Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media
In the pH range 6.6-8.6, [MnL 2 (H 2 O) 2 ] + and [MnL 2 (H 2 O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox 2− ) to CO 2 through the inner-sphere intermediates [MnL 2 (ox)] − and [MnL 2 (OH)(ox′)] 2− , where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition...
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| Veröffentlicht in: | Canadian journal of chemistry 1993-12, Vol.71 (12), p.2155-2159 |
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| creator | Mukhopadhyay, Subrata Chaudhuri, Swapan Das, Rina Banerjee, Rupendranath |
| description | In the pH range 6.6-8.6, [MnL
2
(H
2
O)
2
]
+
and [MnL
2
(H
2
O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox
2−
) to CO
2
through the inner-sphere intermediates [MnL
2
(ox)]
−
and [MnL
2
(OH)(ox′)]
2−
, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10
−4
s
−1
and 11.2 × 10
−2
M
−1
s
−1
at 30 °C and at I = 1.0 M (NaClO
4
). Decomposition of these mixed complexes produces free radicals, presumably CO
2
−
, which is further oxidized to CO
2
by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)
3
]
3−
is produced quantitatively when [ox]
0
≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10
−4
s
−1
at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10
−4
s
−1
at 25 °C and I = 1.0 M). |
| doi_str_mv | 10.1139/v93-268 |
| format | Article |
| fullrecord | <record><control><sourceid>pascalfrancis_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1139_v93_268</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>3967970</sourcerecordid><originalsourceid>FETCH-LOGICAL-c283t-1a211ab4c1fdbe814c768c932e8cac64cbab5af59ab7caf29b9c7e40eda4d9673</originalsourceid><addsrcrecordid>eNp1kMFq3DAQhkVpIds05BV0KO1uwIlke9fWMSxtsySQS3I249G4q2JLW0m7xK-Sp62cDTkUcplhxMf3o5-xcykupSzU1UEVWb6qP7CZLGuRFbmSH9lMCFFnpSjzE_Y5hD_prES-nLHnW2MpGgwcrOYD4RasCQN3HY9b4u7JaIjG2enBPUEPkfh0tiOP3oQ5IMWxn6azEN0iG8D-BkuB5pvNZvFiNTHw7ai968eUxDV5c0jSAwVuLIe_e3L7wHfkcds7PyUMpA18YZ866AOdve5T9vjzx8P6Jru7_7VZX99lmNdFzCTkUkJboux0S7UssVrVqIqcagRcldhCu4RuqaCtELpctQorKgVpKLVaVcUp-370oncheOqanTcD-LGRopkqbVKlTao0kV-P5A4CQt95sGjCG14km6pEwr4dMevRpyYgfewNenU1O90l8OJ98P_wf2rKlks</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media</title><source>Free Full-Text Journals in Chemistry</source><source>EZB Electronic Journals Library</source><source>Canadian Science Publishing</source><creator>Mukhopadhyay, Subrata ; Chaudhuri, Swapan ; Das, Rina ; Banerjee, Rupendranath</creator><creatorcontrib>Mukhopadhyay, Subrata ; Chaudhuri, Swapan ; Das, Rina ; Banerjee, Rupendranath</creatorcontrib><description>In the pH range 6.6-8.6, [MnL
2
(H
2
O)
2
]
+
and [MnL
2
(H
2
O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox
2−
) to CO
2
through the inner-sphere intermediates [MnL
2
(ox)]
−
and [MnL
2
(OH)(ox′)]
2−
, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10
−4
s
−1
and 11.2 × 10
−2
M
−1
s
−1
at 30 °C and at I = 1.0 M (NaClO
4
). Decomposition of these mixed complexes produces free radicals, presumably CO
2
−
, which is further oxidized to CO
2
by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)
3
]
3−
is produced quantitatively when [ox]
0
≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10
−4
s
−1
at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10
−4
s
−1
at 25 °C and I = 1.0 M).</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v93-268</identifier><identifier>CODEN: CJCHAG</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Chemistry ; Exact sciences and technology ; Inorganic chemistry and origins of life ; Kinetics and mechanism of reactions</subject><ispartof>Canadian journal of chemistry, 1993-12, Vol.71 (12), p.2155-2159</ispartof><rights>1994 INIST-CNRS</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c283t-1a211ab4c1fdbe814c768c932e8cac64cbab5af59ab7caf29b9c7e40eda4d9673</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://cdnsciencepub.com/doi/pdf/10.1139/v93-268$$EPDF$$P50$$Gnrcresearch$$H</linktopdf><linktohtml>$$Uhttps://cdnsciencepub.com/doi/full/10.1139/v93-268$$EHTML$$P50$$Gnrcresearch$$H</linktohtml><link.rule.ids>314,776,780,2919,27901,27902,64401,64979</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=3967970$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Mukhopadhyay, Subrata</creatorcontrib><creatorcontrib>Chaudhuri, Swapan</creatorcontrib><creatorcontrib>Das, Rina</creatorcontrib><creatorcontrib>Banerjee, Rupendranath</creatorcontrib><title>Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>In the pH range 6.6-8.6, [MnL
