CVEN 5424 Environmental Organic Chemistry Lecture 24 – Redox Reactions: Reduction
Announcements Reading Chapter 14, Sections Problem sets PS 8 due Thursday PS 9 out Thursday Office hours (starting next week) Tuesday 11:30 am-1 pm Wednesday 9-10 am by appointment
Reduction Reactions Predicting kinetics with rate LFERs k R redox potential (Marcus) E H 1 ; usually first electron transfer (Eqn ) log k R E H 1 / 0.059
Reduction Reactions Predicting kinetics with rate LFERs k R redox potential (Marcus) E H 1 ; usually first electron transfer (Eqn ) log k R E H 1 / Reduction: faster at higher E H (lower {e - }); able to give e - to compound at lower {e - }
Reduction Reactions Predicting kinetics with rate LFERs k R redox potential (Marcus) E H 1 ; usually first electron transfer k R (Hammett) (Eqn ) log k R E H 1 / log k R Reduction: faster at higher E H (lower {e - }); able to give e - to compound at lower {e - }
Reduction Reactions Predicting kinetics with rate LFERs k R redox potential (Marcus) E H 1 ; usually first electron transfer k R (Hammett) (Eqn ) log k R E H 1 / log k R Reduction: faster at higher E H (lower {e - }); able to give e - to compound at lower {e - } Reduction: faster at higher ; easier to give electrons if more e - - withdrawing
Reduction Reactions reductive dehalogenation (C reduced, X released) R—X R—H R—CHX—CHX—R R—CH=CH—R
Reduction Reactions Reduction of carbon: reductive dehalogenation R—X R—H CCl 4 + H e - = CHCl 3 + Cl - R—CHX—CHX—R R—CH=CH—R
Reduction Reactions Reduction of carbon: reductive dehalogenation reducing conditions (e.g., anoxic) promote breakdown of RX, removal of halogens usually, products are less toxic aliphatic (C 1 and C 2 ) – fast olefinic (R=R-X) – relatively fast aromatic (Ar-X) – slow (e.g., PCBs, chlorinated benzenes) most reductants capable of reducing RX high redox potentials mean easy to reduce
Reduction Reactions Reductive dehalogenation rate affected strongly by ease of breaking the C—X bond C—X bond strength stability of carbon radical formed electron-withdrawing substituents stabilize carbon radical
Reduction Reactions Reductive dehalogenation rate affected strongly by ease of breaking the C—X bond C—X bond strength stability of carbon radical formed electron-withdrawing substituents stabilize carbon radical rate affected weakly by tendency of C—X to accept electron (electronegativity) stabilization of carbon radical by geminal halogen
Reduction Reactions Rank the following three halogenated ethanes by order of reductive dehalogenation rate from slowest to fastest: compound X electro- negativity bond strength (kJ mol -1 ) 1,2-dibromoethane ,2-dichloroethane ,2-diiodoethane
compound t 1/2 (h) X electro- negativity bond strength (kJ mol -1 ) 1,2-dichloroethane>> ,2-dibromoethane ,2-diiodoethane << slowestfastest Reduction Reactions
Predicting kinetics – one example Reductive dehalogenation k R bond strength and electron withdrawal BS: C—X bond strength (kcal mol -1 ) *: Taft constant (Table 12.4, SGI, 1993) BE: C—C or C=C bond energy (kcal mol -1 ) Peijnenburg et al. (1991) Science of the Total Environment 109/110,
Reduction Reactions
compoundBS (kcal mol -1 ) ** BE (kcal mol -1 ) tetraiodoethene ,2-diodoethane ,2-dichloro-1,2-dibromoethane hexachloroethane ,3-dibromobutane ,2-dibromoethane -hexachlorocyclohexane tetrachloromethane sym-tetrachloroethane tetrachloroethene -hexachlorocyclohexane ,2-dichloroethane ,1-dichloroethene ,2-dichloroethene perfluorohexane perfluorodecaline Peijnenburg et al. (1991) Science of the Total Environment 109/110, Reduction Reactions
