Academic literature on the topic 'Nitrates – Reactivity'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the lists of relevant articles, books, theses, conference reports, and other scholarly sources on the topic 'Nitrates – Reactivity.'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Journal articles on the topic "Nitrates – Reactivity"
1
González-Sánchez, Juan Miguel, Nicolas Brun, Junteng Wu, Julien Morin, Brice Temime-Roussel, Sylvain Ravier, Camille Mouchel-Vallon, Jean-Louis Clément, and Anne Monod. "On the importance of atmospheric loss of organic nitrates by aqueous-phase ●OH oxidation." Atmospheric Chemistry and Physics 21, no. 6 (March 30, 2021): 4915–37. http://dx.doi.org/10.5194/acp-21-4915-2021.
Full textAbstract:
Abstract. Organic nitrates are secondary species in the atmosphere. Their fate is related to the chemical transport of pollutants from polluted areas to more distant zones. While their gas-phase chemistry has been studied, their reactivity in condensed phases is far from being understood. However, these compounds represent an important fraction of organic matter in condensed phases. In particular, their partition to the aqueous phase may be especially important for oxidized organic nitrates for which water solubility increases with functionalization. This work has studied for the first time the aqueous-phase ⚫OH-oxidation kinetics of four alkyl nitrates (isopropyl nitrate, isobutyl nitrate, 1-pentyl nitrate, and isopentyl nitrate) and three functionalized organic nitrates (α-nitrooxyacetone, 1-nitrooxy-2-propanol, and isosorbide 5-mononitrate) by developing a novel and accurate competition kinetic method. Low reactivity was observed, with kOH ranging from 8×107 to 3.1×109 L mol−1 s−1 at 296±2 K. Using these results, a previously developed aqueous-phase structure–activity relationship (SAR) was extended, and the resulting parameters confirmed the extreme deactivating effect of the nitrate group, up to two adjacent carbon atoms. The achieved extended SAR was then used to determine the ⚫OH-oxidation rate constants of 49 organic nitrates, including hydroxy nitrates, ketonitrates, aldehyde nitrates, nitrooxy carboxylic acids, and more functionalized organic nitrates such as isoprene and terpene nitrates. Their multiphase atmospheric lifetimes towards ⚫OH oxidation were calculated using these rate constants, and they were compared to their gas-phase lifetimes. Large differences were observed, especially for polyfunctional organic nitrates: for 50 % of the proposed organic nitrates for which the ⚫OH reaction occurs mainly in the aqueous phase (more than 50 % of the overall removal), their ⚫OH-oxidation lifetimes increased by 20 % to 155 % under cloud/fog conditions (liquid water content LWC = 0.35 g m−3). In particular, for 83 % of the proposed terpene nitrates, the reactivity towards ⚫OH occurred mostly (>98 %) in the aqueous phase, while for 60 % of these terpene nitrates, their lifetimes increased by 25 % to 140 % compared to their gas-phase reactivity. We demonstrate that these effects are of importance under cloud/fog conditions but also under wet aerosol conditions, especially for the terpene nitrates. These results suggest that considering aqueous-phase ⚫OH-oxidation reactivity of biogenic nitrates is necessary to improve the predictions of their atmospheric fate.
2
Rindelaub, Joel D., Carlos H. Borca, Matthew A. Hostetler, Jonathan H. Slade, Mark A. Lipton, Lyudmila V. Slipchenko, and Paul B. Shepson. "The acid-catalyzed hydrolysis of an <i>α</i>-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact." Atmospheric Chemistry and Physics 16, no. 23 (December 13, 2016): 15425–32. http://dx.doi.org/10.5194/acp-16-15425-2016.
Full textAbstract:
Abstract. The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.
3
Bew, Sean P., Glyn D. Hiatt-Gipson, Graham P. Mills, and Claire E. Reeves. "Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate." Beilstein Journal of Organic Chemistry 12 (May 27, 2016): 1081–95. http://dx.doi.org/10.3762/bjoc.12.103.
Full textAbstract:
Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a ’halide for nitrate’ substitution. Employing readily available starting materials, reagents and Horner–Wadsworth–Emmons chemistry the synthesis of easily separable, synthetically versatile ‘key building blocks’ (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, ’off the shelf’ materials. Exploiting their reactivity we have studied their ability to undergo an ‘allylic halide for allylic nitrate’ substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates (‘isoprene nitrates’) in 66–80% overall yields. Using NOESY experiments the elucidation of the carbon–carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our ‘halide for nitrate’ substitution chemistry we outline the straightforward transformation of (1R,2S)-(−)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(−)-myrtenol nitrate.
4
Romanova, Svetlana M., and Liliya A. Fatykhova. "INVESTIGATION OF REACTIONS OF INTERACTION OF CELLULOSE NITRIC ESTERS WITH CARBOXYLIC ACID CHLORIDES." IZVESTIYA VYSSHIKH UCHEBNYKH ZAVEDENII KHIMIYA KHIMICHESKAYA TEKHNOLOGIYA 64, no. 5 (May 13, 2021): 30–34. http://dx.doi.org/10.6060/ivkkt.20216405.6313.
