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oai:www.ideals.illinois.edu:2142/44797 2023-07-11 col_2142_5131 col_2142_14770 com_2142_5130 com_2142_3518 com_2142_234

Mariñas, Benito J. Mariñas, Benito J. Plewa, Michael J. Nguyen, Thanh H. Echigo, Shinya Kimura Hara, Susana 2013-05-28T19:20:18Z 2013-05-28T19:20:18Z 2015-05-28T10:01:18Z 2013-05 2013-05-28T19:20:18Z 2013-05 Chloramination is increasingly being used in the United States as a secondary disinfectant as a result of tighter regulations on selected disinfection by-products (DBPs) that include four trihalomethanes and five haloacetic acids. However, recent research suggests that unregulated nitrogen-containing DBPs formed by combined chlorine, such as haloacetonitriles and haloacetamides, might be more toxic than regulated DBPs. Monochloramine has been shown to react with aldehydes, common DBPs formed from ozone and free chlorine disinfection, to form carbinolamines that slowly dehydrate to imines which undergo fast decomposition to nitriles. It is also known that nitriles can hydrolyze to its corresponding amides. However, in this study the formation rate of amides was found to be significantly higher and independent of nitrile hydrolysis. The formation pathways of acetonitrile and two haloacetonitriles (chloro- and bromo-) and three haloacetamides (N,2-dichloroacetamide, 2-bromo-N-chloroacetamide, and N-chloroacetamide) from the reaction of monochloramine with acetaldehyde and two haloacetaldehydes (chloro- and bromo-) were investigated. Chloroacetaldehyde and monochloramine were found to quickly react to form and reach equilibrium with the carbinolamine 2-chloro-1-(chloroamino)ethanol. 2-chloro-1-(chloroamino)ethanol then decomposed through two concurrent pathways 1) slow dehydration to 1-chloro-2-(chloroimino)ethane, which in turn decomposed quickly to chloroacetonitrile, and 2) oxidation by monochloramine to form the previously unreported DBP N,2-dichloroacetamide. Similar pathway was found to take place for the formation of bromoacetonitrile and 2-bromo-N-chloroacetamide from the reaction between bromoacetaldehyde and monochloramine, and acetonitrile and N-chloroacetamide formation from the reaction of acetaldehyde and monochloramine. These parallel reactions are acid/base catalyzed, and therefore, the influence of pH on (halo)acetonitrile and (halo)acetamide formation was investigated. A kinetic model was proposed. Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2013-04-10T20:31:39Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 2 Kimura Hara_Susana.docx: 1647489 bytes, checksum: 9bc300b3d7c1890becc123f8b5d08d46 (MD5) Kimura Hara_Susana.pdf: 2370126 bytes, checksum: 7d88d30c3d129679aedc44aaf403d45a (MD5) Made available in DSpace on 2013-05-28T19:20:18Z (GMT). No. of bitstreams: 3 Susana_Kimura Hara.pdf: 2371904 bytes, checksum: d36219c409b47257107f3740e6388704 (MD5) Kimura Hara_Susana.docx: 1651485 bytes, checksum: e2cfc9dbddec415f31cf290ec0ee023b (MD5) license.txt: 4068 bytes, checksum: b7be5a091160749f34cae4ac0ecf078f (MD5) Restriction data tranferred 2014-07-01T11:17:08-05:00 Original Data Group with Access Administrator Release Date: 2015-05-28 14:21:22 UTC Reason: Author requested closed access (OA after 2yrs) in Vireo ETD system Item marked as restricted to the 'Administrator' Group (id=1) by Seth Robbins (srobbins@illinois.edu) on 2013-05-28T19:21:57Z Item is restricted until 2015-05-28T19:21:22Z Limited Restriction Lifted for Item 44772 on 2015-05-28T10:01:18Z. http://hdl.handle.net/2142/44797 en Copyright 2013, Susana Y. Kimura Hara haloacetamides haloacetonitriles chloramination disinfection by-products monochloramine oxidative amidation carbinolamine carbinolamine oxidation chloroacetonitrile bromoacetonitrile acetonitrile N-haloacetamides N,2-dichloroacetamide N-chloroacetamide 2-bromo-N-chloroacetamide kinetics drinking water Formation of (halo)acetamides and (halo)acetonitriles from the reaction of monochloramine and (halo)acetaldehydes in water text Civil & Environmental Eng 1251 Environ Engr in Civil Engr 0231 University of Illinois at Urbana-Champaign Dissertation Ph.D. PHD:Env Engr Civil Engr -UIUC 10KS0231PHD