{"id":{"repo_id":"lsu-thes","oai_identifier":"oai:repository.lsu.edu:gradschool_dissertations-1380"},"canonical_url":"https://search.dev.ndltd.org/etd/lsu-thes/oai:repository.lsu.edu:gradschool_dissertations-1380","repository":{"repo_id":"lsu-thes","name":"Lousiana State University","base_url":"https://repository.lsu.edu/do/oai/"},"display":{"title":"Iron (III) Oxide and Copper (II) Oxide Mediated Formation of PCDD/Fs from Thermal Degradation of 2-MCP and 1,2-DCBz","abstract":"Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) which occurs inexorably from most thermal and combustion processes constitutes a major toxic component of environmental pollutants. Generally, it is well established that transition metal-mediated reactions account for the majority of PCDD/F emissions from combustion sources. Specifically, both copper and iron ions, which occur abundantly in combustion generated particulate matter, are considered probably the most active in promoting PCDD/F formation typically in the low temperature post-combustion zone and flue gas pollution control devices. It has also been demonstrated that chlorinated phenols are key intermediates in essentially all pathways of PCDD/F formation. Chlorinated benzenes have been presumed to be potent precursors that form PCDD/Fs and are among the most abundant aromatic compounds in incinerator exhaust. Notably, numerous studies have been reported in regard to surface-mediated processes of PCDD/F formation via de novo synthesis and transition metal-mediated processes from reactions of chlorinated phenols. However, few experimental studies have been conducted on chlorinated benzenes. In addition, even though iron oxide is present at 2-50 times higher concentrations than copper oxide, virtually no studies of the iron oxide mediated formation of PCDD/Fs have been reported in the literature. For this study, PCDD/F formation over iron oxide and copper oxide surfaces were investigated using the reactants 2-MCP and 1,2-DCBz in pure and mixture form. The surface-mediated reactions were studied under pyrolytic and oxidative conditions over a temperature range of 200 to 550 oC. For the entire study, simplified model surfaces of 5% copper (II) oxide on silica and 5% iron (III) oxide on silica were used in order to facilitate comparison with previous data from similar experiments performed with pure samples of 2-MCP and 1,2-DCBz. Precursor 2-MCP is useful as a model chlorinated phenol, while 1,2-DCBz was selected because it has been found to be present in high concentration in relation to other congeners of polychlorinated benzenes in combustion exhaust and is nearly isoeletronic with 2-MCP, that provides a basis for comparison of product distributions and yields. Reaction pathways of PCDD/F products as well as the intermediates involved are comprehensively analyzed and discussed.","abstract_html":"Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) which occurs inexorably from most thermal and combustion processes constitutes a major toxic component of environmental pollutants. Generally, it is well established that transition metal-mediated reactions account for the majority of PCDD/F emissions from combustion sources. Specifically, both copper and iron ions, which occur abundantly in combustion generated particulate matter, are considered probably the most active in promoting PCDD/F formation typically in the low temperature post-combustion zone and flue gas pollution control devices. It has also been demonstrated that chlorinated phenols are key intermediates in essentially all pathways of PCDD/F formation. Chlorinated benzenes have been presumed to be potent precursors that form PCDD/Fs and are among the most abundant aromatic compounds in incinerator exhaust. Notably, numerous studies have been reported in regard to surface-mediated processes of PCDD/F formation via de novo synthesis and transition metal-mediated processes from reactions of chlorinated phenols. However, few experimental studies have been conducted on chlorinated benzenes. In addition, even though iron oxide is present at 2-50 times higher concentrations than copper oxide, virtually no studies of the iron oxide mediated formation of PCDD/Fs have been reported in the literature. For this study, PCDD/F formation over iron oxide and copper oxide surfaces were investigated using the reactants 2-MCP and 1,2-DCBz in pure and mixture form. The surface-mediated reactions were studied under pyrolytic and oxidative conditions over a temperature range of 200 to 550 oC. For the entire study, simplified model surfaces of 5% copper (II) oxide on silica and 5% iron (III) oxide on silica were used in order to facilitate comparison with previous data from similar experiments performed with pure samples of 2-MCP and 1,2-DCBz. Precursor 2-MCP is useful as a model chlorinated phenol, while 1,2-DCBz was selected because it has been found to be present in high concentration in relation to other congeners of polychlorinated benzenes in combustion exhaust and is nearly isoeletronic with 2-MCP, that provides a basis for comparison of product distributions and yields. Reaction pathways of PCDD/F products as well as the intermediates involved are comprehensively analyzed and discussed.","abstract_has_math":false,"creators":["Nganai, Shadrack Kirwa"],"institution":"Chemistry","degree_name":"Doctor of Philosophy (PhD)","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010-01-01T08:00:00Z","date_published":"2010-01-01T08:00:00Z","updated_at":"2026-07-24T02:57:30Z","subjects":["PCDD/Fs","Thermal Degradation"],"languages":[],"rights":["unrestricted","Release the entire work immediately for access worldwide."],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["etd-09182010-105119","https://repository.lsu.edu/gradschool_dissertations/381"],"render_values":[{"text":"etd-09182010-105119","href":null,"code":true},{"text":"https://repository.lsu.edu/gradschool_dissertations/381","href":"https://repository.lsu.edu/gradschool_dissertations/381","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.31390/gradschool_dissertations.381","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Nganai, Shadrack Kirwa"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010-08-26"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2022-05-12T23:08:37Z"]},{"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":["Doctor of Philosophy (PhD)"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Chemistry"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["PCDD/Fs","Thermal Degradation"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["unrestricted","Release the entire work immediately for access worldwide."