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Title: Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate]

Abstract

Task 1: methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2: methods development for the speciation of dithionite and polythionates. Electrochemical reduction of tetrathionate and pentathionate at the dropping mercury electrode (DME) proceeds through a mechanism involving specific adsorption of the reactant at the DME surface and yielding polarographic waves at -0.2 volt (versus the saturated calomel electrode) in aqueous solution. Ethanol interferes with the specific adsorption of tetrathionate and pentathionate in a range of potentials between 0.0 and -1.1 volt, because EtOH is preferentially adsorbed. This results in a shift of the polarographic half-wave potentials of tetrathionate and pentathionate, which facilitates their determination in polythionate mixtures. On the other hand, the polarographic reduction of trithionate is unaffected by ethanol, because it occurs at -1.5 volt where ethanol is not adsorbed at the surface of the DME. Task 3: total accounting of the sulfur balance in representative samples of synfuel process streams. Analyses of two aqueous gasifier effluents from Grand Forks, ND, were performed. An untreated specimen contained sulfidic and polysulfidic sulfur, thiosulfate and thiocyanate. On the other hand, sulfite, sulfate, and thiocyanate weremore » the only sulfur moieties observed in the Grand Forks sample which had been stripped at PETC. 7 references, 1 figure, 3 tables.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park (USA). Dept. of Chemistry
OSTI Identifier:
6659721
Alternate Identifier(s):
OSTI ID: 6659721; Legacy ID: DE84015882
Report Number(s):
DOE/PC/40783-T15
ON: DE84015882
DOE Contract Number:
FG22-81PC40783
Resource Type:
Technical Report
Resource Relation:
Other Information: Portions are illegible in microfiche products. Original copy available until stock is exhausted
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COAL LIQUEFACTION; PROCESS SOLUTIONS; WASTE WATER; CHEMICAL ANALYSIS; SULFUR; POLAROGRAPHY; SULFUR COMPOUNDS; QUANTITATIVE CHEMICAL ANALYSIS; EXPERIMENTAL DATA; RESEARCH PROGRAMS; DATA; DISPERSIONS; ELEMENTS; HYDROGEN COMPOUNDS; INFORMATION; LIQUEFACTION; LIQUID WASTES; MIXTURES; NONMETALS; NUMERICAL DATA; OXYGEN COMPOUNDS; SOLUTIONS; THERMOCHEMICAL PROCESSES; WASTES; WATER 010600* -- Coal, Lignite, & Peat-- Properties & Composition; 400102 -- Chemical & Spectral Procedures

Citation Formats

Jordan, J., Sexton, E., Talbott, J., and Yakupkovic, J.. Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate]. United States: N. p., 1984. Web. doi:10.2172/6659721.
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Jordan, J., Sexton, E., Talbott, J., & Yakupkovic, J.. Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate]. United States. doi:10.2172/6659721.
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Jordan, J., Sexton, E., Talbott, J., and Yakupkovic, J.. Sun . "Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate]". United States. doi:10.2172/6659721. https://www.osti.gov/servlets/purl/6659721.
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@article{osti_6659721,
title = {Instrumental methods of analysis of sulfur compounds in synfuel process streams. Quarterly technical progress report for April-June 1984. [Sulfidic, polysulfidic, thiosulfate, sulfite, sulfate, thiocyanate]},
author = {Jordan, J. and Sexton, E. and Talbott, J. and Yakupkovic, J.},
abstractNote = {Task 1: methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2: methods development for the speciation of dithionite and polythionates. Electrochemical reduction of tetrathionate and pentathionate at the dropping mercury electrode (DME) proceeds through a mechanism involving specific adsorption of the reactant at the DME surface and yielding polarographic waves at -0.2 volt (versus the saturated calomel electrode) in aqueous solution. Ethanol interferes with the specific adsorption of tetrathionate and pentathionate in a range of potentials between 0.0 and -1.1 volt, because EtOH is preferentially adsorbed. This results in a shift of the polarographic half-wave potentials of tetrathionate and pentathionate, which facilitates their determination in polythionate mixtures. On the other hand, the polarographic reduction of trithionate is unaffected by ethanol, because it occurs at -1.5 volt where ethanol is not adsorbed at the surface of the DME. Task 3: total accounting of the sulfur balance in representative samples of synfuel process streams. Analyses of two aqueous gasifier effluents from Grand Forks, ND, were performed. An untreated specimen contained sulfidic and polysulfidic sulfur, thiosulfate and thiocyanate. On the other hand, sulfite, sulfate, and thiocyanate were the only sulfur moieties observed in the Grand Forks sample which had been stripped at PETC. 7 references, 1 figure, 3 tables.},
doi = {10.2172/6659721},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Jul 01 00:00:00 EDT 1984},
month = {Sun Jul 01 00:00:00 EDT 1984}
}
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DOI:  10.2172/6659721
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  • ; ;
    Task 1. The thermodynamics of competing reactions, which may interfere with the thermometric titration of polysulfides (with the reagent p-hydroxymercuribenzoate), were investigated. The crucial property is nucleophilic character (Lewis basicity) for which log K of the displacement of OH/sup -/ from HMB provides a convenient quantitative measure. The following sequence was found to prevail: S/sup =/ > CN/sup -/ > S/sub 2/O/sub 3//sup =/ > OH/sup -/ = O > I/sup -/ > SO/sub 3//sup =/ > NH/sub 3/ congruent to SCN/sup -/. Task 2. Trithionate, tetrathionate, pentathionate, and hexathionate yield well defined polarographic electroreduction waves at the dropping mercurymore » electrode. Furthermore, tetrathionate, pentathionate and hexathionate were found to be electrooxidizable at glassy carbon anodes, while trithionate was not. Task 3. Inquiries have been sent to industrial, government, and academic organizations, soliciting appropriate specimens. Responses have been received from thirteen individuals, who have access to diverse samples in various locations, ranging from Washington and Oregon and California to New York, Delaware, and the Carolinas. A nitrogen dry-box facility has been readied for storing samples. A five-step protocol has been formulated for speciating and quantitating the major and minor moieties which contribute to the total sulfur content.« less

