Nitratoethyl-5H-tetrazoles: Improving Oxygen Balance through Application of Organic Nitrates in Energetic Coordination Compounds

2021 ◽  
Author(s):  
Joerg Stierstorfer ◽  
Michael S. Gruhne ◽  
Thomas M. Klapoetke ◽  
Tobias Lenz ◽  
Markus Rösch ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Coordination Compounds ◽  
Organic Nitrates ◽  
Oxygen Balance

1- and 2-Nitratoethyl-5H-tetrazole (1-NET, 2-NET) were prepared through nitration of the respective alkyl alcohol using 100% nitric acid. A mixture of 1- and 2-hydroxyethyl-5H-tetrazole was obtained after alkylation of 1,5H-tetrazole....

Group separation of organic nitrates on a new nitric acid ester NP-LC stationary phase

1998 ◽  
Vol 47 (3-4) ◽  
pp. 157-163 ◽  
Author(s):  
J. Kastler ◽  
V. Dubourg ◽  
R. Deisenhofer ◽  
K. Ballschmiter
Keyword(s):  
Nitric Acid ◽  
Stationary Phase ◽  
Acid Ester ◽  
Organic Nitrates ◽  
Group Separation ◽  
Nitric Acid Ester

scholarly journals Uptake of nitric acid, ammonia, and organics in orographic clouds: mass spectrometric analyses of droplet residual and interstitial aerosol particles

2017 ◽  
Vol 17 (2) ◽  
pp. 1571-1593 ◽  
Author(s):  
Johannes Schneider ◽  
Stephan Mertes ◽  
Dominik van Pinxteren ◽  
Hartmut Herrmann ◽  
Stephan Borrmann
Keyword(s):  
Nitric Acid ◽  
Black Carbon ◽  
Aqueous Phase ◽  
Aerosol Particles ◽  
Organic Nitrates ◽  
Temperature Dependent ◽  
Cloud Droplets ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Mass Fractions

Abstract. Concurrent in situ analyses of interstitial aerosol and cloud droplet residues have been conducted at the Schmücke mountain site during the Hill Cap Cloud Thuringia campaign in central Germany in September and October 2010. Cloud droplets were sampled from warm clouds (temperatures between −3 and +16 °C) by a counterflow virtual impactor and the submicron-sized residues were analyzed by a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), while the interstitial aerosol composition was measured by an high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). During cloud-free periods, the submicron out-of-cloud aerosol was analyzed using both instruments, allowing for intercomparison between the two instruments. Further instrumentation included black carbon measurements and optical particle counters for the aerosol particles as well as optical sizing instrumentation for the cloud droplets. The results show that, under cloud conditions, on average 85 % of the submicron aerosol mass partitioned into the cloud liquid phase. Scavenging efficiencies of nitrate, ammonium, sulfate, and organics ranged between 60 and 100 %, with nitrate having, in general, the highest values. For black carbon, the scavenging efficiency was markedly lower (about 24 %). The nitrate and ammonium mass fractions were found to be markedly enhanced in cloud residues, indicating uptake of gaseous nitric acid and ammonia into the aqueous phase. This effect was found to be temperature dependent: at lower temperatures, the nitrate and ammonium mass fractions in the residues were higher. Also, the oxidation state of the organic matter in cloud residues was found to be temperature dependent: the O : C ratio was lower at higher temperatures. A possible explanation for this observation is a more effective uptake and/or higher concentrations of low-oxidized water-soluble volatile organic compounds, possibly of biogenic origin, at higher temperatures. Organic nitrates were observed in cloud residuals as well as in the out-of-cloud aerosol, but no indication of a preferred partitioning of organic nitrates into the aqueous phase or into the gas phase was detected. Assuming the uptake of nitric acid and ammonia in cloud droplets will be reversible, it will lead to a redistribution of nitrate and ammonium among the aerosol particles, leading to more uniform, internally mixed particles after several cloud passages.

scholarly journals Uptake of nitric acid, ammonia, and organics in orographic clouds: Mass spectrometric analyses of droplet residual and interstitial aerosol particles

2016 ◽  
Author(s):  
Johannes Schneider ◽  
Stephan Mertes ◽  
Dominik van Pinxteren ◽  
Hartmut Herrmann ◽  
Stephan Borrmann
Keyword(s):  
Nitric Acid ◽  
Black Carbon ◽  
Aqueous Phase ◽  
Aerosol Particles ◽  
Water Soluble ◽  
Organic Nitrates ◽  
Temperature Dependent ◽  
Cloud Droplets ◽  
Mass Fractions ◽  
Orographic Clouds