Full textAbstract:
The chemical interaction of high-nitrogen cellulose ether with acetic, propionic, butyric and isobutyric acids has been studied. The general laws and features of the electrophilic substitution of functional groups of cellulose nitroesters are revealed. The preferred directions of the chemical interaction of cellulose nitrate with carboxylic acid chlorides are established: O-acylation of nitrate and hydroxyl groups; O-acylation of the glucopyranose ring; O-acylation of the ether bond with depolymerization of the chain of an SC molecule; hydrolysis of nitrate groups; destruction of the chain of a macromolecule of nitric acid ester with the formation of water-soluble organic compounds. The structure, properties and possibilities of using synthesized mixed cellulose ethers were studied. Effective methods have been developed for the chemical modification of cellulose nitrates with carboxylic acid chlorides. The probable directions of the reaction of the interaction of cellulose nitrates with electrophilic reagents are predicted based on quantum-chemical calculations of point charges on the atoms of the reacting molecules. The reactivity of highly substituted cellulose nitrates in reactions with carboxylic acid chlorides has been established. The optimal conditions for the interaction of cellulose nitrates with carboxylic acid chlorides have been identified and a mathematical model of the reaction kinetics has been constructed. The possibility of a directed change in the composition of chemically modified cellulose nitrates depending on the synthesis conditions has been established. As a result of the combined use of physicochemical research methods, the chemical composition was determined and the structure of the synthesized compounds was determined: cellulose acetyl nitrates, cellulose propionyl nitrates, cellulose butyryl nitrates, and cellulose isobutyryl nitrates. Using gel chromatography, it was found that the molecular weight characteristics of the synthesized samples are directly dependent on the conditions of their synthesis. It was found that electrophilic substitution of the functional groups of cellulose nitrate proceeds more intensively in the pyridine medium.
5
Liebmann, Jonathan, Nicolas Sobanski, Jan Schuladen, Einar Karu, Heidi Hellén, Hannele Hakola, Qiaozhi Zha, et al. "Alkyl nitrates in the boreal forest: formation via the NO<sub>3</sub>-, OH- and O<sub>3</sub>-induced oxidation of biogenic volatile organic compounds and ambient lifetimes." Atmospheric Chemistry and Physics 19, no. 15 (August 15, 2019): 10391–403. http://dx.doi.org/10.5194/acp-19-10391-2019.
Full textAbstract:
Abstract. The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (ΣANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.
6
Lockwood, A. L., P. B. Shepson, M. N. Fiddler, and M. Alaghmand. "Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry." Atmospheric Chemistry and Physics 10, no. 13 (July 8, 2010): 6169–78. http://dx.doi.org/10.5194/acp-10-6169-2010.
Full textAbstract:
Abstract. Isoprene is an important atmospheric volatile organic compound involved in ozone production and NOx (NO+NO2) sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene hydroxy nitrates ("isoprene nitrates") or convert NO to NO2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NOx in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/−0.015). Three isomers, representing nitrates resulting from OH addition to a terminal carbon, represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ~1–2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.
7
Ren, Qiang, Xiu Lan Wu, and Xuan Meng He. "Effects of Adding Form of Additives on the Structure and Properties of High-Purity Alumina Ceramics." Key Engineering Materials 336-338 (April 2007): 1130–32. http://dx.doi.org/10.4028/www.scientific.net/kem.336-338.1130.
Full textAbstract:
High-purity alumina ceramics was prepared using high-purity α-Al2O3 powder as raw material, nitrates or oxides of magnesium, chromium and copper as additives by a wet ball milling with a later dry pressing forming and normal pressure sintering process. The influence of additives on the sintering temperature, microstructure and bending strength of the prepared alumina ceramics was studies. The results showed that the additive doped with nitrate can be dispersed uniformly in the body with molecule scale, and the oxides obtained by decomposing of nitrates have the higher reactivity. Thus, the nitrate additives have better capacity than oxide additives in reducing the sintering temperature and inhibiting the abnormal grain growth, and the alumina ceramics prepared by adding of nitrate additives have higher density and bending strength.
8
Perring, A. E., T. H. Bertram, P. J. Wooldridge, A. Fried, B. G. Heikes, J. Dibb, J. D. Crounse, et al. "Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates." Atmospheric Chemistry and Physics Discussions 8, no. 3 (June 24, 2008): 12313–41. http://dx.doi.org/10.5194/acpd-8-12313-2008.
Full textAbstract:
Abstract. Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunction nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, H2CO, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed VOC to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least 76% of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We recommend sets of production rates, lifetimes and recycling efficiencies of INs as follows [4.4%, 5 h, 92%], [8%, 2.5 h, 84%] and [12%, 90 min, 74%]. The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.
9
Lockwood, A. L., P. B. Shepson, M. N. Fiddler, and M. Alaghmand. "Isoprene nitrates: preparation, separation, identification, yields, and atmospheric chemistry." Atmospheric Chemistry and Physics Discussions 10, no. 4 (April 22, 2010): 10625–51. http://dx.doi.org/10.5194/acpd-10-10625-2010.
Full textAbstract:
Abstract. Isoprene is an important atmospheric volatile organic compound involved in ozone production and NOx (NO+NO2) sequestration and transport. Isoprene reaction with OH in the presence of NO can form either isoprene nitrates or convert NO to NO2 which can photolyze to form ozone. While it has been shown that isoprene nitrate production can represent an important sink for NOx in forest impacted environments, there is little experimental knowledge of the relative importance of the individual isoprene nitrate isomers, each of which has a different fate and reactivity. In this work, we have identified the 8 individual isomers and determined their total and individual production yields. The overall yield of isoprene nitrates at atmospheric pressure and 295 K was found to be 0.070(+0.025/–0.015). Three isomers, the (4,3)-IN, (1,2)-IN and Z-(4,1)-IN represent 90% of the total IN yield. We also determined the ozone rate constants for three of the isomers, and have calculated their atmospheric lifetimes, which range from ~1–2 h, making their oxidation products likely more important as atmospheric organic nitrates and sinks for nitrogen.
