Academic literature on the topic 'Nitrogen compounds – Reactivity'

This article describes the synthesis, characterization and environmental applications of nanocrystalline zeolites. It begins by considering the use of nanocrystalline zeolites as building blocks in the preparation of hierarchical zeolite structures, followed by a discussion of the synthesis of silicalite-1 with systematically varied crystal sizes, along with the synthesis of nanocrystalline aluminosilicates, NaZSM-5 and NaY. It then looks at the various applications of nanozeolites and hierarchical zeolite structures for environmental catalysis, adsorption of volatile organic compounds and oth

AbstractNitrogen-containing compounds are prevalent in the key components of various functional materials and compounds such as pharmaceutical drugs. Therefore, it is extremely important to develop versatile synthetic methodologies capable of constructing C—N bonds in an efficient manner under milder reaction conditions. Apart from common ionic C—N bond-forming reactions (i.e., nucleophilic and electrophilic amination, as well as transition-metal-catalyzed C—N cross-coupling processes), leveraging of nitrogen-centered radicals for C—N bond-forming process has created another dimension to the modern synthesis of nitrogen-containing compounds. In particular, recent development of novel catalytic strategies and the design of new nitrogen-radical precursors have rendered their generation and use for C—N bond formation more practical and user-friendly for synthesis of wider array of nitrogen-containing compounds of potential use. This chapter highlights the latest developments in synthetic methods for C—N bond construction using nitrogen-centered radicals by showing selected reactions, mostly reported in the last five years, based on their structural and reactivity features as well as the method of radical generation.

A chemical mechanism is a critical component of an air quality model. Tropospheric gas phase chemical mechanisms for air quality modeling are designed to simulate the production of ozone, acids, and aerosol precursors. Therefore, their focus is on the oxidation chemistry of ozone, nitrogen oxides, sulfur compounds, and organic compounds. Figure IX-A-1 is an overview of the most important cycles of radicals that must be represented in a chemical mechanism for air quality modeling. The processes shown schematically on one level may appear to be relatively simple, but, in reality, the chemical mechanism is extremely complicated due to the very large number of organic compounds present in the atmosphere. Atmospheric chemistry mechanisms are based on laboratory data and tested against environmental experiments and field measurements (Stockwell et al., 2012). Usually, the mechanism is considered to consist of chemical species and their reactions and rate coefficients, along with the photochemical data (used to calculate photolysis frequencies). An atmospheric chemical mechanism employed in an air quality model could be considered to include the rules for aggregating emissions and initial concentrations into species (Middleton et al., 1990). There are many thousands of volatile organic compounds (VOCs) emitted into the atmosphere, and each has its own decomposition mechanism that determines the effect of the VOC on ozone production. It is critical for a chemical mechanism to characterize the chemistry of the VOCs and their differences in chemical reactivity as accurately as possible. Middleton et al. (1990) pointed out that air quality models have only a limited number of species compared to emission inventories. An emissions aggregation scheme is the process of mapping a detailed emissions inventory into the limited number of species used in an air quality model. The scheme is an important component of any model chemical mechanism. Middleton et al. published their aggregation process for the mechanism used in the Regional Acid Deposition Model (RADM2, Stockwell et al., 1990), but, too often, the emissions aggregation scheme for a given chemical mechanism is in the gray literature and difficult to access.