Abstract. Concurrent in-situ analyses of interstitial aerosol and cloud droplet residues have been conducted at the Schmücke mountain site during the Hill Cap Cloud Thuringia campaign in central Germany in September and October 2010. Cloud droplets were sampled from warm clouds (temperatures between −3 and +16 °C) by a counterflow virtual impactor and the submicron-sized residues were analyzed by a C-ToF-AMS, while the interstitial aerosol composition was measured by an HR-ToF-AMS. During cloud-free periods the submicron out-of-cloud aerosol was analyzed using both instruments, allowing for intercomparison between the two instruments. Further instrumentation included black carbon measurements and optical particle counters for the aerosol particles as well as optical sizing instrumentation for the cloud droplets. The results show that under cloud conditions on average 85 % of the submicron aerosol mass partitioned into the cloud liquid phase. Scavenging efficiencies of nitrate, ammonium, sulfate, and organics ranged between 60 and 100 %, with nitrate having in general the highest values. For black carbon, the scavenging efficiency was markedly lower (about 24 %). The nitrate and ammonium mass fractions were found to be markedly enhanced in cloud residues, indicating uptake of gaseous nitric acid and ammonia into the aqueous phase. This effect was found to be temperature dependent: At lower temperatures the nitrate and ammonium mass fractions in the residues were higher. Also, the oxidation state of the organic matter in cloud residues was found to be temperature dependent: The O:C ratio was lower at higher temperatures. A possible explanation for this observation is a more effective uptake and/or higher concentrations of low-oxidized water soluble volatile organic compounds, possibly of biogenic origin, at higher temperatures. Organic nitrates were observed in cloud residuals as well as in the out-of-cloud aerosol, but no indication of a preferred partitioning of organic nitrates into the aqueous phase or into the gas phase was detected. Assuming the uptake of nitric acid and ammonia in cloud droplets to be reversible, it will lead to a redistribution of nitrate and ammonium among the aerosol particles, leading to more uniform, internally mixed particles after several cloud passages.

Organic nitrates, thionitrates, peroxynitrites, and nitric oxide: a molecular orbital study of the (X = O, S) rearrangement, a reaction of potential biological significance

1995 ◽  
Vol 73 (10) ◽  
pp. 1627-1638 ◽  
Author(s):  
Dale R. Cameron ◽  
Alison M.P. Borrajo ◽  
Gregory R.J. Thatcher ◽  
Brian M. Bennett
Keyword(s):  
Nitric Oxide ◽  
Nitric Acid ◽  
Molecular Orbital ◽  
Biological Significance ◽  
Intrinsic Reaction Coordinate ◽  
Organic Nitrates ◽  
Molecular Orbital Calculations ◽  
Peroxynitrous Acid ◽  
Structural Reorganization

The rearrangement of organic thionitrate to sulfenyl nitrite potentially mediates the release of nitric oxide from organic nitrates, such as nitroglycerin, in the presence of thiol. The biological activity of these nitrovasodilators is proposed to result from release of nitric oxide in vivo. The thionitrate rearrangement bears analogy to the rearrangement of peroxynitrous acid to nitric acid, which has been proposed to mediate the biological toxicity of nitric oxide and superoxide. In this paper, the two concerted rearrangement processes and competing homolytic reactions are explored using molecular orbital calculations at levels up to MP4SDQ/6-31G*//MP2/6-31G*. Examination of structure and energy for all conformers and isomers of RSONO2 (R = H, Me), models for organic thionitrates and their isomers, demonstrates that structures corresponding to thionitrates and sulfenyl nitrates are of similar energy. Free energies of reaction for homolysis of these compounds are low (ΔG0 < 19 kcal/mol), whereas the barrier for concerted rearrangement is large (ΔG≠(aq.) = 56 kcal/mol). The larger barrier for concerted rearrangement of peroxynitrous acid to nitric acid (ΔG≠(aq.) = 60 kcal/mol) again compares unfavourably with homolysis (ΔG0 < 11 kcal/mol for homolysis to NO2 or •NO). The transition state structures, confirmed by normal mode and intrinsic reaction coordinate analysis, indicate that considerable structural reorganization is required for concerted rearrangement of the ground state species. These results suggest that concerted rearrangement is not likely to be a viable step in either biological process. However, rearrangement via homolysis and radical recombination may provide an energetically accessible pathway for peroxynitrous acid rearrangement to nitric acid and rearrangement of thionitrate to sulfenyl nitrite. In this case, NO2 will be a primary product of both reactions. Keywords: thionitrate, nitric oxide, peroxynitrite, nitrovasodilator, nitrate.

scholarly journals Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO<sub>2</sub>, total peroxy nitrate, total alkyl nitrate, and HNO<sub>3</sub>

