Radiation chemistry of aqueous solutions of dicyandiamide
Oxygen-free aqueous solutions of dicyandiamide, DCDA, were exposed to /sup 60/Co ..gamma.. rays or a pulsed 10-MeV electron beam. Fast kinetic spectrophotometry was used for the study of free-radical intermediates, and computer simulation of the reaction mechanism for evaluation of experimental data...
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| Veröffentlicht in: | J. Phys. Chem.; (United States) 1979-01, Vol.83 (2), p.220-224 |
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| creator | Draganic, Z. D Draganic, I. G Sehested, K |
| description | Oxygen-free aqueous solutions of dicyandiamide, DCDA, were exposed to /sup 60/Co ..gamma.. rays or a pulsed 10-MeV electron beam. Fast kinetic spectrophotometry was used for the study of free-radical intermediates, and computer simulation of the reaction mechanism for evaluation of experimental data. The hydrated electron reacts by addition, k(e/sub aq//sup -/ + DCDA) = 1.1 x 10/sup 10/M/sup -1/s/sup -1/; the anion radical (NH/sub 2/C(=NH)NHCN)/sup -/ absorbs in the UV region with lambda/sub max/ |
| doi_str_mv | 10.1021/j100465a003 |
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D ; Draganic, I. G ; Sehested, K</creator><creatorcontrib>Draganic, Z. D ; Draganic, I. G ; Sehested, K ; Boris Kidric Inst. of Nuclear Sciences, Beograd, Yugoslavia</creatorcontrib><description>Oxygen-free aqueous solutions of dicyandiamide, DCDA, were exposed to /sup 60/Co ..gamma.. rays or a pulsed 10-MeV electron beam. Fast kinetic spectrophotometry was used for the study of free-radical intermediates, and computer simulation of the reaction mechanism for evaluation of experimental data. The hydrated electron reacts by addition, k(e/sub aq//sup -/ + DCDA) = 1.1 x 10/sup 10/M/sup -1/s/sup -1/; the anion radical (NH/sub 2/C(=NH)NHCN)/sup -/ absorbs in the UV region with lambda/sub max/<255nm and an epsilon (255) of 1150 M/sup -1/cm/sup -1/. It disappears with 2k = 1 x 10/sup 9/M/sup -1/s/sup -1/ by forming a product which absorbs with lambda/sub max/<255nm and an epsilon (255) of 2400 M/sup -1/cm/sup -1/. The hydrogen atom also reacts by addition, k(H + DCDA) = 2.7 x 10/sup 6/ M/sup -1/s/sup -1/, and the radical intermediate has a lambda/sub max/ of 350nm and an epsilon (350) of 1250 M/sup -1/cm/sup -1/; it disappears with 2k greater than or equal to 10/sup 9/M/sup -1/s/sup -1/. Hydroxyl radicals react both by addition and by abstraction, k(OH + DCDA) = 5.6 x 10/sup 6/M/sup -1/s/sup -1/, and two transients with lambda/sub max/ at 450 and 355nm appear. It is estimated that about 90% of OH radicals react by abstraction. It has also been found that the radical-anion SO/sub 4//sup -/ reacts efficiently with DCDA and the product of this reaction, NH/sub 2//sup +/C(=O)NHCN, absorbs light with a lambda/sub max/ of 355nm and epsilon (355) of 1150 M/sup -1/cm/sup -1/. The OH adduct of DCDA has a lambda/sub max/ of 450nm and epsilon (450) of 1700 M/sup -1/cm/sup -1/; it disappears by a second-order process with 2k less than or equal to 4 x 10/sup 9/M/sup -1/s/sup -1/. The search for stable radiolytic products in the kilorad-megarad dose range has shown the presence of only a few smaller molecules and in low yields.