitrous oxide. It also includes the estimates of hydrofluorocarbons, perfluorocarbons and sulphur hexafluoride at the national level from various sectors, viz, energy, industrial process and product use, agriculture, land-use, land-use change and forestry (LULUCF), and waste. In 2007, emissions were of the order of 2008.67 Tg (note 2) of CO(2) equivalents without emissions from the LULUCF sector. Whereas with LULUCF the emissions were about 1831.65 Tg CO(2) equivalents. The energy sector accounted for 69% of the total emissions, the agriculture sector contributed 19% of the emissions, 9% of the emissions was from the industrial processes and product use, and only 3% of the emissions was attributable to the waste sector. The LULUCF sector on the whole was net sink category for CO(2). The study tracks the improvements made in inventory estimates at the national level through the years, in terms of the expanding coverage of sources, reducing uncertainties and inclusion of new methodologies, including some elements of future areas of work.

Ru(4+) ion in CeO(2) (Ce(0.95)Ru(0.05)O(2-delta)): A non-deactivating, non-platinum catalyst for water gas shift reaction

Hydrogen is a clean energy carrier and highest energy density fuel. Water gas shift (WGS) reaction is an important reaction to generate hydrogen from steam reforming of CO. A new WGS catalyst, Ce(1-x)Ru(x)O(2-delta) (0 <= x <= 0.1) was prepared by hydrothermal method using melamine as a complexing agent. The Catalyst does not require any pre-treatment. Among the several compositions prepared and tested, Ce(0.95)Ru(0.05)O(2-delta) (5% Ru(4+) ion substituted in CeO(2)) showed very high WGS activity in terms of high conversion rate (20.5 mu mol.g(-1).s(-1) at 275 degrees C) and low activation energy (12.1 kcal/mol). Over 99% conversion of CO to CO(2) by H(2)O is observed with 100% H(2) selectivity at >= 275 degrees C. In presence of externally fed CO(2) and H(2) also, complete conversion of CO to CO(2) was observed with 100% H(2) selectivity in the temperature range of 305-385 degrees C. Catalyst does not deactivate in long duration on/off WGS reaction cycle due to absence of surface carbon and carbonate formation and sintering of Ru. Due to highly acidic nature of Ru(4+) ion, surface carbonate formation is also inhibited. Sintering of noble metal (Ru) is avoided in this catalyst because Ru remains in Ru(4+) ionic state in the Ce(1-x)Ru(x)O(2-delta) catalyst.

Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta): New water gas shift (WGS) catalysts

Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) and Ce(0.67)Fe(0.33)O(2-delta) have been synthesized by a new low temperature sonochemical method using diethylenetriamine as a complexing agent. Due to the substitution of Fe and Pt ions in CeO(2), lattice oxygen is activated in Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). Hydrogen uptake studies show strong reduction peaks at 125 C in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) against a hydrogen uptake peak at 420 degrees C in Ce(0.67)Fe(0.33)O(2-delta). Fe substituted ceria, Ce(0.67)Fe(0.33)O(2-delta) itself acts as a catalyst for CO oxidation and water gas shift (WGS) reactions at moderate temperatures. The rate of CO conversion in WGS with Pt free Ce(0.65)Fe(0.33)O(2-delta) is 2.8 mu mol g(-1) s(-1) at 450 C and with Pt substituted Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) is 4.05 mu mol g(-1) s(-1) at 275 degrees C. Due to the synergistic interaction of the Pt ion with Ce and Fe ions in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta), the catalyst showed much higher activity for CO oxidation and WGS reactions compared to Ce(0.67)Fe(0.33)O(2-delta). A reverse WGS reaction does not occur over Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). The catalyst also does not deactivate even when operated for a long time. Nearly 100% conversion of CO to CO(2) with 100% H(2) selectivity is observed in WGS reactions even up to 550 degrees C. (C) 2011 Elsevier B.V. All rights reserved.