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["etd-09182010-105119","10.31390/gradschool_dissertations.381","https://repository.lsu.edu/gradschool_dissertations/381"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) which occurs inexorably from most thermal and combustion processes constitutes a major toxic component of environmental pollutants. Generally, it is well established that transition metal-mediated reactions account for the majority of PCDD/F emissions from combustion sources. Specifically, both copper and iron ions, which occur abundantly in combustion generated particulate matter, are considered probably the most active in promoting PCDD/F formation typically in the low temperature post-combustion zone and flue gas pollution control devices. It has also been demonstrated that chlorinated phenols are key intermediates in essentially all pathways of PCDD/F formation. Chlorinated benzenes have been presumed to be potent precursors that form PCDD/Fs and are among the most abundant aromatic compounds in incinerator exhaust. Notably, numerous studies have been reported in regard to surface-mediated processes of PCDD/F formation via de novo synthesis and transition metal-mediated processes from reactions of chlorinated phenols. However, few experimental studies have been conducted on chlorinated benzenes. In addition, even though iron oxide is present at 2-50 times higher concentrations than copper oxide, virtually no studies of the iron oxide mediated formation of PCDD/Fs have been reported in the literature. For this study, PCDD/F formation over iron oxide and copper oxide surfaces were investigated using the reactants 2-MCP and 1,2-DCBz in pure and mixture form. The surface-mediated reactions were studied under pyrolytic and oxidative conditions over a temperature range of 200 to 550 oC. For the entire study, simplified model surfaces of 5% copper (II) oxide on silica and 5% iron (III) oxide on silica were used in order to facilitate comparison with previous data from similar experiments performed with pure samples of 2-MCP and 1,2-DCBz. Precursor 2-MCP is useful as a model chlorinated phenol, while 1,2-DCBz was selected because it has been found to be present in high concentration in relation to other congeners of polychlorinated benzenes in combustion exhaust and is nearly isoeletronic with 2-MCP, that provides a basis for comparison of product distributions and yields. Reaction pathways of PCDD/F products as well as the intermediates involved are comprehensively analyzed and discussed."]},{"key":"dc:title","label":"Title","values":["Iron (III) Oxide and Copper (II) Oxide Mediated Formation of PCDD/Fs from Thermal Degradation of 2-MCP and 1,2-DCBz"]}]}],"canonical_facts":{"dc:creator":["Nganai, Shadrack Kirwa"],"dc:date":["2010-08-26"],"dc:date.available":["2022-05-12T23:08:37Z"],"dc:description.abstract":["Formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) which occurs inexorably from most thermal and combustion processes constitutes a major toxic component of environmental pollutants. Generally, it is well established that transition metal-mediated reactions account for the majority of PCDD/F emissions from combustion sources. Specifically, both copper and iron ions, which occur abundantly in combustion generated particulate matter, are considered probably the most active in promoting PCDD/F formation typically in the low temperature post-combustion zone and flue gas pollution control devices. It has also been demonstrated that chlorinated phenols are key intermediates in essentially all pathways of PCDD/F formation. Chlorinated benzenes have been presumed to be potent precursors that form PCDD/Fs and are among the most abundant aromatic compounds in incinerator exhaust. Notably, numerous studies have been reported in regard to surface-mediated processes of PCDD/F formation via de novo synthesis and transition metal-mediated processes from reactions of chlorinated phenols. However, few experimental studies have been conducted on chlorinated benzenes. In addition, even though iron oxide is present at 2-50 times higher concentrations than copper oxide, virtually no studies of the iron oxide mediated formation of PCDD/Fs have been reported in the literature. For this study, PCDD/F formation over iron oxide and copper oxide surfaces were investigated using the reactants 2-MCP and 1,2-DCBz in pure and mixture form. The surface-mediated reactions were studied under pyrolytic and oxidative conditions over a temperature range of 200 to 550 oC. For the entire study, simplified model surfaces of 5% copper (II) oxide on silica and 5% iron (III) oxide on silica were used in order to facilitate comparison with previous data from similar experiments performed with pure samples of 2-MCP and 1,2-DCBz. Precursor 2-MCP is useful as a model chlorinated phenol, while 1,2-DCBz was selected because it has been found to be present in high concentration in relation to other congeners of polychlorinated benzenes in combustion exhaust and is nearly isoeletronic with 2-MCP, that provides a basis for comparison of product distributions and yields. Reaction pathways of PCDD/F products as well as the intermediates involved are comprehensively analyzed and discussed."],"dc:identifier":["etd-09182010-105119","10.31390/gradschool_dissertations.381","https://repository.lsu.edu/gradschool_dissertations/381"],"dc:rights":["unrestricted","Release the entire work immediately for access worldwide."],"dc:subject":["PCDD/Fs","Thermal Degradation"],"dc:title":["Iron (III) Oxide and Copper (II) Oxide Mediated Formation of PCDD/Fs from Thermal Degradation of 2-MCP and 1,2-DCBz"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy (PhD)"],"thesis:institution_name":["Chemistry"]},"updated_at":"2026-07-24T02:57:30Z"}