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100465a003</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400600 - Radiation Chemistry ; ABSORPTION SPECTRA ; ANIONS ; AQUEOUS SOLUTIONS ; BEAMS ; CARBONIC ACID DERIVATIVES ; CHARGED PARTICLES ; CHEMICAL RADIATION EFFECTS ; CHEMICAL REACTION KINETICS ; CHEMICAL REACTIONS ; CHEMISTRY ; CYANAMIDES ; DATA ; DATA FORMS ; DECOMPOSITION ; DISPERSIONS ; ELECTROMAGNETIC RADIATION ; ELECTRON BEAMS ; ELECTRONS ; ELEMENTARY PARTICLES ; EXPERIMENTAL DATA ; FERMIONS ; GAMMA RADIATION ; GRAPHS ; HYDRATION ; HYDROXYL RADICALS ; INFORMATION ; IONIZING RADIATIONS ; IONS ; ISOLATED VALUES ; KINETICS ; LEPTON BEAMS ; LEPTONS ; MIXTURES ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC NITROGEN COMPOUNDS ; PARTICLE BEAMS ; RADIATION CHEMISTRY ; RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY ; RADIATION EFFECTS ; RADIATIONS ; RADICALS ; RADIOLYSIS ; REACTION INTERMEDIATES ; REACTION KINETICS ; SOLUTIONS ; SOLVATED ELECTRONS ; SOLVATION ; SPECTRA ; SPECTROPHOTOMETRY</subject><ispartof>J. Phys. Chem.; (United States), 1979-01, Vol.83 (2), p.220-224</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a330t-718e3b9cfbecb64ef5dbca664cc7bee6215365850fc240916b737b69169ed7273</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/j100465a003$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/j100465a003$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/6281019$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Draganic, Z. D</creatorcontrib><creatorcontrib>Draganic, I. G</creatorcontrib><creatorcontrib>Sehested, K</creatorcontrib><creatorcontrib>Boris Kidric Inst. of Nuclear Sciences, Beograd, Yugoslavia</creatorcontrib><title>Radiation chemistry of aqueous solutions of dicyandiamide</title><title>J. Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>Oxygen-free aqueous solutions of dicyandiamide, DCDA, were exposed to /sup 60/Co ..gamma.. rays or a pulsed 10-MeV electron beam. Fast kinetic spectrophotometry was used for the study of free-radical intermediates, and computer simulation of the reaction mechanism for evaluation of experimental data. The hydrated electron reacts by addition, k(e/sub aq//sup -/ + DCDA) = 1.1 x 10/sup 10/M/sup -1/s/sup -1/; the anion radical (NH/sub 2/C(=NH)NHCN)/sup -/ absorbs in the UV region with lambda/sub max/<255nm and an epsilon (255) of 1150 M/sup -1/cm/sup -1/. It disappears with 2k = 1 x 10/sup 9/M/sup -1/s/sup -1/ by forming a product which absorbs with lambda/sub max/<255nm and an epsilon (255) of 2400 M/sup -1/cm/sup -1/. The hydrogen atom also reacts by addition, k(H + DCDA) = 2.7 x 10/sup 6/ M/sup -1/s/sup -1/, and the radical intermediate has a lambda/sub max/ of 350nm and an epsilon (350) of 1250 M/sup -1/cm/sup -1/; it disappears with 2k greater than or equal to 10/sup 9/M/sup -1/s/sup -1/. Hydroxyl radicals react both by addition and by abstraction, k(OH + DCDA) = 5.6 x 10/sup 6/M/sup -1/s/sup -1/, and two transients with lambda/sub max/ at 450 and 355nm appear. It is estimated that about 90% of OH radicals react by abstraction. It has also been found that the radical-anion SO/sub 4//sup -/ reacts efficiently with DCDA and the product of this reaction, NH/sub 2//sup +/C(=O)NHCN, absorbs light with a lambda/sub max/ of 355nm and epsilon (355) of 1150 M/sup -1/cm/sup -1/. The OH adduct of DCDA has a lambda/sub max/ of 450nm and epsilon (450) of 1700 M/sup -1/cm/sup -1/; it disappears by a second-order process with 2k less than or equal to 4 x 10/sup 9/M/sup -1/s/sup -1/. The search for stable radiolytic products in the kilorad-megarad dose range has shown the presence of only a few smaller molecules and in low yields.</description><subject>400600 - Radiation Chemistry</subject><subject>ABSORPTION SPECTRA</subject><subject>ANIONS</subject><subject>AQUEOUS SOLUTIONS</subject><subject>BEAMS</subject><subject>CARBONIC ACID DERIVATIVES</subject><subject>CHARGED PARTICLES</subject><subject>CHEMICAL RADIATION EFFECTS</subject><subject>CHEMICAL REACTION KINETICS</subject><subject>CHEMICAL REACTIONS</subject><subject>CHEMISTRY</subject><subject>CYANAMIDES</subject><subject>DATA</subject><subject>DATA FORMS</subject><subject>DECOMPOSITION</subject><subject>DISPERSIONS</subject><subject>ELECTROMAGNETIC RADIATION</subject><subject>ELECTRON