10
Perring, A. E., T. H. Bertram, P. J. Wooldridge, A. Fried, B. G. Heikes, J. Dibb, J. D. Crounse, et al. "Airborne observations of total RONO<sub>2</sub>: new constraints on the yield and lifetime of isoprene nitrates." Atmospheric Chemistry and Physics 9, no. 4 (February 23, 2009): 1451–63. http://dx.doi.org/10.5194/acp-9-1451-2009.
Full textAbstract:
Abstract. Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5 h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.
Dissertations / Theses on the topic "Nitrates – Reactivity"
1
Mattei, Coraline. "Réactivité hétérogène de pesticides adsorbés sur des particules atmosphériques : influence des paramètres environnementaux sur les cinétiques." Thesis, Aix-Marseille, 2019. http://www.theses.fr/2019AIXM0181.
Full textAbstract:
La contamination de l’environnement par les pesticides est ubiquiste et les preuves d’impacts sanitaires et environnementaux s’accumulent. Après application, une fraction des pesticides passe dans l’atmosphère où ils sont répartis entre les phases gazeuse, aqueuse et particulaire. La plupart des pesticides utilisés aujourd’hui sont semi-volatils et sont donc en partie adsorbés en surface de particules atmosphériques où ont lieu des réactions hétérogènes. La réactivité en phase gazeuse des pesticides est documentée contrairement à celle en phase particulaire qui est mal décrite. Ce travail expérimental a permis d’étudier l’influence de paramètres environnementaux (humidité relative, nature des particules, taux de recouvrement) sur la réactivité hétérogène de 8 pesticides (cyprodinil deltaméthrine difénoconazole fipronil oxadiazon pendiméthaline perméthrine tétraconazole). Ces composés étaient adsorbés sur des particules minérales (silices hydrophobe et hydrophile, sable d’Arizona) et ont été exposés aux principaux oxydants atmosphériques (ozone, radicaux hydroxyles (OH) et nitrates (NO3)). Les résultats ont montré que l’humidité relative, la nature des particules et le taux de recouvrement peuvent influencer les cinétiques de dégradation hétérogène par l’ozone et les radicaux OH. Ils ont aussi permis de mettre en évidence l’efficacité des radicaux NO3 pour la dégradation hétérogène des pesticides (temps de demi-vie hétérogène avec NO3 : 2 à 16 j contre 0,4 à >800 j avec l’ozone et 3 à >100 j avec OH). Ces résultats permettent une meilleure compréhension du devenir atmosphérique des pesticides et contribueront à la prédiction de la pollution de l’air par les pesticidesEnvironmental contamination by pesticides is ubiquitous and induces health and environmental impacts. Once applied, some of the pesticides reach the atmosphere, where they distribute between the aqueous, gaseous and particle phases. Most of the currently used pesticides are semi-volatiles and are therefore partially adsorbed on the atmospheric particle surfaces and undergo heterogeneous degradation reactions. If their reactivity in the gaseous phase is often known, their reactivity in the particle phase remains poorly described. This experimental work allowed studying the influence of environmental parameters (relative humidity, type of particles, pesticides surface concentration) on the reactivity of eight pesticides (cyprodinil, deltamethrin, difenoconazole, fipronil, oxadiazon, pendimethalin, permethrin, tetraconazole). They were adsorbed on mineral surfaces mimicking mineral aerosol particles (hydrophobic and hydrophilic silica, Arizona sand) to simulate atmospheric degradation by the mains atmospheric oxidants (ozone, hydroxyl radicals (OH) and nitrate radicals (NO3)). Results showed that relative humidity, particle type, and pesticide concentration can influence the heterogeneous degradation of pesticides with ozone and OH radicals. They also showed the efficiency of NO3 radicals for the atmospheric heterogeneous degradation of pesticides (half-lives in the particle phase from 2 to 16 d with NO3 compared to 0.4 to > 800 d with ozone and to 3 to > 100 d with OH). Results obtained allow a better understanding of the atmospheric fate of pesticides and will contribute to predict of atmospheric contamination
2
Kalalian, Carmen. "Réactivité atmosphérique des composés organiques volatils oxygénés biogéniques (aldéhydes et alcools insaturés). Etudes cinétiques de la réaction entre les radicaux peroxyles et le radical nitrate." Thesis, Reims, 2018. http://www.theses.fr/2018REIMS023/document.
