Matches in SemOpenAlex for { <https://semopenalex.org/work/W2085452253> ?p ?o ?g. }
- W2085452253 endingPage "340" @default.
- W2085452253 startingPage "331" @default.
- W2085452253 abstract "According to most theories of the slow gas-phase oxidation of hydrocarbons, the major product producing reactions are homogeneous and it is supposed that the main effect of surface is on kinetically important reactions which produce relatively little final product. According to one theory of hydrocarbon oxidation all primary products arise from the homogeneous unimolecular decomposition of peroxy radicals or from reactions of radicals produced from such decompositions. If this is so, the distribution of the products formed directly from the peroxy radicals should be unaffected by reactant pressures (in particular, oxygen pressure) and should change gradually with temperature provided that conditions are chosen to avoid secondary oxidation. By analyzing the reaction products from the oxidation of isobutane and isobutene between 250° and 350°C when the extent of oxidation is sufficiently small that secondary oxidation is negligible we have found that, while the percentage yields of the major products (about 80% isobutene from isobutane, and about 75% acetone+formaldehyde from isobutene) are little affected, reactant pressure and temperature have such profound effects on the distribution of the minor products that the simple hypothesis outlined above is untenable. Furthermore, investigations of the effect of change of surface have revealed that the initial distribution of minor products is highly sensitive to the nature of the reaction vessel wall: the surfaces investigated were clean Pyrex; HF washed Pyrex; KCl-, B2O3−, and NaOH-coated Pyrex; and silverplated Pyrex. It is concluded that, contrary to general belief, a considerable part, if not the whole, of the minor products arise in heterogeneous processes which by consequence play a very important part in the reactions between 250° and 350°C. However, general considerations demand that the heterogeneous processes are not independent but are consequent on primary homogeneous processes involving free radicals. It is proposed that three primary homogeneous reactions occur in the early stages of the oxidation of isobutane and three in the oxidation of isobutene: Isobutane C4H10+X=C4H9+HX C4H9+O2=C4H8+HO2 C4H9+O2=C4H9OO Isobutene C4H8+HO2=Me2CO+CH2OH C4H8+HO2=Me2COH+CH2O C4H8+HO2=C4H8OOH and that these homogeneous reactions are followed by the heterogeneous decompositions of the peroxy radicals into complex surface sensitive mixtures of products, C4H9OO+wall=complex mixture A C4H8OOH+wall=complex mixture B With isobutene there will necessarily be secondary homogeneous processes producing formaldehyde or CO by oxidation of CH2OH and acetone by oxidation of Me2COH. This mechanism explains why the ratio of major to minor products is little affected by composition, total pressure, temperature, or surface while the distribution of minor products is highly sensitive to these parameters." @default.
- W2085452253 created "2016-06-24" @default.
- W2085452253 creator A5019518808 @default.
- W2085452253 creator A5049188218 @default.
- W2085452253 creator A5074841127 @default.
- W2085452253 date "1965-01-01" @default.
- W2085452253 modified "2023-10-14" @default.
- W2085452253 title "Homogeneous and heterogeneous processes in the gas-phase oxidation of isobutane and isobutene" @default.
- W2085452253 cites W1972165944 @default.
- W2085452253 cites W1983263855 @default.
- W2085452253 cites W1989323632 @default.
- W2085452253 cites W1990572948 @default.
- W2085452253 cites W1990837669 @default.
- W2085452253 cites W1993864078 @default.
- W2085452253 cites W2009982028 @default.
- W2085452253 cites W2031570579 @default.
- W2085452253 cites W2036755294 @default.
- W2085452253 cites W2039710165 @default.
- W2085452253 cites W2041068053 @default.
- W2085452253 cites W2042118896 @default.
- W2085452253 cites W2042179119 @default.
- W2085452253 cites W2044398691 @default.
- W2085452253 cites W2050434333 @default.
- W2085452253 cites W2053575982 @default.
- W2085452253 cites W2075322714 @default.
- W2085452253 cites W2080684770 @default.
- W2085452253 cites W2084374506 @default.
- W2085452253 cites W2092758442 @default.
- W2085452253 cites W2101547299 @default.