BEAMS</subject><subject>ELECTRONS</subject><subject>ELEMENTARY PARTICLES</subject><subject>EXPERIMENTAL DATA</subject><subject>FERMIONS</subject><subject>GAMMA RADIATION</subject><subject>GRAPHS</subject><subject>HYDRATION</subject><subject>HYDROXYL RADICALS</subject><subject>INFORMATION</subject><subject>IONIZING RADIATIONS</subject><subject>IONS</subject><subject>ISOLATED VALUES</subject><subject>KINETICS</subject><subject>LEPTON BEAMS</subject><subject>LEPTONS</subject><subject>MIXTURES</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC NITROGEN COMPOUNDS</subject><subject>PARTICLE BEAMS</subject><subject>RADIATION CHEMISTRY</subject><subject>RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY</subject><subject>RADIATION EFFECTS</subject><subject>RADIATIONS</subject><subject>RADICALS</subject><subject>RADIOLYSIS</subject><subject>REACTION INTERMEDIATES</subject><subject>REACTION KINETICS</subject><subject>SOLUTIONS</subject><subject>SOLVATED ELECTRONS</subject><subject>SOLVATION</subject><subject>SPECTRA</subject><subject>SPECTROPHOTOMETRY</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1979</creationdate><recordtype>article</recordtype><recordid>eNptkE1LAzEQhoMoWKsn_8DixYOsTr67R6kfFQrKWvUYstksTW03muyC_femrIgHTzPMPLwz74vQKYZLDARfrTAAE1wD0D00wpzhnEsG-2gEQEhOBWeH6CjGFQBgSvEIFaWune6cbzOztBsXu7DNfJPpz976PmbRr_vdNu6GtTNb3SZ-42p7jA4avY725KeO0cvd7WI6y-eP9w_T63muKYUul3hiaVWYprKmEsw2vK6MFoIZIytrBcE8vTXh0BjCoMCiklRWIjWFrSWRdIzOBl0fO6eicZ01S-Pb1ppOCTLBgIsEXQyQCT7GYBv1EdxGh63CoHbRqD_RJDof6GTXfv2iOrwrka5ztXh6VuLmbVbK10KViT8feG2iWvk-tMnwv8rfbSBxDA</recordid><startdate>19790101</startdate><enddate>19790101</enddate><creator>Draganic, Z. D</creator><creator>Draganic, I. G</creator><creator>Sehested, K</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19790101</creationdate><title>Radiation chemistry of aqueous solutions of dicyandiamide</title><author>Draganic, Z. D ; Draganic, I. G ; Sehested, K</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a330t-718e3b9cfbecb64ef5dbca664cc7bee6215365850fc240916b737b69169ed7273</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1979</creationdate><topic>400600 - Radiation Chemistry</topic><topic>ABSORPTION SPECTRA</topic><topic>ANIONS</topic><topic>AQUEOUS SOLUTIONS</topic><topic>BEAMS</topic><topic>CARBONIC ACID DERIVATIVES</topic><topic>CHARGED PARTICLES</topic><topic>CHEMICAL RADIATION EFFECTS</topic><topic>CHEMICAL REACTION KINETICS</topic><topic>CHEMICAL REACTIONS</topic><topic>CHEMISTRY</topic><topic>CYANAMIDES</topic><topic>DATA</topic><topic>DATA FORMS</topic><topic>DECOMPOSITION</topic><topic>DISPERSIONS</topic><topic>ELECTROMAGNETIC RADIATION</topic><topic>ELECTRON BEAMS</topic><topic>ELECTRONS</topic><topic>ELEMENTARY PARTICLES</topic><topic>EXPERIMENTAL DATA</topic><topic>FERMIONS</topic><topic>GAMMA RADIATION</topic><topic>GRAPHS</topic><topic>HYDRATION</topic><topic>HYDROXYL RADICALS</topic><topic>INFORMATION</topic><topic>IONIZING RADIATIONS</topic><topic>IONS</topic><topic>ISOLATED VALUES</topic><topic>KINETICS</topic><topic>LEPTON BEAMS</topic><topic>LEPTONS</topic><topic>MIXTURES</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC NITROGEN COMPOUNDS</topic><topic>PARTICLE BEAMS</topic><topic>RADIATION CHEMISTRY</topic><topic>RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY</topic><topic>RADIATION EFFECTS</topic><topic>RADIATIONS</topic><topic>RADICALS</topic><topic>RADIOLYSIS</topic><topic>REACTION INTERMEDIATES</topic><topic>REACTION KINETICS</topic><topic>SOLUTIONS</topic><topic>SOLVATED ELECTRONS</topic><topic>SOLVATION</topic><topic>SPECTRA</topic><topic>SPECTROPHOTOMETRY</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Draganic, Z. D</creatorcontrib><creatorcontrib>Draganic, I. G</creatorcontrib><creatorcontrib>Sehested, K</creatorcontrib><creatorcontrib>Boris