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

Synthesis, Structure, and Magnetic Properties of a New Eight-Connected Metal-Organic Framework (MOF) based on Co-4 Clusters

A hydrothermal reaction of cobalt nitrate, 4,4'-oxybis(benzoic acid) (OBA), 1,2,4-triazole, and NaOH gave rise to a deep purple colored compound Co-4(triazolate)(2)(OBA)(3)], I, possessing Co-4 clusters. The Co-4 clusters are connected together through the tirazolate moieties forming a two-dimensional layer that closely resembles the TiS2 layer. The layers are pillared by the OBA units forming the three-dimensional structure. To the best of our knowledge, this is the first observation of a pillared TiS2 layer in a metal-organic framework compound. Magnetic studies in the temperature range 1.8-300 K indicate strong antiferromagetic interactions for Co-4 clusters. The structure as well as the magnetic behavior of the present compound has been compared with the previously reported related compound Co-2(mu 3-OH)(mu(2)-H2O)(pyrazine)(OBA)(OBAH)] prepared using pyrazine as the linker between the Co-4 clusters.

New rock salt-related oxides Li3M2RuO6 (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3M2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co-2/Ru)O-6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3CO2RuO6. Interestingly high first charge capacities (between ca. 160 and 180 mAh g(-1)) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. (C) 2013 Elsevier Inc. All rights reserved.

GHG footprint of major cities in India

Concentration of greenhouse gases (GHG) in the atmosphere has been increasing rapidly during the last century due to ever increasing anthropogenic activities resulting in significant increases in the temperature of the Earth causing global warming. Major sources of GHG are forests (due to human induced land cover changes leading to deforestation), power generation (burning of fossil fuels), transportation (burning fossil fuel), agriculture (livestock, farming, rice cultivation and burning of crop residues), water bodies (wetlands), industry and urban activities (building, construction, transport, solid and liquid waste). Aggregation of GHG (CO2 and non-CO2 gases), in terms of Carbon dioxide equivalent (CO(2)e), indicate the GHG footprint. GHG footprint is thus a measure of the impact of human activities on the environment in terms of the amount of greenhouse gases produced. This study focuses on accounting of the amount of three important greenhouses gases namely carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) and thereby developing GHG footprint of the major cities in India. National GHG inventories have been used for quantification of sector-wise greenhouse gas emissions. Country specific emission factors are used where all the emission factors are available. Default emission factors from IPCC guidelines are used when there are no country specific emission factors. Emission of each greenhouse gas is estimated by multiplying fuel consumption by the corresponding emission factor. The current study estimates GHG footprint or GHG emissions (in terms of CO2 equivalent) for Indian major cities and explores the linkages with the population and GDP. GHG footprint (Aggregation of Carbon dioxide equivalent emissions of GHG's) of Delhi, Greater Mumbai, Kolkata, Chennai, Greater Bangalore, Hyderabad and Ahmedabad are found to be 38,633.2 Gg, 22,783.08 Gg, 14,812.10 Gg, 22,090.55 Gg, 19,796.5 Gg, 13,734.59 Gg and 91,24.45 Gg CO2 eq., respectively. The major contributors sectors are transportation sector (contributing 32%, 17.4%, 13.3%, 19.5%, 43.5%, 56.86% and 25%), domestic sector (contributing 30.26%, 37.2%, 42.78%, 39%, 21.6%, 17.05% and 27.9%) and industrial sector (contributing 7.9%, 7.9%, 17.66%, 20.25%, 1231%, 11.38% and 22.41%) of the total emissions in Delhi, Greater Mumbai, Kolkata, Chennai, Greater Bangalore, Hyderabad and Ahmedabad, respectively. Chennai emits 4.79 t of CO2 equivalent emissions per capita, the highest among all the cities followed by Kolkata which emits 3.29 t of CO2 equivalent emissions per capita. Also Chennai emits the highest CO2 equivalent emissions per GDP (2.55 t CO2 eq./Lakh Rs.) followed by Greater Bangalore which emits 2.18 t CO2 eq./Lakh Rs. (C) 2015 Elsevier Ltd. All rights reserved.