Example: 1,1,2,2-tetrachloroethane a.k.a., “sym-tetrachloroethane” C-X bond strength, BS = 81 kcal mol -1 stronger C-X bond (e.g., C-F) slower rate Taft constant, * = 4.20 more electron-withdrawing faster rate C-C bond energy, BE = 63.2 kcal mol -1 stronger C-C bond faster rate Reduction Reactions
Example: 1,1,2,2-tetrachloroethane a.k.a., “sym-tetrachloroethane” BS = 81 kcal mol -1 * = 4.20 BE = 63.2 kcal mol -1 Reduction Reactions
reductive dehalogenation (C) R—X R—H R—CHX—CHX—R R—CH=CH—R quinone reduction (C reduction) O=Ar=O HO—Ar—OH
Reduction Reactions Reduction of carbon: quinone reduction O=Ar=O HO—Ar—OH
Reduction Reactions reductive dehalogenation (C) R—X R—H R—CHX—CHX—R R—CH=CH—R quinone reduction (C) O=Ar=O HO—Ar—OH nitroaromatic reduction (N reduction) Ar—NO 2 Ar—NH 2 aromatic azo reduction (N reduction) Ar-N=N-Ar 2 Ar—NH 2
Reduction Reactions Reduction of nitrogen: nitroaromatic reduction Ar—NO 2 Ar—NH 2 aromatic azo reduction Ar-N=N-Ar 2 Ar—NH 2
Reduction Reactions Reduction of nitrogen: nitroaromatic reduction
Reduction Reactions reductive dehalogenation (C) R—X R—H R—CHX—CHX—R R—CH=CH—R quinone reduction (C) O=Ar=O HO—Ar—OH nitroaromatic reduction (N) Ar—NO 2 Ar—NH 2 aromatic azo reduction (N) Ar-N=N-Ar 2 Ar—NH 2 sulfoxide reduction (S reduction) R—S(=O)—R R—S—R
Reduction Reactions Reduction of sulfur sulfone reduction R—S(=O) 2 —R R—S(=O)—R sulfoxide reduction R—S(=O)—R R—S—R sulindac (a NSAID) sulfide sulfoxide sulfone
Reduction Reactions Need electron donors for reduction aqueous species H 2 S, HS - Fe(II) Mn(II) NH 3 minerals, etc. sulfide minerals (e.g., pyrite) Fe(II) minerals (e.g., biotite) Fe(0) in remediation
reduction of organic contaminants oxidation of reductants
Reduction Reactions Zero-valent iron permeable reactive barrier remediation other metals also (Sn, Zn, etc.) iron metal is oxidized “rusting” corrosion Fe 0 = Fe e - E H 0 (W) ~ -0.6 V Promotes reductive dechlorination
Reduction Reactions Permeable reactive barrier maintain redox potential (Fe 0 supply) avoid clogging Commercialization ARS Technologies ARS Technologies
CCl 4 + H e - = CHCl 3 + Cl - Fe(0) = Fe e - CCl 4 + H + + Fe(0) = CHCl 3 + Cl - + Fe 2+ CHCl 3 + H + + Fe(0) = CH 2 Cl 2 + Cl - + Fe 2+ CH 2 Cl 2 + H + + Fe(0) = CH 3 Cl + Cl - + Fe 2+ CH 3 Cl + H + + Fe(0) = CH 4 + Cl - + Fe 2+
Reduction Reactions Demonstrations for ZVI halogenated alkanes, alkenes DDT, DDD, DDE pentachlorophenol triazines (e.g., atrazine, RDX) metals Cr(VI), As(V) U(IV)
Fe
Fe(0) reduction of chlorinated compounds: methanes ethanes propanes ethenes (Johnson et al., 1996, ES&T 30, ) Reduction Reactions
Accounting for Fe(0) surface area better correlation indicates surface process (Johnson et al., 1996, ES&T 30, ) Reduction Reactions
Rate of reduction by Fe(0) depends on compound concentration depends on iron surface area, a s (m 2 g -1 ) k obs (h -1 )= k SA (L m -2 h -1 ) a Fe(0) (m 2 L -1 ) (Johnson et al., 1996, ES&T 30, ) Reduction Reactions
Fe(0) mechanism(s)? A) direct electron transfer from Fe(0) at surface B) reduction by Fe 2+ generated by Fe(0), resulting in metal corrosion C) catalyzed hydrogenolysis by H 2 formed by reduction of H 2 O during corrosion iron surface, mineral surface, or organic matter Reduction Reactions
LFER? relating k SA to two-electron redox potential (E) of compounds ? (Johnson et al., 1996, ES&T 30, ) Reduction Reactions
More representative redox potentials (Scherer et al., 1998, ES&T 32, ) Reduction Reactions
LFERs E LUMO, R 2 = 0.83 E 1, R 2 = 0.81 (Scherer et al., 1998, ES&T 32, ) Reduction Reactions
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