2013 ◽  
Vol 6 (4) ◽  
pp. 971-980 ◽  
Author(s):  
P. Di Carlo ◽  
E. Aruffo ◽  
M. Busilacchio ◽  
F. Giammaria ◽  
C. Dari-Salisburgo ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Thermal Dissociation ◽  
Laser Induced Fluorescence ◽  
Organic Nitrates ◽  
Fast Time ◽  
Atmospheric Measurements ◽  
Inlet Channel ◽  
Enhanced Absorption ◽  
Simultaneous Measurements ◽  
Alkyl Nitrate

Abstract. A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (∑PNs), total alkyl nitrate (∑ANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations, including (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment; and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ∑PNs, ∑ANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO2 and used to fix the dissociation temperatures of each heated inlet to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ∑PNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF.

scholarly journals Comment on “Isotopic evidence for dominant secondary production of HONO in near-ground wildfire plumes” by Chai et al. (2021)

2021 ◽  
Vol 21 (22) ◽  
pp. 16793-16795
Author(s):  
James M. Roberts
Keyword(s):  
Nitric Oxide ◽  
Nitric Acid ◽  
Secondary Production ◽  
Nitrous Acid ◽  
Nitrogen Compound ◽  
Decomposition Reaction ◽  
Organic Radicals ◽  
Organic Nitrates ◽  
Oxides Of Nitrogen ◽  
Model Reactions

Abstract. Chai et al. (2021) recently published measurements of wildfire-derived (WF) oxides of nitrogen (NOx) and nitrous acid (HONO) and their isotopic composition. The method used to sample NOx, collection in alkaline solution, has a known 1:1 interference from another reactive nitrogen compound, acetyl peroxynitrate (PAN). Although PAN is thermally unstable, subsequent reactions with nitrogen dioxide (NO2) in effect extend the lifetime of PAN many times longer than the initial decomposition reaction would indicate. This, coupled with the rapid and efficient formation of PAN in WF plumes, means the NOx measurements reported by Chai et al.​​​​​​​ were severely impacted by PAN. In addition, the model reactions in the original paper included neither the reactions of NO2 with hydroxyl radical (OH) to form nitric acid nor the efficient reaction of larger organic radicals with nitric oxide to form organic nitrates (RONO2).

scholarly journals Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO<sub>2</sub>, total peroxy nitrate, total alkyl nitrate, and HNO<sub>3</sub>

2012 ◽  
Vol 5 (6) ◽  
pp. 8759-8787 ◽  
Author(s):  
P. Di Carlo ◽  
E. Aruffo ◽  
M. Busilacchio ◽  
F. Giammaria ◽  
C. Dari-Salisburgo ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Thermal Dissociation ◽  
Laser Induced Fluorescence ◽  
Organic Nitrates ◽  
Fast Time ◽  
Atmospheric Measurements ◽  
Inlet Channel ◽  
Enhanced Absorption ◽  
Simultaneous Measurements ◽  
Alkyl Nitrate

Abstract. A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (∑PNs), total alkyl nitrate (∑ANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations including: (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ∑PNs, ∑ANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO2 and used to fix the dissociation temperatures of each heated inlet, to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ∑PNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF.

Ectodesmata as Revealed By Freeze-Etch Preparations of Plant Epidermal Cell Walls

1973 ◽  
Vol 31 ◽  
pp. 468-469
Author(s):  
N.C. Lyon ◽  
W. C. Mueller
Keyword(s):  
Electron Microscopy ◽  
Acetic Acid ◽  
Nitric Acid ◽  
Oxalic Acid ◽  
Light Microscopy ◽  
Epidermal Cell ◽  
Cell Walls ◽  
Plant Viruses ◽  
Plant Leaves ◽  
Thin Sections

Schumacher and Halbsguth first demonstrated ectodesmata as pores or channels in the epidermal cell walls in haustoria of Cuscuta odorata L. by light microscopy in tissues fixed in a sublimate fixative (30% ethyl alcohol, 30 ml:glacial acetic acid, 10 ml: 65% nitric acid, 1 ml: 40% formaldehyde, 5 ml: oxalic acid, 2 g: mecuric chloride to saturation 2-3 g). Other workers have published electron micrographs of structures transversing the outer epidermal cell in thin sections of plant leaves that have been interpreted as ectodesmata. Such structures are evident following treatment with Hg++ or Ag+ salts and are only rarely observed by electron microscopy. If ectodesmata exist without such treatment, and are not artefacts, they would afford natural pathways of entry for applied foliar solutions and plant viruses.

The Action of Nitric Acid on Aluminium

1916 ◽  
Vol 82 (2122supp) ◽  
pp. 150-150
Author(s):  
R. Seligman ◽  
P. Williams
Keyword(s):  
Nitric Acid
Sign in / Sign up

Export Citation Format

Share Document