{"id":{"repo_id":"njit","oai_identifier":"oai:digitalcommons.njit.edu:theses-1304"},"canonical_url":"https://search.dev.ndltd.org/etd/njit/oai:digitalcommons.njit.edu:theses-1304","repository":{"repo_id":"njit","name":"NJIT","base_url":"https://digitalcommons.njit.edu/do/oai/"},"display":{"title":"Thermochemistry and bond energies of nitro -alkanes, -alkenes, -carbonyls and corresponding nitrites","abstract":"Density functional and ab initio theory based calculations were performed on a series of nitro -alkanes, -alkenes, carbonyl and corresponding nitrites representing large-scale primary, secondary and tertiary nitro compounds and their radicals resulting from the loss of skeletal hydrogen atoms. Geometries, vibration frequencies and thermochemical properties, [Delta]fH _{298}, S (T) and C p(T) (10K T 5 5000K) are calculated at the individual B3LYP/6-31G(d,p), B3LYP /6-31+G(2d,2p) and composite CBS-QB3 levels. Potential energy barriers for the internal rotations have been computed at the B3LYP/6-31G(d, p) level of theory and the lower barrier contributions are incorporated into entropy and heat capacity data. The standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Recommended values derived from the most stable conformers of respective nitro- and nitrite isomers include: -30.6 and -28.4 kcal moil for n-propane-, -33.9 and -32.3 kcal mol^{-1} for iso-propane-, -42.8 and -41.4 kcal mol^{-1} for tert-butane-nitro compounds and nitrites, respectively. Entropy and heat capacity values are also reported for the lower homologues: nitromethane, nitroethane and corresponding nitrites. C--H bond energies are decreased by ~ 5 kcal moil alpha to the nitro or nitrite groups and increased by ~ 0.5 kcal moil beta to the nitro and nitrite groups. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone, acetonitrite, nitroacetate and acetyl nitrite are -51.6 kcal mol^{-1}, -51.26 kcal mol^{-1}, -45.4 kcal mol^{-1} and -58.2 kcal mol^{-1}, respectively. The calculated [Delta]fH _{298} for nitroethylene is 7.6 kcal mol^{-1} and for vinyl nitrite is 7.2 kcal mol^{-1}. The carbonyl and olefin groups retain the major influence on the C-H bond energies. Radicals on carbon adjacent to a nitrite (RC.ONO) group do not exist; they dissociate to the corresponding carbonyl (RC=O + NO) with 38 kcal mol^{-1} exothermic and no apparent barrier. This results from formation of the strong carbonyl (it bond ~ 80 kcal mol^{-1}) with dissociation of the weak RO--NO bond (-43 kcal mol^{-1}).","abstract_html":"Density functional and ab initio theory based calculations were performed on a series of nitro -alkanes, -alkenes, carbonyl and corresponding nitrites representing large-scale primary, secondary and tertiary nitro compounds and their radicals resulting from the loss of skeletal hydrogen atoms. Geometries, vibration frequencies and thermochemical properties, [Delta]fH _{298}, S (T) and C p(T) (10K T 5 5000K) are calculated at the individual B3LYP/6-31G(d,p), B3LYP /6-31+G(2d,2p) and composite CBS-QB3 levels. Potential energy barriers for the internal rotations have been computed at the B3LYP/6-31G(d, p) level of theory and the lower barrier contributions are incorporated into entropy and heat capacity data. The standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Recommended values derived from the most stable conformers of respective nitro- and nitrite isomers include: -30.6 and -28.4 kcal moil for n-propane-, -33.9 and -32.3 kcal mol^{-1} for iso-propane-, -42.8 and -41.4 kcal mol^{-1} for tert-butane-nitro compounds and nitrites, respectively. Entropy and heat capacity values are also reported for the lower homologues: nitromethane, nitroethane and corresponding nitrites. C--H bond energies are decreased by ~ 5 kcal moil alpha to the nitro or nitrite groups and increased by ~ 0.5 kcal moil beta to the nitro and nitrite groups. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone, acetonitrite, nitroacetate and acetyl nitrite are -51.6 kcal mol^{-1}, -51.26 kcal mol^{-1}, -45.4 kcal mol^{-1} and -58.2 kcal mol^{-1}, respectively. The calculated [Delta]fH _{298} for nitroethylene is 7.6 kcal mol^{-1} and for vinyl nitrite is 7.2 kcal mol^{-1}. The carbonyl and olefin groups retain the major influence on the C-H bond energies. Radicals on carbon adjacent to a nitrite (RC.ONO) group do not exist; they dissociate to the corresponding carbonyl (RC=O + NO) with 38 kcal mol^{-1} exothermic and no apparent barrier. This results from formation of the strong carbonyl (it bond ~ 80 kcal mol^{-1}) with dissociation of the weak RO--NO bond (-43 kcal mol^{-1}).","abstract_has_math":false,"creators":["Snitsiriwat, Surawee"],"institution":null,"degree_name":"Master of Science in Environmental Science - (M.S.)","degree_level":null,"degree_discipline":"Chemistry and Environmental Science","degree_department":null,"school":null,"contributors":["Joseph W. Bozzelli","Carol A. Venanzi","Tamara M. Gund"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-01-31T08:00:00Z","date_published":"2009-01-31T08:00:00Z","updated_at":"2026-07-24T03:23:16Z","subjects":["Thermochemistry","Bond energy","Environmental Sciences"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://digitalcommons.njit.edu/theses/305","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Joseph W. Bozzelli","Carol A. Venanzi","Tamara M. Gund"]},{"key":"dc:creator","label":"Author","values":["Snitsiriwat, Surawee"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry and Environmental Science"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science in Environmental Science - (M.S.)