Cost effectiveness of a combination of instruments for global warming: a quantitative approach for Spain

Climate change is an important environmental problem and one whose economic implications are many and varied. This paper starts with the presumption that mitigation of greenhouse gases is a necessary policy that has to be designed in a cost effective way. It is well known that market instruments are the best option for cost effectiveness. But the discussion regarding which of the various market instruments should be used, how they may interact and what combinations of policies should be implemented is still open and very lively. In this paper we propose a combination of instruments: the marketable emission permits already in place in Europe for major economic sectors and a CO(2) tax for economic sectors not included in the emissions permit scheme. The study uses an applied general equilibrium model for the Spanish economy to compute the results obtained with the new mix of instruments proposed. As the combination of the market for emission permits and the CO(2) tax admits different possibilities that depend on how the mitigation is distributed among the economic sectors, we concentrate on four possibilities: cost-effective, equalitarian, proportional to emissions, and proportional to output distributions. Other alternatives to the CO(2) tax are also analysed (tax on energy, on oil and on electricity). Our findings suggest that careful, well designed policies are needed as any deviation imposes significant additional costs that increase more than proportionally to the level of emissions reduction targeted by the EU.

Infrared (1.2-1.6 mu m) luminescence in Cr4+: Yb3Al5O12 single crystal with 940 nm diode pumping

Infrared (1.2-1.6 mu m) luminescence in a ytterbium aluminium garnet (YbAG) crystal, doped with Cr (0.05 at.%) ions, was investigated under CW laser diode pumping (lambda = 940 nm). The Cr4+ emission band was observed with its peak at 1.34 mu m and measured to be about 1.3 times with respect to Yb3+ IR luminescence (lambda = 1.03 mu m). We demonstrate that for the excitation wavelength of 940 nm Yb3+ ions act as sensitizers of the B-3(2)(T-3(2))-B-3(1)((3)A(2)) emission of Cr4+ ions. This crystal is promising as a high-efficient system for tunable laser (1.2-1.6 mu m) output. (c) 2004 Elsevier B.V. All rights reserved.

Assessing the potential of yield improvements, through process scrap reduction, for energy and CO2 abatement in the steel and aluminium sectors

Targets to cut 2050 CO2 emissions in the steel and aluminium sectors by 50%, whilst demand is expected to double, cannot be met by energy efficiency measures alone, so options that reduce total demand for liquid metal production must also be considered. Such reductions could occur through reduced demand for final goods (for instance by life extension), reduced demand for material use in each product (for instance by lightweight design) or reduced demand for material to make existing products. The last option, improving the yield of manufacturing processes from liquid metal to final product, is attractive in being invisible to the final customer, but has had little attention to date. Accordingly this paper aims to provide an estimate of the potential to make existing products with less liquid metal production. Yield ratios have been measured for five case study products, through a series of detailed factory visits, along each supply chain. The results of these studies, presented on graphs of cumulative energy against yield, demonstrate how the embodied energy in final products may be up to 15 times greater than the energy required to make liquid metal, due to yield losses. A top-down evaluation of the global flows of steel and aluminium showed that 26% of liquid steel and 41% of liquid aluminium produced does not make it into final products, but is diverted as process scrap and recycled. Reducing scrap substitutes production by recycling and could reduce total energy use by 17% and 6% and total CO 2 emissions by 16% and 7% for the steel and aluminium industries respectively, using forming and fabrication energy values from the case studies. The abatement potential of process scrap elimination is similar in magnitude to worldwide implementation of best available standards of energy efficiency and demonstrates how decreasing the recycled content may sometimes result in emission reductions. Evidence from the case studies suggests that whilst most companies are aware of their own yield ratios, few, if any, are fully aware of cumulative losses along their whole supply chain. Addressing yield losses requires this awareness to motivate collaborative approaches to improvement. © 2011 Elsevier B.V. All rights reserved.