- W2085452253 cites W2104604769 @default.
- W2085452253 cites W2112343068 @default.
- W2085452253 cites W2117670491 @default.
- W2085452253 cites W2119373073 @default.
- W2085452253 cites W2145495523 @default.
- W2085452253 cites W2161989057 @default.
- W2085452253 cites W4243146009 @default.
- W2085452253 cites W1987916855 @default.
- W2085452253 cites W2114388096 @default.
- W2085452253 doi "https://doi.org/10.1016/s0082-0784(65)80180-1" @default.
- W2085452253 hasPublicationYear "1965" @default.
- W2085452253 type Work @default.
- W2085452253 sameAs 2085452253 @default.
- W2085452253 citedByCount "5" @default.
- W2085452253 crossrefType "journal-article" @default.
- W2085452253 hasAuthorship W2085452253A5019518808 @default.
- W2085452253 hasAuthorship W2085452253A5049188218 @default.
- W2085452253 hasAuthorship W2085452253A5074841127 @default.
- W2085452253 hasConcept C121332964 @default.
- W2085452253 hasConcept C124681953 @default.
- W2085452253 hasConcept C139066938 @default.
- W2085452253 hasConcept C161790260 @default.
- W2085452253 hasConcept C166940927 @default.
- W2085452253 hasConcept C17112743 @default.
- W2085452253 hasConcept C178790620 @default.
- W2085452253 hasConcept C179104552 @default.
- W2085452253 hasConcept C185592680 @default.
- W2085452253 hasConcept C2775930285 @default.
- W2085452253 hasConcept C2775968528 @default.
- W2085452253 hasConcept C2777207669 @default.
- W2085452253 hasConcept C2778861962 @default.
- W2085452253 hasConcept C2780115832 @default.
- W2085452253 hasConcept C2781213060 @default.
- W2085452253 hasConcept C521977710 @default.
- W2085452253 hasConcept C66882249 @default.
- W2085452253 hasConcept C75473681 @default.
- W2085452253 hasConcept C97355855 @default.
- W2085452253 hasConceptScore W2085452253C121332964 @default.
- W2085452253 hasConceptScore W2085452253C124681953 @default.
- W2085452253 hasConceptScore W2085452253C139066938 @default.
- W2085452253 hasConceptScore W2085452253C161790260 @default.
- W2085452253 hasConceptScore W2085452253C166940927 @default.
- W2085452253 hasConceptScore W2085452253C17112743 @default.
- W2085452253 hasConceptScore W2085452253C178790620 @default.
- W2085452253 hasConceptScore W2085452253C179104552 @default.
- W2085452253 hasConceptScore W2085452253C185592680 @default.
- W2085452253 hasConceptScore W2085452253C2775930285 @default.
- W2085452253 hasConceptScore W2085452253C2775968528 @default.
- W2085452253 hasConceptScore W2085452253C2777207669 @default.
- W2085452253 hasConceptScore W2085452253C2778861962 @default.
- W2085452253 hasConceptScore W2085452253C2780115832 @default.
- W2085452253 hasConceptScore W2085452253C2781213060 @default.
- W2085452253 hasConceptScore W2085452253C521977710 @default.
- W2085452253 hasConceptScore W2085452253C66882249 @default.
- W2085452253 hasConceptScore W2085452253C75473681 @default.
- W2085452253 hasConceptScore W2085452253C97355855 @default.
- W2085452253 hasIssue "1" @default.
- W2085452253 hasLocation W20854522531 @default.
- W2085452253 hasOpenAccess W2085452253 @default.
- W2085452253 hasPrimaryLocation W20854522531 @default.
- W2085452253 hasRelatedWork W1966073701 @default.
- W2085452253 hasRelatedWork W1991908559 @default.
- W2085452253 hasRelatedWork W1994302964 @default.
- W2085452253 hasRelatedWork W2046666166 @default.
- W2085452253 hasRelatedWork W2059243999 @default.
- W2085452253 hasRelatedWork W2059883105 @default.
- W2085452253 hasRelatedWork W2075783374 @default.
- W2085452253 hasRelatedWork W2087731782 @default.
- W2085452253 hasRelatedWork W914054627 @default.