Kidric Inst. of Nuclear Sciences, Beograd, Yugoslavia</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Draganic, Z. D</au><au>Draganic, I. G</au><au>Sehested, K</au><aucorp>Boris Kidric Inst. of Nuclear Sciences, Beograd, Yugoslavia</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Radiation chemistry of aqueous solutions of dicyandiamide</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1979-01-01</date><risdate>1979</risdate><volume>83</volume><issue>2</issue><spage>220</spage><epage>224</epage><pages>220-224</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><abstract>Oxygen-free aqueous solutions of dicyandiamide, DCDA, were exposed to /sup 60/Co ..gamma.. rays or a pulsed 10-MeV electron beam. Fast kinetic spectrophotometry was used for the study of free-radical intermediates, and computer simulation of the reaction mechanism for evaluation of experimental data. The hydrated electron reacts by addition, k(e/sub aq//sup -/ + DCDA) = 1.1 x 10/sup 10/M/sup -1/s/sup -1/; the anion radical (NH/sub 2/C(=NH)NHCN)/sup -/ absorbs in the UV region with lambda/sub max/<255nm and an epsilon (255) of 1150 M/sup -1/cm/sup -1/. It disappears with 2k = 1 x 10/sup 9/M/sup -1/s/sup -1/ by forming a product which absorbs with lambda/sub max/<255nm and an epsilon (255) of 2400 M/sup -1/cm/sup -1/. The hydrogen atom also reacts by addition, k(H + DCDA) = 2.7 x 10/sup 6/ M/sup -1/s/sup -1/, and the radical intermediate has a lambda/sub max/ of 350nm and an epsilon (350) of 1250 M/sup -1/cm/sup -1/; it disappears with 2k greater than or equal to 10/sup 9/M/sup -1/s/sup -1/. Hydroxyl radicals react both by addition and by abstraction, k(OH + DCDA) = 5.6 x 10/sup 6/M/sup -1/s/sup -1/, and two transients with lambda/sub max/ at 450 and 355nm appear. It is estimated that about 90% of OH radicals react by abstraction. It has also been found that the radical-anion SO/sub 4//sup -/ reacts efficiently with DCDA and the product of this reaction, NH/sub 2//sup +/C(=O)NHCN, absorbs light with a lambda/sub max/ of 355nm and epsilon (355) of 1150 M/sup -1/cm/sup -1/. The OH adduct of DCDA has a lambda/sub max/ of 450nm and epsilon (450) of 1700 M/sup -1/cm/sup -1/; it disappears by a second-order process with 2k less than or equal to 4 x 10/sup 9/M/sup -1/s/sup -1/. The search for stable radiolytic products in the kilorad-megarad dose range has shown the presence of only a few smaller molecules and in low yields.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/j100465a003</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0022-3654 |
| ispartof | J. Phys. Chem.; (United States), 1979-01, Vol.83 (2), p.220-224 |
| issn | 0022-3654 1541-5740 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_j100465a003 |
| source | American Chemical Society Journals |
| subjects | 400600 - Radiation Chemistry ABSORPTION SPECTRA ANIONS AQUEOUS SOLUTIONS BEAMS CARBONIC ACID DERIVATIVES CHARGED PARTICLES CHEMICAL RADIATION EFFECTS CHEMICAL REACTION KINETICS CHEMICAL REACTIONS CHEMISTRY CYANAMIDES DATA DATA FORMS DECOMPOSITION DISPERSIONS ELECTROMAGNETIC RADIATION ELECTRON BEAMS ELECTRONS ELEMENTARY PARTICLES EXPERIMENTAL DATA FERMIONS GAMMA RADIATION GRAPHS HYDRATION HYDROXYL RADICALS INFORMATION IONIZING RADIATIONS IONS ISOLATED VALUES KINETICS LEPTON BEAMS LEPTONS MIXTURES NUMERICAL DATA ORGANIC COMPOUNDS ORGANIC NITROGEN COMPOUNDS PARTICLE BEAMS RADIATION CHEMISTRY RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY RADIATION EFFECTS RADIATIONS RADICALS RADIOLYSIS REACTION INTERMEDIATES REACTION KINETICS SOLUTIONS SOLVATED ELECTRONS SOLVATION SPECTRA SPECTROPHOTOMETRY |
| title | Radiation chemistry of aqueous solutions of dicyandiamide |
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