Full textAbstract:
Les composés organiques volatils d’origine biogénique (COVB) contribuent à plus de 90% des émissions des COV dans l'atmosphère. Ces composés sont éliminés de l’atmosphère par réaction avec les photo-oxydants (OH, NO3, Cl et O3) et par photolyse. Ces processus sont gouvernés par un mécanisme en chaîne dont les porteurs sont des radicaux libres tels que les radicaux peroxyles RO2 qui jouent un rôle clé dans la dégradation atmosphérique des COV. Dans ce contexte, cette thèse se concentre d’une part sur l’étude cinétique en température et mécanistique de la réaction d’ozonolyse, la détermination des spectres UV et la photolyse de six COV oxygénés insaturés (trans-2-pentènal, trans-2-hexènal, 2-méthyl-2-pentènal, 1-pentèn-3-ol, cis- 2-pentèn-1-ol et trans-3-hexèn-1-ol), et d’autre part l’étude de la réactivité de trois radicaux peroxyles (CH3OCH2O2, CH3C(O)CH2O2 et (CH3)2C(OH)CH2O2) vis-à-vis des radicaux nitrates à différentes températures. Trois dispositifs expérimentaux sont utilisés : une chambre de simulation atmosphérique couplée à une spectroscopie infrarouge à transformée de Fourier (FTIR) et à une chromatographie en phase gazeuse associée à une spectrométrie de masse (GC/MS), un dispositif de mesure des spectres UV-Visible et la photolyse laser couplée à une spectrométrie UV-visible et diode laser. Ces dispositifs associés à des méthodes de traitement permettent d'extraire des données cinétiques en température, mécanistiques et spectroscopiques. Les paramètres cinétiques obtenus sont utilisés pour estimer les durées de vie atmosphériques des espèces étudiées. Les résultats mécanistiques sont utilisés pour élaborer les mécanismes d’ozonolyse de ces composés. Toutes ces données permettent d’enrichir les bases de données cinétiques, mécanistiques et spectroscopiques qui alimentent les modèles atmosphériquesBiogenic volatile organic compounds (BVOC) account for 90% of VOC emissions in the atmosphere. These VOCs can be removed from the atmosphere by reaction with photo-oxidants (OH, NO3, Cl and O3) as well as by photolysis. All these processes are governed by a chain mechanism whose carriers are mainly free radicals such as peroxy radicals RO2. Hence the importance of characterizing the reactivity of these species that play a key role in the atmospheric degradation of VOCs. In this context, this thesis focuses on the determination of the temperature dependent kinetic data as well as the mechanism of the ozonolysis reaction and the UV absorption spectra along the photolysis of six unsaturated oxygenated VOCs (trans- 2-pentenal, trans-2-hexenal, 2-methyl-2-pentenal, 1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol). Likewise, the temperature dependent kinetic parameters of the reaction of three peroxy radicals (CH3OCH2O2, CH3C(O)CH2O2 et (CH3)2C(OH)CH2O2) with nitrate radicals were also determined. Three experimental setups coupled to treatment methods were used to extract these data: an atmospheric simulation chamber coupled to both a Fourier-transform infrared spectroscopy (FTIR) and a gas chromatography connected to a mass spectrometry (GC/MS), a device for measuring UV-Visible spectra and a laser photolysis coupled with UV-visible spectrometry and laser diode spectroscopy. The kinetic parameters were used to estimate the atmospheric lifetimes of the studied species. While the mechanistic data were used to establish their ozonolysis mechanisms. All the collected data enrich kinetic, mechanistic and spectroscopic databases, improving atmospheric models specially those involving VOCs
3
Dhakal, Prakash. "ABIOTIC NITRATE AND NITRITE REACTIVITY WITH IRON OXIDE MINERALS." UKnowledge, 2013. http://uknowledge.uky.edu/pss_etds/30.
Full textAbstract:
Under iron (Fe3+)-reducing conditions where aqueous Fe2+ and unreduced solid Fe3+-oxides commonly coexist, soil Fe2+ oxidation has been shown to be coupled with nitrate (NO3-) reduction. One possible secondary reaction is the involvement of NO3- and nitrite (NO2-) with Fe-oxide minerals found in many natural environments. Yet, spectroscopic measurements and kinetic data on reactivity of NO3- and NO2- with Fe-containing oxide minerals such as goethite (a-FeOOH), and magnetite (Fe3O4) are not found in the literature. The reactivity of goethite and magnetite with NO3- and NO2- was studied over a range of environmentally relevant pH conditions (5.5-7.5) with and without added Fe2+(aq) under anoxic conditions. Laboratory experiments were conducted using stirred batch experiments and reaction products were analyzed using ion chromatography (IC), gas chromatography (GC), ultraviolet visible near infrared spectroscopy (UV-VIS-NIR), x-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer, and Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy. Nitrate removal by goethite and magnetite was much slower when compared with NO2-. There was a pH-dependence in the reduction of NO2-, and the initial rate of NO2- removal was nearly 2 and 8 times faster at pH 5.5 than at pH 7.5 by magnetite and goethite, respectively. Nitric oxide (NO) and nitrous oxide (N2O) were identified as products when NO2- has reacted with magnetite, whereas N2O is the major reaction product in the experiment with goethite. In comparison to experiments containing magnetite or goethite alone, addition of Fe2+ greatly accelerated the NO2- removal rate. Wet chemical experiments combined with the Mössbauer study reveals that NO2- reduction to NO and subsequently to N2O by magnetite occurs via a heterogeneous electron transfer process. ATR-FTIR and diffuse reflectance spectroscopy (DRS) results from the studies with goethite indicate that NO2- was removed from solution by adsorption in a surface complex involving the oxygen atoms, and a portion of the nitrite is reduced to NO and N2O.
This study suggests that under anaerobic conditions soil and sediments that contain goethite, magnetite, and other Fe3+-oxides can catalyze abiotic NO2- reduction and the kinetics data from this study can be used to predict the NO2- removal under such conditions.
4
DAMIANO, JEAN-PIERRE. "Synthese et reactivite de complexes nitrato du fer." Nice, 1995. http://www.theses.fr/1995NICE4886.
