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Title: Characterization of oxidized coal surfaces: Quarterly report, May 1988--September 1988

Abstract

Laser mass spectra have been obtained of 2-fluoro-1-methylpyridinium (FMP) derivatized coal consistent with a prime objective of this research. This reagent, specific for the hydroxy functionality, produced major peaks at m/z 184 and 199 in the spectra of Pocahontas coal following derivatization. A gas phase reactor was built in order to enhance coal derivatization. Gas phase derivatization was accomplished on model compounds. Derivatization was carried out on Illinois No. 6 coal and analyzed with DRIFTS to determine the extent of derivatization. Oxidation indices of the oxidized coal decreased upon reacting with 2,4-dinitrophenylhydrazine, a derivatizing agent specific for carbonyl groups, confirming that the derivatization reaction had taken place. 5 refs., 5 figs.

Authors:
Publication Date:
Research Org.:
Pittsburgh Univ., PA (USA). Dept. of Chemistry
Sponsoring Org.:
USDOE
OSTI Identifier:
6315595
Report Number(s):
DOE/PC/90527-T7
ON: DE89012498
DOE Contract Number:
FG22-86PC90527
Resource Type:
Technical Report
Resource Relation:
Other Information: Portions of this document are illegible in microfiche products
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COAL; CHEMICAL REACTIONS; DERIVATIZATION; CHEMICAL REACTION YIELD; HYDRAZINE; MASS SPECTRA; OXIDATION; PHENOLS; PROGRESS REPORT; PYRIDINIUM COMPOUNDS; SPECTROSCOPY; SURFACES; AMINES; AMMONIUM COMPOUNDS; AROMATICS; AZINES; CARBONACEOUS MATERIALS; DOCUMENT TYPES; ENERGY SOURCES; FOSSIL FUELS; FUELS; HETEROCYCLIC COMPOUNDS; HYDROXY COMPOUNDS; MATERIALS; NITROGEN COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PYRIDINES; QUATERNARY COMPOUNDS; SPECTRA; YIELDS; 010600* - Coal, Lignite, & Peat- Properties & Composition; 400201 - Chemical & Physicochemical Properties

Citation Formats

Hercules, D. M. Characterization of oxidized coal surfaces: Quarterly report, May 1988--September 1988. United States: N. p., 1988. Web. doi:10.2172/6315595.
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Hercules, D. M. Characterization of oxidized coal surfaces: Quarterly report, May 1988--September 1988. United States. doi:10.2172/6315595.
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Hercules, D. M. Fri . "Characterization of oxidized coal surfaces: Quarterly report, May 1988--September 1988". United States. doi:10.2172/6315595. https://www.osti.gov/servlets/purl/6315595.
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@article{osti_6315595,
title = {Characterization of oxidized coal surfaces: Quarterly report, May 1988--September 1988},
author = {Hercules, D. M.},
abstractNote = {Laser mass spectra have been obtained of 2-fluoro-1-methylpyridinium (FMP) derivatized coal consistent with a prime objective of this research. This reagent, specific for the hydroxy functionality, produced major peaks at m/z 184 and 199 in the spectra of Pocahontas coal following derivatization. A gas phase reactor was built in order to enhance coal derivatization. Gas phase derivatization was accomplished on model compounds. Derivatization was carried out on Illinois No. 6 coal and analyzed with DRIFTS to determine the extent of derivatization. Oxidation indices of the oxidized coal decreased upon reacting with 2,4-dinitrophenylhydrazine, a derivatizing agent specific for carbonyl groups, confirming that the derivatization reaction had taken place. 5 refs., 5 figs.},
doi = {10.2172/6315595},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Jan 01 00:00:00 EST 1988},
month = {Fri Jan 01 00:00:00 EST 1988}
}
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Technical Report:
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DOI:  10.2172/6315595
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  • Work has progressed in the area of applying derivatization and analytical procedures developed for model compounds to oxidized coal samples. Both SIMS (Secondary Ion Mass Spectrometry) analysis have been pursued. Data obtained with TAB (4-triethylammonium-1-chloro-2-butene) derivatization is particularly encouraging. Coal samples have been oxidized in the reactor described in previous quarterly reports. The progress of the oxidation was monitored using Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy. DRIFT results confirmed that changes in oxygen functionality were occurring under the conditions and in the time frame of the reactor experiments. The potential of 2-fluoro-1-methyl pyridinium (FMP) as a derivatizing reagent formore » alcohols was also explored. Preliminary results show it to be useful. 7 refs., 4 figs.« less

