{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21567"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21567","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"I. An oxygen-17 NMR study on oxygen exchange in yttrium barium(2) copper(3) oxygen(7-x). II. Synthesis of transition metal polysulfide complexes from metal powders","abstract":"Covellite, $\\rm Cu\\sp{I}\\sb2(S\\sb2)Cu\\sp{II}S$ (T$\\sb{\\rm c}$ = 1.66 K) and $\\rm YBa\\sb2Cu\\sp{II}\\sb2Cu\\sp{III}O\\sb{7-x}\\ (T\\sb{c}$ = 92 K) are similar in that both are superconductors containing layered structures and mixed valent copper centers. Our studies on YBa$\\sb2$Cu$\\sb3$O$\\sb{\\rm 7-x}$ focused on $\\sp{17}$O-labelling of samples of $\\rm YBa\\sb2 Cu\\sb3 O\\sb{7-x}$ and the $\\sp{17}$O NMR studies of these samples. The $\\sp{17}$O-labelling process was carried out using a specially designed glass apparatus. Powder X-ray diffraction and magnetic susceptibility measurements showed that our samples were highly pure. $\\sp{17}$O NMR spectroscopy showed that we were able to prepare samples which have uniform and non-uniform distribution of $\\sp{17}$O atoms.","abstract_html":"Covellite, $\\rm Cu\\sp{I}\\sb2(S\\sb2)Cu\\sp{II}S$ (T$\\sb{\\rm c}$ = 1.66 K) and <span class=\"etd-inline-math\">\\rm YBa\\sb2Cu\\sp{II}\\sb2Cu\\sp{III}O\\sb{7-x} (T\\sb{c}</span> = 92 K) are similar in that both are superconductors containing layered structures and mixed valent copper centers. Our studies on YBa$\\sb2$Cu$\\sb3$O$\\sb{\\rm 7-x}$ focused on $\\sp{17}$O-labelling of samples of $\\rm YBa\\sb2 Cu\\sb3 O\\sb{7-x}$ and the $\\sp{17}$O NMR studies of these samples. The $\\sp{17}$O-labelling process was carried out using a specially designed glass apparatus. Powder X-ray diffraction and magnetic susceptibility measurements showed that our samples were highly pure. $\\sp{17}$O NMR spectroscopy showed that we were able to prepare samples which have uniform and non-uniform distribution of $\\sp{17}$O atoms.","abstract_has_math":true,"creators":["Ramli, Emannuel"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Rauchfuss, Thomas B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:12:27Z","date_published":"2011-05-07T13:12:27Z","updated_at":"2026-07-22T22:25:18Z","subjects":["Chemistry, Inorganic"],"languages":["eng"],"rights":["Copyright 1991 Ramli, Emannuel"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9124471","(UMI)AAI9124471"],"render_values":[{"text":"AAI9124471","href":null,"code":true},{"text":"(UMI)AAI9124471","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21567","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Rauchfuss, Thomas B."]},{"key":"dc:creator","label":"Author","values":["Ramli, Emannuel"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:12:27Z","10000-01-01","1991"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Inorganic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Ramli, Emannuel"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9124471","(UMI)AAI9124471","http://hdl.handle.net/2142/21567"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Covellite, $\\rm Cu\\sp{I}\\sb2(S\\sb2)Cu\\sp{II}S$ (T$\\sb{\\rm c}$ = 1.66 K) and $\\rm YBa\\sb2Cu\\sp{II}\\sb2Cu\\sp{III}O\\sb{7-x}\\ (T\\sb{c}$ = 92 K) are similar in that both are superconductors containing layered structures and mixed valent copper centers. Our studies on YBa$\\sb2$Cu$\\sb3$O$\\sb{\\rm 7-x}$ focused on $\\sp{17}$O-labelling of samples of $\\rm YBa\\sb2 Cu\\sb3 O\\sb{7-x}$ and the $\\sp{17}$O NMR studies of these samples. The $\\sp{17}$O-labelling process was carried out using a specially designed glass apparatus. Powder X-ray diffraction and magnetic susceptibility measurements showed that our samples were highly pure. $\\sp{17}$O NMR spectroscopy showed that we were able to prepare samples which have uniform and non-uniform distribution of $\\sp{17}$O atoms.","Our work on covellite began with studies of its synthesis at low temperatures. This work led to the discovery of a low temperature route to metal sulfides. We initially prepared covellite by the reaction of a suspension of copper metal and elemental sulfur in refluxing pyridine. When the same reaction was conducted at room temperature we obtained amorphous CuS and (Cu(S$\\sb5$)$\\sb2$(pyridine)) $\\sb4$. (Cu(S$\\sb5)\\sb2$(pyridine)) $\\sb4$ was shown to be a molecular intermediate in the