Full textAbstract:
Le travail reporte dans ce memoire concerne la synthese et l'evaluation des proprietes oxydantes de complexes nitrato du fer concus pour l'activation et le transfert de l'oxygene moleculaire sur des composes organiques. Afin de definir l'environnement optimal autour du fer, deux types de ligands ont ete testes: un bidente dissymetrique, 2-(diphenylphosphine oxyde)pyridine (opph#2#p#y) et un ligand bidente susceptible de participer comme relais electronique a l'acte catalytique, 1,1'-bis(diphenylphosphine oxyde)ferrocene (fcp#2o#2) et son oxyde fc#+p#2o#2. Les complexes mono et dinitrates du ligand opph#2#p#y, ainsi que le complexe dinitrate du ligand fcp#2o#2 ont ete obtenus, alors que nous n'avons pas reussi a oxyder le ligand fcp#2o#2 en fc#+p#2o#2. Ces complexes nitrates transferent les atomes d'oxygene de leurs groupements no#3 sur les phosphines et ce transfert genere le motif fe-no#2 et non fe-no. Ils catalysent l'oxydation par l'oxygene moleculaire du cyclohexene, pour conduire majoritairement au cyclohexene-2-ol et a la cyclohexene-2-one. D'autre part, nous avons tente de synthetiser des complexes nitrates chiraux, au niveau d'un ligand (fecl(no#3)#2diop(o#2)), ou au niveau du metal (fecl#4 feclno#3(fcp#2o#2)#2), avec pour objectif l'oxydation asymetrique de substrats organiques, la structure rx du complexe fecl#4#- fecl#2(fcp#2o#2)#2#+ nous ayant montre le caractere prochiral de l'atome de fer central du cation. Ces complexes ne sont pas de bons agents de transfert d'oxygene meme sur les phosphines. Nous avons experimente une nouvelle methode d'hydratation des alcynes par fecl#3 en presence de trois equivalents d'eau. Cette reaction stchiometrique permet l'hydratation des alcynes terminaux en methylcetones
5
DUVIVIER, STEPHANE. "Reactivite en solution et aux interfaces dans les liquides ioniques eau - nitrate d'ethylammonium fondu." Paris 6, 2000. http://www.theses.fr/2000PA066564.
Full textAbstract:
Le travail presente concerne la reactivite dans les milieux eau-nitrate d'ethylammonium (nea). Le nea est un sel fondu a temperature ordinaire, miscible a l'eau en toutes proportions, ce qui permet d'obtenir des liquides ioniques utilisables comme milieux reactionnels pour des procedes chimiques ou electrochimiques dans une large gamme de temperature (10 a + 50\c). Ces solvants presentent l'avantage de posseder une conductivite proche de celle des solutions salines concentrees et un pouvoir solubilisant comparable a celui des solvants organiques comme le methanol. Ces solvants possedent de nombreuses proprietes proches de l'eau, en particulier les phenomenes d'agregation micellaire. Apres avoir etudie les comportements des tensioactifs envers une molecule complexante (la -cyclodextrine), nous nous sommes interesses a l'adsorption des amphiphiles sur une argile synthetique, la laponite. Ceci nous a conduit a developper une approche thermodynamique complete des phenomenes d'adsorption solide-liquide et liquide-vapeur pour les solutions de tensioactifs neutres et ioniques dans ces milieux. Nous avons ainsi montre par l'etude du coefficient calorimetrique b t , p l'existence d'une transition a basse concentration pour les tensioactifs neutres dans l'eau. La transition disparait au fur et a mesure que la concentration en nea augmente par constitution d'une couche mixte en surface (cation ethylammium-tensioactif). La mouillabilite de solutions de tensioactif et son evolution avec la concentration en amphiphile a ete etudiee et interpretee sur differents solides hydrophobes et hydrophiles. La derniere partie de ce travail concerne l'aspect cinetique. Les vitesses de reaction de substitution nucleophile aromatique d'une base sur le fluorodinitrobenzene ont ete determinees dans les melanges eau-nea. Les effets catalytiques sont relativement faibles. Le nea est un solvant oxydant. Nous avons illustre cette propriete en determinant les vitesses d'oxydation du ferrocene dans le nea pur en fonction de l'acidite du milieu.
6
Zeamari, Kamal. "Investigation par spectroscopie RPE des bases moléculaires de la réactivité d'une enzyme à molybdène : la nitrate réductase périplasmique de Rhodobacter sphaeroides." Thesis, Aix-Marseille, 2018. http://www.theses.fr/2018AIXM0546/document.
Full textAbstract:
La nitrate réductase périplasmique de Rhodobacter sphaeroides possède, un cofacteur à Mo (site actif), un centre [4Fe-4S] et deux hèmes de type c formant une chaîne de transfert électronique intramoléculaire. Ce travail est centré sur deux aspects moléculaires de la catalyse de cette enzyme : la réactivité au niveau du site actif de l’enzyme et les processus de transfert d’électrons intramoléculaires. Ces questions sont abordées en s’appuyant parallèlement sur des approches de mutagénèse dirigée, d’activités enzymatiques, de spectroscopie de résonance paramagnétique électronique (RPE) en onde continue et impulsionnelle et sur des mesures de potentiels redox associés aux cofacteurs de l’enzyme. La première partie de ce travail est consacrée à la caractérisation spectroscopique et physico-chimique d’intermédiaires Mo(V) du site actif afin de déterminer leur structure et leur positionnement possible dans le cycle catalytique. Nous avons ainsi étudiée de manière détaillée deux intermédiaires Mo(V) en présence de nitrate dont nous montrons qu’ils présentent des différences structurales au-delà de la première sphère de coordination du Mo. Dans la seconde partie, nous mettons en évidence le rôle d'un acide aminé très conservé (Lys) dans le transfert d'électrons intramoléculaire. Cet acide aminé chargé positivement est situé dans la seconde sphère de coordination du centre [4Fe-4S] et joue un rôle majeur dans la modulation des propriétés rédox du centre [4Fe-4S], ce qui affecte fortement les propriétés catalytiques de l'enzyme. L’ensemble de nos résultats permettent ainsi d’identifier dans l’environnement du Mo des éléments déterminants dans la réactivité de l’enzymeThe periplasmic nitrate reductase from Rhodobacter sphaeroides contains, in addition to the Mo-cofactor, a [4Fe-4S] center and two c-type hemes defining an intramolecular electron transfer chain. This work focuses on two molecular aspects of the catalysis: the reactivity of the Mo-cofactor, and the intramolecular electron transfer step. These issues are dealt by combining approaches as site-directed mutagenesis, enzymatic activities, continuous-waves (CW) and pulse electron paramagnetic resonance spectroscopy (EPR), UV-Vis spectroscopy and redox titration of metal cofactors of the enzyme. A first part of this work is devoted to the spectroscopic and physicochemical characterization (thermodynamic and kinetic properties) of Mo (V) intermediates of the active site in order to determine their structure and their catalytic relevance. We have undertaken a detailed characterization of two Mo(V) intermediates generated in presence of nitrate, which display some structural differences beyond the first coordination sphere of the Mo(V) ion. In a second part, we highlight the role of a highly conserved amino acid (Lys) in intramolecular electron transfer. This positively-charged amino acid is located in the second coordination sphere of the [4Fe-4S] center and plays a major role in the redox properties tuning of the [4Fe-4S] center thus strongly affecting the catalytic properties of the enzyme. All together, these data provide some structural insights on the enzyme reactivity beyond the first coordination sphere of the Mo-cofactor
7
Scarfogliero, Michaël. "Étude en atmosphère simulée de la chimie troposphérique nocturne de composés organiques volatils oxygénés." Thesis, Paris Est, 2008. http://www.theses.fr/2008PEST0010.