  • Work has progressed in the areas of (1) exploration of derivatization reactions for ambient temperature in situ derivatization of phenols, alcohols, and acids on carbon surfaces, (2) analysis of the derivatives by secondary ion mass spectrometry (SIMS), (3) exploration of analysis of known mixtures on carbon surfaces, and (4) initial testing of the reactor for controlled oxidation of coal. Useful results have been obtained with three of the derivatizations. Girard's reagent for positive ion SIMS analysis and 2,4-dinitrophenylhydrazine for negative ion LMS analysis are informative for a wide range of carbonyl compounds. 4-triethylammonium-1-chloro-2-butene (TAB) is highly specific for phenolic compoundsmore » in positive ion SIMS analysis if the reaction is performed at high pH and for acids if the reaction is performed at low pH. Analysis on both metal foil and carbon sheets are successful. The use of the carbon support in SIMS analysis is somewhat advantageous in that a good spectrum is obtained, and potentially interfering silver ions are not present. On the basis of the above information, a specific plan for coal analysis has been formulated. The reactor for controlled oxidation of coal was slightly modified, and a sample of Illinois number 6 coal was weathered for 48 hours to test basic operation of the apparatus. 5 refs., 4 figs.« less

  • Work has progressed in the areas of (1) exploration or derivatization reactions for ambient temperature in-situ derivatization of aldehydes, ketones, and phenols on carbon surfaces; (2) analysis of these derivatives by secondary ion mass spectrometry (SIMS) and laser mass spectrometry (LMS); (3) derivatization and analysis of a naturally weathered coal; (4) construction of a reactor for controlled low temperature oxidation of coal; and (5) design of a protocol for handling coal samples. Specific derivatization reactions studied in this period included reactions of Girard's reagent, 2,4-dinitrophenylhydrazine and bisulfite with aldehydes and ketones and 4-triethylammonium-2-butene (TAB), trimethylsilyl ethers (TMS) and dimethylsilyl ethersmore » (DMS) with phenols and alcohols. Positive ion SIMS analysis of Girard's reagent derivatives and TAB derivatives on a silver support yielded molecular ion species (e.g., cations from the salts) for a wide range of carbonyl and phenolic compounds, respectively. Comparison of negative ion LMS spectra of naturally weathered Illinois No. 6 coal before and after treatment with 2,4-dinitrophenylhydrazine reveals the presence of two high mass ions in the spectrum of treated coal that are not present in the spectra of either the untreated coal or the derivatizing reagent. This provides both evidence for carbonyl functionality on the surface of naturally weathered Illinois No. 6 coal and support for the feasibility of in-situ derivatization and analysis of organic components in the coal matrix. 5 refs.« less

  • The work performed during this reporting period has focused primarily on defining derivatization reactions for initial investigation. The necessary reagents (Girard's Reagent P and NaHSO/sub 3/) and high purity charcoal were procured and the laser mass spectra (LMS) obtained. The LMS of the charcoal was obtained using a wide range of laser energy and focusing conditions. The information obtained will be applied in future work once the derivatization of model compounds on Zn foils and on charcoal commences. Paralleling the developments mentioned above were efforts in establishing a collaboration between Conoco (Pittsburgh, PA) and our research group. The collaboration ismore » expected to result in a mutually beneficial exchange of information regarding coal oxidation studies. 4 figs.« less

  • The work has focused on exploration of ambient temperature in-situ derivatization of aldehydes and ketones on carbon surfaces. 2,4-Dinitrophenylhydrazine, bisulfite, -ylium dichloro-iodate, and iminium perchlorate derivatizations were performed on a set of model aldehydes and ketones. Positive and negative ion laser mass spectra (LMS) of the 2,4-dinitrophenylhydrazine derivatives were obtained on zinic which is a common metal support used for LMS analysis. Although positive ion spectra were informative, negative ion spectra were more satisfactory as most compounds yielded molecular ion species in negative ion analysis. Spectra of selected preformed derivatives placed on charcoal and of benzaldehyde derivatized on charcoal weremore » also obtained. Molecular ion species that can be distinguished readily from carbon background ions were observed. Thus, the results established that in-situ derivatization followed by analysis is indeed possible. 3 refs., 8 figs.« less