  • ; ; ; ...
    Task 1: Methods Development for the Speciation of Polysulfides. The contributions of this project in fundamental thermochemistry and thermodynamics of Lewis acid-base reactions are reviewed and summarized. The use of the reagent p-hydroxymercuribenzoate, p-HMB (/sup -/OOC phi Hg-OH), as a preferred analytical reagent for polysulfides is warranted on considerations of specificity, selectivity, and its monovalent coordination number. p-HMB is a Lewis acid-base adduct. The Lewis acidity of /sup -/OOC phi Hg/sup +/ measured as log K of a reaction with a given Lewis base was found to be 15% greater than that of the classical Lewis acid H/sub 3/CHg/sup +/.more » Task 2: Methods Development for the Speciation of Dithionite and Polythionates. A new electroanalytical method has been developed for the speciation of trithionate, tetrathionate, and pentathionate. Five well-resolved differential pulse polarographic peaks were obtained at the dropping mercury electrode in a mixed solvent (60% water, 40% ethanol) containing trithionate, tetrathionate, and pentathionate at comparable concentration levels. Two peaks were accounted for by the electroreduction of trithionate and tetrathionate, respectively. Pentathionate yielded three peaks. Trithionate, tetrathionate and pentathionate concentrations were linearly correlated to selected differential peak currents. Task 3: Total Accounting of the Sulfur Balance in Representative Samples of Synfuel Process Streams. Analyses of two aqueous specimens, a gasification effluent from Grand Forks, ND, and an H-Coal liquefaction process effluent were carried out. The liquefaction effluent contained predominantly hydrogen sulfide and no thiosulfate. A variety of sulfur species were observed in the gasification effluent, including thiocyanate. 9 references, 11 figures, 5 tables.« less

  • ; ; ; ...
    Task 1. Methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2. Methods development for the speciation of dithionite and polythionates. Work is in progress on the polarography of the polythionates. Results will be presented in a forthcoming Quarterly Report. Task 3. Total accounting of the sulfur balance in representative samples of synfuel process streams. Two aqueous samples emanating from different stages of the Lummus Process were analyzed. As expected, total sulfur content was low, viz., 0.006 M and 0.001 M. Concentrations of sulfidic sulfur,more » polysulfidic sulfur, thiosulfate, sulfite, trithionate, tetrathionate, and pentathionate were less than 0.001 M each. 5 references, 3 tables.« less

  • ;
    Task 1. Methods development for the speciation of the polysulfides. Work on this task has been completed in December 1983 and reported accordingly in DOE/PC/40783-T13. Task 2. Methods development for the speciation of dithionite and polythionates. Work on Task 2 has been completed in June 1984 and has been reported accordingly in DOE/PC/40783-T15. Task 3. Total accounting of the sulfur balance in representative samples of synfuel process streams. A systematic and critical comparison of results, obtained in the analysis of sulfur moieties in representative samples of coal conversion process streams, revealed the following general trends. (a) In specimens of highmore » pH (9-10) and low redox potential (-0.3 to -0.4 volt versus NHE) sulfidic and polysulfidic sulfur moieties predominate. (b) In process streams of lower pH and more positive redox potential, higher oxidation states of sulfur (notably sulfate) account for most of the total sulfur present. (c) Oxidative wastewater treatment procedures by the PETC stripping process convert lower oxidation states of sulfur into thiosulfate and sulfate. In this context, remarkable similarities were observed between liquefaction and gasification process streams. However, the thiocyanate present in samples from the Grand Forks gasifier were impervious to the PETC stripping process. (d) Total sulfur contaminant levels in coal conversion process stream wastewater samples are primarily determined by the abundance of sulfur in the coal used as starting material than by the nature of the conversion process (liquefaction or gasification). 13 references.« less

  • Full implementation of an algorithm for calculating thermodynamic estimates of sulfur moiety concentrations is reported. The scope of the algorithm is unrestricted, including mononuclear and polynuclear sulfur species. Implementation is achieved through the use of substantiated numerical approximation. In Voltammetric Method Development, equations describing the analytic geometry of differential pulse voltammograms are reviewed critically. Work on appropriate refinements has been initiated. The analysis of mixtures of Bronsted-base moieties (OH/sup -/, CO/sub 3//sup =/, SO/sub 3//sup =/ S/sup =/, SO/sub 4//sup =/, S/sub 2/O/sub 3//sup =/) by simultaneous thermometric and potentiometric (pH) titration with a strong acid has been explored. Sulfidemore » or sulfite can be determined in the presence of hydroxide and carbonate with an accuracy of 4%, with the aid of simultaneous thermometric and potentiometric titrations. Sulfide in concentrations as high as 67% and thiosulfate in concentrations as high as 3.9% have been successfully determined in by-product waters from liquefaction and gasification processes by differential pulse polarography at a dropping mercury electrode. The samples were remarkable in that the concentration of sulfite is less than 12 ppM in all cases.« less