Full textAbstract:
L’oxydation troposphérique des composés organiques volatils (COV) constitue une contribution importante à la formation de photooxydants. L’évaluation de l’impact environnemental des COV rend indispensable d’acquérir une bonne compréhension des processus en jeu. Ce travail porte donc sur l’étude en atmosphère simulée de la réactivité troposphérique avec le radical nitrate (NO3) de COV oxygénés appartenant à une série homogène d’éthers vinyliques aliphatiques (méthyl, éthyl, propyl et butyl vinyl éthers), et à une série de trois esters (acétates d’isopropényle, de vinyle, et d’allyle), auxquelles s’ajoute le 2,3,2 méthylbutènol (MBO). Pour tous ces composés, des études cinétiques (destinées à mesurer la constante d’oxydation par NO3 des produits étudiés) ont été menées selon la méthode relative, et pour certains composés selon la méthode absolue. Des études mécanistiques (destinées à identifier et quantifier les produits de la réaction, et à élucider le mécanisme réactionnel) ont également été menées. Une réévaluation de la constante cinétique d’oxydation du propène par NO3, qui a été mesurée selon la méthode absolue, a également été faite. Les expériences ont été menées dans la chambre de simulation atmosphérique du LISA, à température ambiante et à pression atmosphérique. Les durées de vie des composés étudiés vis-à-vis de NO3 ont été calculées, et comparées à celles vis-à-vis du radical OH et de l’ozone. Les résultats montrent que NO3 peut constituer un puits majeur pour les COV les plus réactifs, comme les éthers vinyliques. Par ailleurs, les apports de nos résultats aux règles de réactivité des COV ont été discutésThe tropospheric oxidation of the volatile organic compounds (VOC) constitutes an important contribution to the formation of photooxydants. It is necessary to acquire a good comprehension of the concerned chemical processes in order to correctly evaluate the environmental impact of the VOC. This work thus concerns the study under simulated conditions of the tropospheric reactivity with the nitrate radical (NO3) of oxygenated VOC pertaining to a homologous series of aliphatic vinyl ethers (methyl, éthyl, propyl and butyl vinyl ethers), and to a series of three esters (allyl and vinyl, isopropenyl acetates). In addition, the 2,3,2 méthylbutènol (MBO) has been studied too. For all these compounds, kinetic studies (in order to measure the rate constant of NO3 oxidation of the studied products) were performed according to the relative rate method, and for some compounds according to the absolute method. Mechanistic studies (in order to identify and quantify the reaction products, and to elucidate the chemical mechanism) were also performed. A revaluation of the rate constant of NO3 oxidation of propene, which was measured according to the absolute method, was also performed. The experiments were carried out in the LISA atmospheric simulation chamber, at room temperature and atmospheric pressure. The lifetimes of the studied compounds with respect to NO3 were calculated, and were compared to those with respect to OH radical and to ozone. The results show that NO3 can be a major sink for the most reactive VOC, like the vinyl ethers. In addition, the contributions of our results to the rules of reactivity of the VOC were discussed
8
Semones, Molly Catherine. "Dynamics in the reactivity and photochemical production of hydroxyl radical in treated wastewater effluent and aquatic dissolved organic matter." The Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1482849720513842.
Full text
9
Peerless, B. "Synthesis, characterisation and reactivity of low-valent and hypercoordinate azido, triazenido and nitrato complexes of Group 14 and Group 15 elements." Thesis, University of Sheffield, 2017. http://etheses.whiterose.ac.uk/19019/.
Full text
10
Zhang, Jing. "Analyses of Atmospheric Pollutants in Atlanta and Hong Kong Using Observation-Based Methods." Diss., Georgia Institute of Technology, 2004. http://hdl.handle.net/1853/4768.
Full textAbstract:
There are two parts in this study. The first part is to test the validity of the assumption of thermodynamic equilibrium between fine particulate (PM2.5) nitrate and ammonium and gas-phase nitric acid (HNO3(g)) and ammonia (NH3(g)). A rough estimation of the characteristic time to achieve thermodynamic equilibrium is first carried out, which suggests that PM2.5 and gas-phase species are in thermodynamic equilibrium. Then equilibrium is tested by calculating the equilibrium concentrations of HNO3(g) and NH3(g) implied by the PM2.5 inorganic composition, temperature and relative humidity observed at the Atlanta Supersite 1999 using ISORROPIA model.
