The mechanism of oxidation of 3-mercaptopropionic acid
The mechanism of the oxidation of 3-mercaptopropionic acid (3-MPA) by hydrogen peroxide was studied in the acidic pH range. The nucleophilic attack by sulphur on the peroxide bond controls the rate. Extrapolation of the pH dependency suggests that the rate of attack by the deprotonated dianion is hi...
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| Veröffentlicht in: | Canadian journal of chemistry 1997-01, Vol.75 (1), p.9-13 |
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| creator | Forlano, Paula Olabe, José A Magallanes, Jorge F Blesa, Miguel A |
| description | The mechanism of the oxidation of 3-mercaptopropionic acid (3-MPA) by hydrogen peroxide was studied in the acidic pH range. The nucleophilic attack by sulphur on the peroxide bond controls the rate. Extrapolation of the pH dependency suggests that the rate of attack by the deprotonated dianion is highest. Traces of Fe(III), at levels below 10
−7
mol dm
−3
, do not catalyze efficiently the process through one-electron mechanisms; at higher concentrations, or on the surface of iron(III) oxides, this type of catalysis becomes important. The electrochemical oxidation of 3-MPA was also studied, using differential pulse polarography and cyclic voltammetry techniques. The mechanism is of the EC
2
E type, the second electron transfer step corresponding to the oxidation of the disulphide RS-SR. The rate constant for the dimerization of the RS
*
radicals was 1.8 × 10
3
mol
−1
dm
3
s
−1
; the slowness of this step agrees with the mechanisms observed in the course of one-electron oxidations by metal ions. Keywords: electrochemistry, kinetics, 3-mercaptopropionic acid, autooxidation. |
| doi_str_mv | 10.1139/v97-002 |
| format | Article |
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−7
mol dm
−3
, do not catalyze efficiently the process through one-electron mechanisms; at higher concentrations, or on the surface of iron(III) oxides, this type of catalysis becomes important. The electrochemical oxidation of 3-MPA was also studied, using differential pulse polarography and cyclic voltammetry techniques. The mechanism is of the EC
2
E type, the second electron transfer step corresponding to the oxidation of the disulphide RS-SR. The rate constant for the dimerization of the RS
*
radicals was 1.8 × 10
3
mol
−1
dm
3
s
−1
; the slowness of this step agrees with the mechanisms observed in the course of one-electron oxidations by metal ions. Keywords: electrochemistry, kinetics, 3-mercaptopropionic acid, autooxidation.</description><identifier>ISSN: 0008-4042</identifier><identifier>EISSN: 1480-3291</identifier><identifier>DOI: 10.1139/v97-002</identifier><identifier>CODEN: CJCHAG</identifier><language>eng</language><publisher>Ottawa, Canada: NRC Research Press</publisher><subject>Electrochemistry ; Kinetics ; Oxidation</subject><ispartof>Canadian journal of chemistry, 1997-01, Vol.75 (1), p.9-13</ispartof><rights>Copyright National Research Council of Canada Jan 1997</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c285t-45fb73a67cb63f55124b4bc8f8db54e19507f878d12f5e5f33932d49af79f6aa3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://cdnsciencepub.com/doi/pdf/10.1139/v97-002$$EPDF$$P50$$Gnrcresearch$$H</linktopdf><linktohtml>$$Uhttps://cdnsciencepub.com/doi/full/10.1139/v97-002$$EHTML$$P50$$Gnrcresearch$$H</linktohtml><link.rule.ids>314,776,780,2919,27901,27902,64401,64979</link.rule.ids></links><search><creatorcontrib>Forlano, Paula</creatorcontrib><creatorcontrib>Olabe, José A</creatorcontrib><creatorcontrib>Magallanes, Jorge F</creatorcontrib><creatorcontrib>Blesa, Miguel A</creatorcontrib><title>The mechanism of oxidation of 3-mercaptopropionic acid</title><title>Canadian journal of chemistry</title><addtitle>Revue canadienne de chimie</addtitle><description>The mechanism of the oxidation of 3-mercaptopropionic acid (3-MPA) by hydrogen peroxide was studied in the acidic pH range. The nucleophilic attack by sulphur on the peroxide bond controls the rate. Extrapolation of the pH dependency suggests that the rate of attack by the deprotonated dianion is highest. Traces of Fe(III), at levels below 10
−7
mol dm
−3
, do not catalyze efficiently the process through one-electron mechanisms; at higher concentrations, or on the surface of iron(III) oxides, this type of catalysis becomes important. The electrochemical oxidation of 3-MPA was also studied, using differential pulse polarography and cyclic voltammetry techniques. The mechanism is of the EC
2
E type, the second electron transfer step corresponding to the oxidation of the disulphide RS-SR. The rate constant for the dimerization of the RS
*
radicals was 1.8 × 10
3
mol
−1
dm
3
s
−1