This chapter addresses a case study of long-term assessment of a field application of environmental nanotechnology. Dense Non-Aqueous Phase Liquid (DNAPL) contaminants such as Tetrachloroethene (PCE) and Trichloroethene (TCE) are a type of recalcitrant compounds commonly found at contaminated sites. Recent research has focused on their remediation using environmental nanotechnology in which nanomaterials such as nanoscale Emulsified Zerovalent Iron (EZVI) are added to the subsurface environment to enhance contaminant degradation. Such nanoremediation approach may be mostly applicable to the source zone where the contaminant mass is the greatest and source removal is a critical step in controlling the further spreading of the groundwater plume. Compared to micro-scale and granular counterparts, NZVI exhibits greater degradation rates due to its greater surface area and reactivity from its faster corrosion. While NZVI shows promise in both laboratory and field tests, limited information is available about the long-term effectiveness of nanoremediation because previous field tests are mostly less than two years. Here an update is provided for a six-year performance evaluation of EZVI for treating PCE and its daughter products at a Superfund site at Parris Island, South Carolina, USA. The field test consisted of two side-by-side treatment plots to remedy a shallow PCE source zone (less than 6 m below ground surface) using pneumatic injection and direct injection, separately in October 2006. For the pneumatic injections, a two-step injection procedure was used. First, the formation was fluidized by the injection of nitrogen gas alone, followed by injection of the EZVI with nitrogen gas as the carrier. In the pneumatic injection plot, 2,180 liters of EZVI containing 225 kg of iron (Toda RNIP-10DS), 856 kg of corn oil, and 22.5 kg of surfactant were injected to remedy an estimated 38 kg of chlorinated volatile compounds (CVOC)s. Direct injections were performed using a direct push rig. In the direct injection plot, 572 liters of EZVI were injected to treat an estimated 0.155 kg of CVOCs. Visual inspection of collected soil cores before and after EZVI injections shows that the travel distance of EZVI was dependent on the method of delivery with pneumatic injection achieving a greater distance of 2.1 m than did direct injection reaching a distance of 0.89 m. Significant decreases in PCE and TCE concentrations were observed in downgradient wells with corresponding increases in degradation products including significant increases in ethene. In the pneumatic injection plot, there were significant reductions in the downgradient groundwater mass flux values for chlorinated ethenes (>58%) and a significant increase in the mass flux of ethene (628%). There were significant reductions in total CVOCs mass (78%), which was less than an estimated 86% decrease in total CVOCs made at 2.5 years due to variations in soil cores collected for CVOCs extraction and determination; an estimated reduction of 23% (vs.63% at 2.5 years) in the sorbed and dissolved phases and 95% (vs. 93% at 2.5 years) reduction in the PCE DNAPL mass. Significant increases in dissolved sulfide, volatile fatty acids (VFA), and total organic carbon (TOC) were observed and dissolved sulfate and pH decreased in many monitoring wells. The apparent effective destruction of CVOC was accomplished by a combination of abiotic dechlorination by nanoiron and biological reductive dechlorination stimulated by the oil in the emulsion. No adverse effects of EZVI were observed for the microbes. In contrast, populations of dehalococcoides showed an increase up to 10,000 fold after EZVI injection. The dechlorination reactions were sustained for the six-year period from a single EZVI delivery. Repeated EZVI injections four to six years apart may be cost-effective to more completely remove the source zone contaminant mass. Overall, the advantages of the EZVI technology include an effective “one-two punch” of rapid abiotic dechlorination followed by a sustained biodegradation; contaminants are destroyed rather than transferred to another medium; ability to treat both DNAPL source zones and dissolved-phase contaminants to contain plume migration; ability to deliver reactants to targeted zones not readily accessible by conventional permeable reactive barriers; and potential for lower overall costs relative to alternative technologies such as groundwater pump-and-treat with high operation and maintenance costs or thermal technologies with high capital costs. The main limitations of the EZVI technology are difficulty in effectively distributing the viscous EZVI to all areas impacted with DNAPL; potential decrease in hydraulic conductivity due to iron corrosion products buildup or biofouling; potential to adversely impact secondary groundwater quality through mobilization of metals and production of sulfides or methane; injection of EZVI may displace DNAPL away from the injection point; and repeated injections may be required to completely destroy the contaminants.

Acyl group transfer processes are plentiful in enzymatic reactions. Examples may be found in ATP-dependent ligation in chapter 11, carbon-carbon bond formation in chapter 14, and fatty acid biosynthesis in chapter 18. In this chapter, we begin by presenting the basic chemistry of acyl group transfer. We then consider four major classes of proteases that catalyze acyl group transfer in the hydrolysis of peptide bonds. Acyl group transfer is so common in organic and biochemistry that the chemistry by which it occurs is often taken for granted. Early studies provided evidence for a mechanism initiated by nucleophilic addition of the acyl group acceptor to the carbonyl group to form a tetrahedral intermediate, analogous to the reversible addition of a nucleophilic molecule to the carbonyl group of an aldehyde or ketone. A mechanism of this type is shown in scheme 6-1 for acyl group transfer from a group :X to a nucleophile :G catalyzed by a general base. This mechanism is drawn from a larger family of possible mechanisms involving specific acid-base, general acid, general base, or concerted general acid-base catalysis of nucleophilic addition to an acyl carbonyl group to form a tetrahedral intermediate, followed by the elimination of :X–H to produce the new acyl compound. In enzymatic reactions the nucleophilic atom G in scheme 6-1 is normally nitrogen, oxygen, sulfur, or a carbanionic species. An acyl carbonyl group is less polar and correspondingly less reactive toward nucleophilic addition than an aldehyde or ketone. The reason is the effect on the heteroatom of nonbonding electrons, which reside in p orbitals that overlap the π orbital of the carbonyl group. The consequent delocalization of electrons stabilizes the carbonyl group and attenuates its reactivity with nucleophiles. Other factors being equal, the order of reactivity is thioester > ester > amide, which is the inverse of the degree of delocalization. Delocalization is least in thioesters because of the high energy of the sulfur p orbitals, which reside in the next higher principal quantum number relative to oxygen in the acyl carbonyl group.

Biomass and sewage sludge are attracting increasing interest in power plant technology as a source of carbon dioxide-neutral fuels. A new way to reduce the consumption of fossil fuels could be the co-combustion or co-gasification of coal and biomass or coal and sewage sludge. In both cases, pyrolysis is the first step in the technical process. In order to obtain detailed information about the pyrolysis of coal/biomass and coal/sewage sludge mixtures as well as unblended fuels, the ‘Institut für Verfahrenstechnik und Dampfkesselwesen (IVD)’ at the University of Stuttgart has carried out investi