formation of covellite from its elements. Subsequently it was found that the reaction between copper and sulfur is particularly rapid in N-methylimidazole, affording (Cu(S$\\sb5$)$\\sb2$(N-MeIm)) $\\sb4$ in 50% yield.","Other first row transition metals which react with S$\\sb8$ in N-methylimidazole at room temperature include manganese, iron and nickel. The product in all of these cases is (M(N-MeIm)$\\sb6$) S$\\sb8$ (M = Mn, Fe, Ni). (M(N-MeIm)$\\sb6$) S$\\sb8$ provides the first evidence for S$\\sb8\\sp{2-}$ anion, the product of the 2 e$\\sp-$ reduction of S$\\sb8$.","Zinc metal reacts with S$\\sb8$ in N-methylimidazole at 90$\\sp\\circ$C to form (ZnS(N-MeIm)) $\\sb{\\rm n}$ when Zn: S = 1: 1 and ZnS$\\sb6$(N-MeIm)$\\sb2$ when Zn: S = 1: 6. The two compounds are interconvertible via addition of elemental sulfur or zinc.","Made available in DSpace on 2011-05-07T13:12:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9124471.pdf: 4206704 bytes, checksum: d329bdcc387dfc8044df107cdd7edb7a (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:51:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:44-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["I. An oxygen-17 NMR study on oxygen exchange in yttrium barium(2) copper(3) oxygen(7-x). II. Synthesis of transition metal polysulfide complexes from metal powders"]}]}],"canonical_facts":{"dc:contributor":["Rauchfuss, Thomas B."],"dc:creator":["Ramli, Emannuel"],"dc:date":["2011-05-07T13:12:27Z","10000-01-01","1991"],"dc:description":["Covellite, $\\rm Cu\\sp{I}\\sb2(S\\sb2)Cu\\sp{II}S$ (T$\\sb{\\rm c}$ = 1.66 K) and $\\rm YBa\\sb2Cu\\sp{II}\\sb2Cu\\sp{III}O\\sb{7-x}\\ (T\\sb{c}$ = 92 K) are similar in that both are superconductors containing layered structures and mixed valent copper centers. Our studies on YBa$\\sb2$Cu$\\sb3$O$\\sb{\\rm 7-x}$ focused on $\\sp{17}$O-labelling of samples of $\\rm YBa\\sb2 Cu\\sb3 O\\sb{7-x}$ and the $\\sp{17}$O NMR studies of these samples. The $\\sp{17}$O-labelling process was carried out using a specially designed glass apparatus. Powder X-ray diffraction and magnetic susceptibility measurements showed that our samples were highly pure. $\\sp{17}$O NMR spectroscopy showed that we were able to prepare samples which have uniform and non-uniform distribution of $\\sp{17}$O atoms.","Our work on covellite began with studies of its synthesis at low temperatures. This work led to the discovery of a low temperature route to metal sulfides. We initially prepared covellite by the reaction of a suspension of copper metal and elemental sulfur in refluxing pyridine. When the same reaction was conducted at room temperature we obtained amorphous CuS and (Cu(S$\\sb5$)$\\sb2$(pyridine)) $\\sb4$. (Cu(S$\\sb5)\\sb2$(pyridine)) $\\sb4$ was shown to be a molecular intermediate in the formation of covellite from its elements. Subsequently it was found that the reaction between copper and sulfur is particularly rapid in N-methylimidazole, affording (Cu(S$\\sb5$)$\\sb2$(N-MeIm)) $\\sb4$ in 50% yield.","Other first row transition metals which react with S$\\sb8$ in N-methylimidazole at room temperature include manganese, iron and nickel. The product in all of these cases is (M(N-MeIm)$\\sb6$) S$\\sb8$ (M = Mn, Fe, Ni). (M(N-MeIm)$\\sb6$) S$\\sb8$ provides the first evidence for S$\\sb8\\sp{2-}$ anion, the product of the 2 e$\\sp-$ reduction of S$\\sb8$.","Zinc metal reacts with S$\\sb8$ in N-methylimidazole at 90$\\sp\\circ$C to form (ZnS(N-MeIm)) $\\sb{\\rm n}$ when Zn: S = 1: 1 and ZnS$\\sb6$(N-MeIm)$\\sb2$ when Zn: S = 1: 6. The two compounds are interconvertible via addition of elemental sulfur or zinc.","Made available in DSpace on 2011-05-07T13:12:27Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9124471.pdf: 4206704 bytes, checksum: d329bdcc387dfc8044df107cdd7edb7a (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:51:39Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:23:44-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9124471","(UMI)AAI9124471","http://hdl.handle.net/2142/21567"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Ramli, Emannuel"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["I. An oxygen-17 NMR study on oxygen exchange in yttrium barium(2) copper(3) oxygen(7-x). II. Synthesis of transition metal polysulfide complexes from metal powders"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:18Z"}