The second part of this study is to analyze the ground-level ozone pollution precursor relationships in Hong Kong area. Characteristics of O3 precursors are explored. Trace gases NO and CO, VOCs, absorption coefficient, temperature and solar radiation are associated with the O3 formation. Specific VOC and VOC-sources that contribute most to the formation of photochemical smog are identified. The accuracy of pollutant emission inventories for Hong Kong and PRD region is also assessed. Combined with back trajectory information, dCO/dNOy is used to define whether O3 is locally or regionally occurred. An OBM is used to investigate the relative benefits of various emission-control strategies. Generally the formation of O3 throughout much of Hong Kong area is limited by VOC, in which reactive aromatics are dominant.
Books on the topic "Nitrates – Reactivity"
1
Canada Centre For Mineral and Energy Technology. Administration of the Canada Explosives Act. Studies Into the Thermal Stability and Reactivity of Ammonium Nitrate Part 1: The Reactivity of Various Metals with Ammonium Nitrate Studied by Accelerating Rate Calorimetry. S.l: s.n, 1986.
Find full text
2
Act, Canada Centre For Mineral and Energy Technology Administration of the Canada Explosives. Studies Into the Thermal Stability and Reactivity of Ammonium Nitrate Part 2: Solid State Decomposition of Ammonium Nitrate. S.l: s.n, 1986.
Find full text
3
Dodds, Joseph Neil. DXRD studies of sodium nickel ferrocyanide reactions with equimolar nitrate/nitrite salts. 1993.
Find full textBook chapters on the topic "Nitrates – Reactivity"
1
Wang, Haichao. "NO3 Reactivity and N2O5 Uptake Coefficient." In The Chemistry of Nitrate Radical (NO3) and Dinitrogen Pentoxide (N2O5) in Beijing, 65–94. Singapore: Springer Singapore, 2020. http://dx.doi.org/10.1007/978-981-15-8795-5_4.
Full textConference papers on the topic "Nitrates – Reactivity"
1
Xiaoping, Zhou, Liang Shuhong, and Xia Zhaodong. "A Critical Experimental Study of Bubble Effect in the Process of Spent Fuel Dissolving." In 2018 26th International Conference on Nuclear Engineering. American Society of Mechanical Engineers, 2018. http://dx.doi.org/10.1115/icone26-81644.
Full textAbstract:
The influence of gas introduction on the critical safety of the nuclear fuel system under the condition of cold condition, given reactor material and geometry structure is studied. Refer to bubble effect test experiment on nuclear critical safety test device (YSR) and considering solid-liquid two-phase nuclear fuel system with uranyl nitrate solution - uranium dioxide fuel element as the experimental platform, the dynamic process of the real behavior of bubbles in uranyl nitrate solution has been simulated in the quasi-static way by replacing bubble generator with aluminous bubble simulation elements. Bubble effect is the reactivity change caused by the change of volume of solution, neutron leakage and absorption property in the nuclear fuel system due to the bubbles generated in the solution. In the dissolving process of spent fuel, oxygen or nitrogen are usually added to accelerate the dissolution of fuel element shear section, and some other bubble production are also caused by the heat released during the dissolution process. Here, the bubble production caused by the heat is omitted and only artificial gas introduction is considered in my study. When there are enough bubbles in the uranium solution system, the volume of the solution will increase, which will inevitably influence the absorption and leakage property of the neutrons, and further influence the reactivity of the nuclear fuel system. The corresponding relationship between the bubble-intake rate and the bubble equivalent diameter, arising velocity and bubble share is determined through fluid dynamics modeling to manufacture the aluminous bubble simulation elements. The theoretical calculation by MONK9A and the critical experimental measurements are also compared and analyzed in this paper. The results showed that the reactivity caused by bubbles was negative, and the greater the intake rate, the greater the negative effect. Meanwhile the theoretical calculated value was in good agreement with the experimental value and the maximum deviation was 63.4 pcm.
2
Albers, Dylan, and Mileva Radonjic. "Prevention of Alkali-Silica Reaction (ASR) in Light-Weight Wellbore Cement Comprising Silicate-Based Microspheres." In ASME 2017 36th International Conference on Ocean, Offshore and Arctic Engineering. American Society of Mechanical Engineers, 2017. http://dx.doi.org/10.1115/omae2017-62015.
Full textAbstract:
Drilling through low pressure formations, either offshore or through depleted formations, requires the use of low density fluids to prevent lost circulation and as well as to properly place cement during cementing applications. Achieving these densities in cements can be done through foaming the cement, increasing water content, or through the addition of silica based microspheres. Each of these methods have individual limitations, and in the case of silica based microspheres, their specific fallback is a chemical instability with the microsphere itself reacting with the cement pore fluid. This chemical instability creates a hydrophilic gel that is expansive and creates fractures in the cement as it expands, which is more formally referred to as alkali-silica reactivity (ASR). Prevention of ASR involves the application of additives to the cement that acts as a sink for the alkalinity in which prevents the expansion of ASR. A specific application that this paper investigates for this prevention is the use of Lithium nitrate. This study looks at the effects of a high alkalinity environment onto the microspheres by visualizing the reactions that are occurring using Scanning Electron Microscopy (SEM), and confirming the presence of ASR when silica based microspheres encounter a high pH environment. Then cement samples were created to compare the effects lithium nitrate has on cements created with silica based microspheres. SEM and micro indentation was conducted on these samples, which showed that lithium nitrate prevents reactions, but after 28-day hydration a loss of mechanical properties is present.
3
Gross, Christopher W., and Rolf D. Reitz. "Transient “Single-Fuel” RCCI Operation With Customized Pistons in a Light Duty Multi-Cylinder Engine." In ASME 2015 Internal Combustion Engine Division Fall Technical Conference. American Society of Mechanical Engineers, 2015. http://dx.doi.org/10.1115/icef2015-1051.