Comparative analysis of carbonization drivers in China's megacities

This study investigates the key drivers affecting emission increases in terms of population growth, economic growth, industrial transformation, and energy use in six Chinese megacities: Beijing, Shanghai, Tianjin, Chongqing, Guangzhou, and Hong Kong. The six cities represent the most-developed regions in China and they have similar per capita carbon dioxide (CO 2) emissions as many developed countries. There is an urgent need to quantify the magnitude of each factor in driving the emissions changes in those cities so that a potential bottom-up climate mitigation policy design at the city and sectoral levels can be initiated. We adopt index decomposition analysis and present the results in both additive and multiplicative approaches to reveal the absolute and relative levels of each factor in driving emission changes during 1985-2007. Among all cities, economic effect and energy intensity effect have always been the two dominant factors contributing to the changes in carbon emissions. This study reveals that there are large variations in the ways driving forces contribute to emission levels in different cities and industrial sectors. © 2012 by Yale University.

Carbon source/sink function of a subtropical, eutrophic lake determined from an overall mass balance and a gas exchange and carbon burial balance

Although studies on carbon burial in lake sediments have shown that lakes are disproportionately important carbon sinks, many studies on gaseous carbon exchange across the water-air interface have demonstrated that lakes are supersaturated with CO2 and CH4 causing a net release of CO2 and CH4 to the atmosphere. In order to more accurately estimate the net carbon source/sink function of lake ecosystems, a more comprehensive carbon budget is needed, especially for gaseous carbon exchange across the water-air interface. Using two methods, overall mass balance and gas exchange and carbon burial balance, we assessed the carbon source/sink function of Lake Donghu, a subtropical, eutrophic take, from April 2003 to March 2004. With the overall mass balance calculations, total carbon input was 14 905 t, total carbon output was 4950 1, and net carbon budget was +9955 t, suggesting that Lake Donghu was a great carbon sink. For the gas exchange and carbon burial balance, gaseous carbon (CO2 and CH4) emission across the water-air interface totaled 752 t while carbon burial in the lake sediment was 9477 t. The ratio of carbon emission into the atmosphere to carbon burial into the sediment was only 0.08. This low ratio indicates that Lake Donghu is a great carbon sink. Results showed good agreement between the two methods with both showing Lake Donghu to be a great carbon sink. This results from the high primary production of Lake Donghu, substantive allochthonous carbon inputs and intensive anthropogenic activity. Gaseous carbon emission accounted for about 15% of the total carbon output, indicating that the total output would be underestimated without including gaseous carbon exchange. (C) 2007 Elsevier Ltd. All rights reserved.

The change of gaseous carbon fluxes following the switch of dominant producers from macrophytes to algae in a shallow subtropical lake of China

Successions of lake ecosystems from clear-water, macrophyte-rich conditions into turbid states with abundant phytoplankton have taken place in many shallow lakes in China. However, little is know about the change of carbon fluxes in lakes during such processes. We conducted a case study in Lake Biandantang to investigate the change of carbon fluxes during such a regime shift. Dissolved aquatic carbon and gaseous carbon (methane (CH4) and carbon dioxide (CO2)) across air-water interface in three sites with different vegetation covers and compositions were studied and compared. CH4 emissions from three sites were 0.62 +/- 0.36, 0.70 +/- 0.36, and 1.31 +/- 0.57 mg m(-2) h(-1), respectively. Correlation analysis showed that macrophytes, rather than phytoplankton, directly positively affected CH4 emission. CO2 fluxes of three sites in Lake Biandantang were significantly different, and the average values were 77.8 +/- 20.4, 52.2 +/- 14.1 and 3.6 +/- 26.8 mg m(-2) h(-1), respectively. There were an evident trend that the larger macrophyte biomass, the lower CO2 emissions. Correlation analysis showed that in different sites, dominant plant controlled CO2 flux across air-water interface. In a year cycle, the percents of gaseous carbon release from lake accounting for net primary production were significantly different (from 39.3% to 2.8%), indicating that with the decline of macrophytes and regime shift, the lake will be a larger carbon source to the atmosphere. (c) 2006 Elsevier Ltd. All rights reserved.