2
(H
2
O)
2
]
+
and [MnL
2
(H
2
O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox
2−
) to CO
2
through the inner-sphere intermediates [MnL
2
(ox)]
−
and [MnL
2
(OH)(ox′)]
2−
, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10
−4
s
−1
and 11.2 × 10
−2
M
−1
s
−1
at 30 °C and at I = 1.0 M (NaClO
4
). Decomposition of these mixed complexes produces free radicals, presumably CO
2
−
, which is further oxidized to CO
2
by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)
3
]
3−
is produced quantitatively when [ox]
0
≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10
−4
s
−1
at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10
−4
s
−1
at 25 °C and I = 1.0 M).</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Inorganic chemistry and origins of life</subject><subject>Kinetics and mechanism of reactions</subject><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1993</creationdate><recordtype>article</recordtype><recordid>eNp1kMFq3DAQhkVpIds05BV0KO1uwIlke9fWMSxtsySQS3I249G4q2JLW0m7xK-Sp62cDTkUcplhxMf3o5-xcykupSzU1UEVWb6qP7CZLGuRFbmSH9lMCFFnpSjzE_Y5hD_prES-nLHnW2MpGgwcrOYD4RasCQN3HY9b4u7JaIjG2enBPUEPkfh0tiOP3oQ5IMWxn6azEN0iG8D-BkuB5pvNZvFiNTHw7ai968eUxDV5c0jSAwVuLIe_e3L7wHfkcds7PyUMpA18YZ866AOdve5T9vjzx8P6Jru7_7VZX99lmNdFzCTkUkJboux0S7UssVrVqIqcagRcldhCu4RuqaCtELpctQorKgVpKLVaVcUp-370oncheOqanTcD-LGRopkqbVKlTao0kV-P5A4CQt95sGjCG14km6pEwr4dMevRpyYgfewNenU1O90l8OJ98P_wf2rKlks</recordid><startdate>19931201</startdate><enddate>19931201</enddate><creator>Mukhopadhyay, Subrata</creator><creator>Chaudhuri, Swapan</creator><creator>Das, Rina</creator><creator>Banerjee, Rupendranath</creator><general>NRC Research Press</general><general>National Research Council of Canada</general><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19931201</creationdate><title>Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media</title><author>Mukhopadhyay, Subrata ; Chaudhuri, Swapan ; Das, Rina ; Banerjee, Rupendranath</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c283t-1a211ab4c1fdbe814c768c932e8cac64cbab5af59ab7caf29b9c7e40eda4d9673</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1993</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Inorganic chemistry and origins of life</topic><topic>Kinetics and mechanism of reactions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mukhopadhyay, Subrata</creatorcontrib><creatorcontrib>Chaudhuri, Swapan</creatorcontrib><creatorcontrib>Das, Rina</creatorcontrib><creatorcontrib>Banerjee, Rupendranath</creatorcontrib><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mukhopadhyay, Subrata</au><au>Chaudhuri, Swapan</au><au>Das, Rina</au><au>Banerjee, Rupendranath</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1993-12-01</date><risdate>1993</risdate><volume>71</volume><issue>12</issue><spage>2155</spage><epage>2159</epage><pages>2155-2159</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><coden>CJCHAG</coden><abstract>In the pH range 6.6-8.6, [MnL
2
(H
2
O)
2
]
+
and [MnL
2
(H
2
O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox
2−
) to CO
2
through the inner-sphere intermediates [MnL
2
(ox)]
−
and [MnL
2
(OH)(ox′)]
2−
, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10
−4
s
−1
and 11.2 × 10
−2
M
−1
s
−1
at 30 °C and at I = 1.0 M (NaClO
4
). Decomposition of these mixed complexes produces free radicals, presumably CO
2
−
, which is further oxidized to CO
2
by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)
3
]
3−
is produced quantitatively when [ox]
0
≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10
−4
s
−1
at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10
−4
s
−1
at 25 °C and I = 1.0 M).</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v93-268</doi><tpages>5</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Canadian journal of chemistry, 1993-12, Vol.71 (12), p.2155-2159 |
| issn | 0008-4042 1480-3291 |
| language | eng |
| recordid | cdi_crossref_primary_10_1139_v93_268 |
| source | Free Full-Text Journals in Chemistry; EZB Electronic Journals Library; Canadian Science Publishing |
| subjects | Chemistry Exact sciences and technology Inorganic chemistry and origins of life Kinetics and mechanism of reactions |
| title | Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media |
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