; the slowness of this step agrees with the mechanisms observed in the course of one-electron oxidations by metal ions. Keywords: electrochemistry, kinetics, 3-mercaptopropionic acid, autooxidation.</description><subject>Electrochemistry</subject><subject>Kinetics</subject><subject>Oxidation</subject><issn>0008-4042</issn><issn>1480-3291</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1997</creationdate><recordtype>article</recordtype><sourceid>8G5</sourceid><sourceid>BENPR</sourceid><sourceid>GUQSH</sourceid><sourceid>M2O</sourceid><recordid>eNp1kE1LxDAURYMoWEfxLxQ3ghDNZ5MsZXBUGHAzrkOaJjSDbWrSEf33ZqhbV4_7ONwLB4BrjO4xpurhSwmIEDkBFWYSQUoUPgUVQkhChhg5Bxc570sUiPAKNLve1YOzvRlDHuro6_gdOjOHOB4DhYNL1kxznFKcyjPY2tjQXYIzbz6yu_q7K_C-edqtX-D27fl1_biFlkg-Q8Z9K6hphG0b6jnHhLWstdLLruXMYcWR8FLIDhPPHfeUKko6powXyjfG0BW4WXrL_OfB5Vnv4yGNZVITLBvOMG0KdLtANsWck_N6SmEw6UdjpI9OdHGii5NC3i3kmGxy2Zlk-3_hX4oOYFY</recordid><startdate>19970101</startdate><enddate>19970101</enddate><creator>Forlano, Paula</creator><creator>Olabe, José A</creator><creator>Magallanes, Jorge F</creator><creator>Blesa, Miguel A</creator><general>NRC Research Press</general><general>Canadian Science Publishing NRC Research Press</general><scope>AAYXX</scope><scope>CITATION</scope><scope>3V.</scope><scope>7XB</scope><scope>88I</scope><scope>8AF</scope><scope>8AO</scope><scope>8FE</scope><scope>8FG</scope><scope>8FK</scope><scope>8FQ</scope><scope>8FV</scope><scope>8G5</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AEUYN</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>BKSAR</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>GNUQQ</scope><scope>GUQSH</scope><scope>HCIFZ</scope><scope>KB.</scope><scope>M2O</scope><scope>M2P</scope><scope>M3G</scope><scope>MBDVC</scope><scope>PADUT</scope><scope>PCBAR</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>Q9U</scope></search><sort><creationdate>19970101</creationdate><title>The mechanism of oxidation of 3-mercaptopropionic acid</title><author>Forlano, Paula ; Olabe, José A ; Magallanes, Jorge F ; Blesa, Miguel A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c285t-45fb73a67cb63f55124b4bc8f8db54e19507f878d12f5e5f33932d49af79f6aa3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1997</creationdate><topic>Electrochemistry</topic><topic>Kinetics</topic><topic>Oxidation</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Forlano, Paula</creatorcontrib><creatorcontrib>Olabe, José A</creatorcontrib><creatorcontrib>Magallanes, Jorge F</creatorcontrib><creatorcontrib>Blesa, Miguel A</creatorcontrib><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Science Database (Alumni Edition)</collection><collection>STEM Database</collection><collection>ProQuest Pharma Collection</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Canadian Business & Current Affairs Database</collection><collection>Canadian Business & Current Affairs Database (Alumni Edition)</collection><collection>Research Library (Alumni Edition)</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest One Sustainability</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>Earth, Atmospheric & Aquatic Science Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>ProQuest Central Student</collection><collection>Research Library Prep</collection><collection>SciTech Premium Collection</collection><collection>Materials Science Database</collection><collection>Research Library</collection><collection>Science Database</collection><collection>CBCA Reference & Current Events</collection><collection>Research Library (Corporate)</collection><collection>Research Library China</collection><collection>Earth, Atmospheric & Aquatic Science Database</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>ProQuest Central Basic</collection><jtitle>Canadian journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Forlano, Paula</au><au>Olabe, José A</au><au>Magallanes, Jorge F</au><au>Blesa, Miguel A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The mechanism of oxidation of 3-mercaptopropionic acid</atitle><jtitle>Canadian journal of chemistry</jtitle><addtitle>Revue canadienne de chimie</addtitle><date>1997-01-01</date><risdate>1997</risdate><volume>75</volume><issue>1</issue><spage>9</spage><epage>13</epage><pages>9-13</pages><issn>0008-4042</issn><eissn>1480-3291</eissn><coden>CJCHAG</coden><abstract>The mechanism of the oxidation of 3-mercaptopropionic acid (3-MPA) by hydrogen peroxide was studied in the acidic pH range. The nucleophilic attack by sulphur on the peroxide bond controls the rate. Extrapolation of the pH dependency suggests that the rate of attack by the deprotonated dianion is highest. Traces of Fe(III), at levels below 10
−7
mol dm
−3
, do not catalyze efficiently the process through one-electron mechanisms; at higher concentrations, or on the surface of iron(III) oxides, this type of catalysis becomes important. The electrochemical oxidation of 3-MPA was also studied, using differential pulse polarography and cyclic voltammetry techniques. The mechanism is of the EC
2
E type, the second electron transfer step corresponding to the oxidation of the disulphide RS-SR. The rate constant for the dimerization of the RS
*
radicals was 1.8 × 10
3
mol
−1
dm
3
s
−1
; the slowness of this step agrees with the mechanisms observed in the course of one-electron oxidations by metal ions. Keywords: electrochemistry, kinetics, 3-mercaptopropionic acid, autooxidation.</abstract><cop>Ottawa, Canada</cop><pub>NRC Research Press</pub><doi>10.1139/v97-002</doi><tpages>5</tpages></addata></record> |
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| source | NRC Research Press; Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; Free Full-Text Journals in Chemistry |
| subjects | Electrochemistry Kinetics Oxidation |
| title | The mechanism of oxidation of 3-mercaptopropionic acid |
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