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Thermochemistry","Bond energy","Environmental Sciences"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://digitalcommons.njit.edu/theses/305"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Density functional and ab initio theory based calculations were performed on a series of nitro -alkanes, -alkenes, carbonyl and corresponding nitrites representing large-scale primary, secondary and tertiary nitro compounds and their radicals resulting from the loss of skeletal hydrogen atoms. Geometries, vibration frequencies and thermochemical properties, [Delta]fH _{298}, S (T) and C p(T) (10K T 5 5000K) are calculated at the individual B3LYP/6-31G(d,p), B3LYP /6-31+G(2d,2p) and composite CBS-QB3 levels. Potential energy barriers for the internal rotations have been computed at the B3LYP/6-31G(d, p) level of theory and the lower barrier contributions are incorporated into entropy and heat capacity data. The standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Recommended values derived from the most stable conformers of respective nitro- and nitrite isomers include: -30.6 and -28.4 kcal moil for n-propane-, -33.9 and -32.3 kcal mol^{-1} for iso-propane-, -42.8 and -41.4 kcal mol^{-1} for tert-butane-nitro compounds and nitrites, respectively. Entropy and heat capacity values are also reported for the lower homologues: nitromethane, nitroethane and corresponding nitrites. C--H bond energies are decreased by ~ 5 kcal moil alpha to the nitro or nitrite groups and increased by ~ 0.5 kcal moil beta to the nitro and nitrite groups. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone, acetonitrite, nitroacetate and acetyl nitrite are -51.6 kcal mol^{-1}, -51.26 kcal mol^{-1}, -45.4 kcal mol^{-1} and -58.2 kcal mol^{-1}, respectively. The calculated [Delta]fH _{298} for nitroethylene is 7.6 kcal mol^{-1} and for vinyl nitrite is 7.2 kcal mol^{-1}. The carbonyl and olefin groups retain the major influence on the C-H bond energies. Radicals on carbon adjacent to a nitrite (RC.ONO) group do not exist; they dissociate to the corresponding carbonyl (RC=O + NO) with 38 kcal mol^{-1} exothermic and no apparent barrier. This results from formation of the strong carbonyl (it bond ~ 80 kcal mol^{-1}) with dissociation of the weak RO--NO bond (-43 kcal mol^{-1})."]},{"key":"dc:title","label":"Title","values":["Thermochemistry and bond energies of nitro -alkanes, -alkenes, -carbonyls and corresponding nitrites"]}]}],"canonical_facts":{"dc:contributor":["Joseph W. Bozzelli","Carol A. Venanzi","Tamara M. Gund"],"dc:creator":["Snitsiriwat, Surawee"],"dc:description.abstract":["Density functional and ab initio theory based calculations were performed on a series of nitro -alkanes, -alkenes, carbonyl and corresponding nitrites representing large-scale primary, secondary and tertiary nitro compounds and their radicals resulting from the loss of skeletal hydrogen atoms. Geometries, vibration frequencies and thermochemical properties, [Delta]fH _{298}, S (T) and C p(T) (10K T 5 5000K) are calculated at the individual B3LYP/6-31G(d,p), B3LYP /6-31+G(2d,2p) and composite CBS-QB3 levels. Potential energy barriers for the internal rotations have been computed at the B3LYP/6-31G(d, p) level of theory and the lower barrier contributions are incorporated into entropy and heat capacity data. The standard enthalpies of formation at 298 K are evaluated using isodesmic reaction schemes with several work reactions for each species. Recommended values derived from the most stable conformers of respective nitro- and nitrite isomers include: -30.6 and -28.4 kcal moil for n-propane-, -33.9 and -32.3 kcal mol^{-1} for iso-propane-, -42.8 and -41.4 kcal mol^{-1} for tert-butane-nitro compounds and nitrites, respectively. Entropy and heat capacity values are also reported for the lower homologues: nitromethane, nitroethane and corresponding nitrites. C--H bond energies are decreased by ~ 5 kcal moil alpha to the nitro or nitrite groups and increased by ~ 0.5 kcal moil beta to the nitro and nitrite groups. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone, acetonitrite, nitroacetate and acetyl nitrite are -51.6 kcal mol^{-1}, -51.26 kcal mol^{-1}, -45.4 kcal mol^{-1} and -58.2 kcal mol^{-1}, respectively. The calculated [Delta]fH _{298} for nitroethylene is 7.6 kcal mol^{-1} and for vinyl nitrite is 7.2 kcal mol^{-1}. The carbonyl and olefin groups retain the major influence on the C-H bond energies. Radicals on carbon adjacent to a nitrite (RC.ONO) group do not exist; they dissociate to the corresponding carbonyl (RC=O + NO) with 38 kcal mol^{-1} exothermic and no apparent barrier. This results from formation of the strong carbonyl (it bond ~ 80 kcal mol^{-1}) with dissociation of the weak RO--NO bond (-43 kcal mol^{-1})."],"dc:identifier":["https://digitalcommons.njit.edu/theses/305"],"dc:subject":["Thermochemistry","Bond energy","Environmental Sciences"],"dc:title":["Thermochemistry and bond energies of nitro -alkanes, -alkenes, -carbonyls and corresponding nitrites"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry and Environmental Science"],"thesis:degree_name":["Master of Science in Environmental Science - (M.S.)"]},"updated_at":"2026-07-24T03:23:16Z"}