Full textAbstract:
Reactivity Controlled Compression Ignition (RCCI) combustion in a light-duty multi-cylinder engine over transient operating conditions using fast response exhaust UHC1, NO and PM measurement instruments was investigated. RCCI has demonstrated improvements in efficiency along with low NOx and PM emissions by utilizing in-cylinder fuel blending, generally using two fuels with different reactivity in order to optimize stratification. In the present work, a “single-fuel” approach for RCCI combustion using port-injected gasoline and direct-injected gasoline mixed with a small amount of the cetane improver 2-ethylhexyl nitrate (EHN) was studied with custom designed, compression ratio of 13.75:1, pistons under transient conditions. The EHN volume percentage in the mixture for the direct-injected fuel was set at 3%. In an experimental investigation, comparisons were made to transient RCCI combustion operation with gasoline/diesel. The experiments were performed over a step load change from 1 to 4 bar brake mean effective pressure (BMEP) at constant 1,500 rev/min on a General Motors Z19DTH 1.9 liter diesel engine The transients were conducted by changing the accelerator pedal command to provide a desired torque output with a DRIVVEN engine control unit (ECU) that replaced the original Bosch ECU. All relevant engine parameters are adjusted accordingly, based on 2D-tables. Previous to the transient engine operation, 4 steady-state points were used to obtain performance and emission values. Engine calibration at these 4 points, as well as the interpolation of the intermediate points, allowed for smooth operation during the instantaneous step changes. Differences between the steady-state and transient results indicate the complexity of transient operation and show the need for additional controls to minimize undesirable effects. The steady-state points were calibrated by modifying the fuel injection strategy (actual Start of Injection (aSOI) timing, port-fuel injection (PFI) fraction, etc.), EGR and rail pressure in order to obtain predefined values for the crank angle at 50% of total heat release (CA50). Furthermore, emission targets (HC1 < 1500ppmC3, NO < 10ppm, FSN < 0.1 with a maximum pressure rise rate < 10bar/deg) and noise level targets (<95dB) for RCCI combustion were maintained during the calibration and mapping. The tests were performed with a closed-loop (CL) calibration by using a next-cycle (NC) controller to adjust the PFI ratio of each cycle in order to reach the steady-state CA50 values in the table. The results show that single-fuel RCCI operation can be achieved, but requires significant alteration of the operating conditions, and NOx emissions were significantly elevated for gasoline/gasoline-EHN operation. While combustion phasing could not be matched, UHC1 emissions were at a similar level as for gasoline/diesel combustion. It is expected that the implementation of different injection strategies and boosted operation, combined with use of higher compression ratio pistons in order to compensate for the lower reactivity direct injection (DI) fuel, could raise the potential for improved performance.
4
Gill, David D., Nathan P. Siegel, Robert W. Bradshaw, and Clifford K. Ho. "Design, Fabrication and Testing of an Apparatus for Material Compatibility Testing in Nitrate Salts at Temperatures Up to 700°C." In ASME 2011 5th International Conference on Energy Sustainability. ASMEDC, 2011. http://dx.doi.org/10.1115/es2011-54250.
Full textAbstract:
Thermal energy storage is one of the key differentiators between Concentrating Solar Power (CSP) and other renewable energy technologies. Molten salt is an effective and affordable method of storing thermal energy. Current salt storage systems charge at temperatures between 390°C and 585°C (oil filled parabolic trough systems to molten salt towers). It is highly desirable to increase the operating temperature of salt storage systems in order to increase the efficiency of the power cycle and to permit the use of alternative, high-temperature cycles. However, higher salt temperatures cause increased reactivity and thus increased corrosion rates in many materials. In order to utilize molten salt at higher temperature, it is necessary to test and understand these corrosion interactions at elevated temperature. A corrosion test system has been designed and built for evaluating molten salt/material interactions to 700°C. The primary components of this system are several salt containment vessels that are constructed of 6″ dia. × 24″ long stainless steel, aluminum diffusion treated pipes with flat plate welded to one end and a flanged lid on the other. The vessels are designed to operate with a charge of 10 kg of molten salt and accommodate a “sample tree” on which corrosion test coupons may be suspended. The salt vessels are heated and insulated on the bottom half, roughly to the salt fill level, and cooled on the top half to protect the flange gasket and feedthrough ports. The samples trees have a stainless plate that reduces radiative heat transfer from the molten salt to the lid. Finite element analysis was performed to determine the pipe length and heating and cooling requirements to maintain molten salt at 700°C while limiting the lid gasket to 300°C or less. The vessels are designed to have an oxygen atmosphere in the ullage region to mitigate nitrate decomposition. Oxygen systems for operation at 700°C require careful design including the sizing, routing, cleanliness, and material selection of components in order to reduce risk of fire. Additionally, the system is designed to run at 1–2 psig which requires specialized low pressure / high temperature components. In this paper we present the design of the molten salt corrosion test system including details related to the containment vessels, oxygen handling system, and control software along with a discussion of the safety considerations necessary for these high temperature, high oxygen partial pressure tests.
Reports on the topic "Nitrates – Reactivity"
1
Burger, L. L., and R. D. Scheele. The reactivity of cesium nickel ferrocyanide towards nitrate and nitrite salts. Office of Scientific and Technical Information (OSTI), September 1991. http://dx.doi.org/10.2172/5293537.
Full text
2
Clark, David Lewis, and David John Funk. Chemical Reactivity and Recommended Remediation Strategy for Los Alamos Remediated Nitrate Salt (RNS) Wastes. Office of Scientific and Technical Information (OSTI), April 2015. http://dx.doi.org/10.2172/1177520.
Full text