Vol. 5 No. 1 Feb EL ECTROCHEMISTR Y ( ) ( ) ( EHD), ( FDN) ( TEA- PTS), Tri2 tonx-100 ,FDN. EHD. EHD. RH. RH 2. Guidelli, 1.

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1 EL ECTROCHEMISTR Y Vol 5 No 1 Feb ( ) ( ) ( FDN) ( EHD) ( TEA- PTS) Tri2 tonx-100,fdn 2, TEA- PTS TritonX- 100, 2,, ( EHD), [1,2 Nylon66 ] EHD, R- R,R-, RH, RH 2, EHD EHD [1,2 ] Baizer TEA- PTS EHD Guidelli EHD [3 8 ], 32 [9 12 ] ( FDN) ( Ga) %, ,

2 mol/ L NaOH p H = 8, (D GE),SCE,, ( SCE) N 2 15 min, N 2, AMEL473 H, Ga,, , 0 1 mm, 0 5 mm, [9 ] NaOH ( mol/ L) p H = 8, 4 5 h < 0 8 %, g/ s 1 3 s > 1 3 s, N 2 t = 1 s, m = g/ s 2 mv/ s FDN 0 5 mol/ L LiCl, mol/ L FDN V, : V ; V FDN ; V mol/ L Tri2 tonx-100,, ; V i d FDN, ( mol/ L) ( mol/ L) ( mol/ L) Tri2 tonx [3 FDN EHD ], m Ga m Hg, A Ga = m 2/ 3 t 2/ 3 A Hg = 0 85 m 2/ Hg 3 t 2/ 3, Ga

3 1 : FDN TEA- PTS, 0 5 mol/ L LiCl + TritonX FDN ( mol/ L), TEA- PTS 0 1 mol/ L, i d C 3 R, C 3 R FDN TEA- PTS CTEA- 3 PTS > 0 1 mol/ L C TEA- 3 PTS > 0 6 mol/ L C TEA- 3 PTS > 0 5 mol/ L, C TEA- 3 PTS, 1 i d C TEA- 3 PTS, D (2 5 - x) mol/ L LiCl + x mol/ L TEA- PTS mol/ L FDN ( 1) x, 1 (2 5 - x ) mol/ LiCl + x mol/ L TEA- PTS mol/ L FDN Fig 1 Polarographic wave of (2 5 - x), mol/ L LiCl + x mol/ L TEA- : FDN PTS mol/ L FDN Q ( t) = t i dt 0 t FDN, [10 ] Cottrell, Q ( t) t 1/ 2 FDN, 2, E 1/ 2 lg[ R ] 3 20 mv,[ R ] 3 FDN [ R ] 3 µ [ H + ] E 1/ 2 p H, C PTS- 3 PTS [ R ] 3 HCl NaOH p H 4 11 FDN E 1/ 2 C TEA- 3 PTS 1, C TEA- 3 PTS > 0 6 mol/ L, [ R ] 3,lg C TEA- 3 PTS E 1/ 2 40 mv ( 3) 3 a 10-3 mol/ L FDN E 1/ 2 - lg C TEA- 3 PTS ; b 10-3 mol/ L TritonX-100 E 1/ 2 - lg C TEA- 3 PTS FDN [ 3 ] FDN EHD C TEA- 3 PTS > 0 01 mol/ L 1, C TEA- 3 PTS > 0 05 mol/ L 1, C TEA- 3 PTS > 0 1 mol/ L 1, C TEA- 3 PTS > 0 6 mol/ L 1

4 mol/ L TEA- PTS FDN E 1/ 2 3 FDN (10-3 mol/ L) E 1/ 2 - lg CTEA- 3 PTS (a) lg[ R ] 3 Fig 2 Relation between E 1/ 2 and lg [ R ] 3 in the FDN aqueous solution of 0 5 mol/ L TEA- PTS [ R ] 3 is FDN concentration TritonX-100 (10-3 mol/ L) E 1/ 2 - lg C 3 LiCl (b) Fig 3 E 1/ 2 - lg C 3 TEA- PTS curve(a) of 10-3 mol/ L FDN and E 1/ 2 - lg C 3 LiCl curve ( b) of 10-3 mol/ L TritonX FDN [3 ] ( TEA) R-,, FDN EHD, Tri2 tonx-100 4, FDN (Li- PTS) ( b) TEA- PTS ( a) TritonX-100 ( d) ( c) 1, 4 FDN (10-3 mol/ L) 1, Fig 4 Polarographic reduction wave of TritonX mol/ L FDN in the differ2 FDN ent surfactants C TEA- 3 PTS 0 6 mol/ L (a) TEA- PTS,(b) Li- PTS, (c) lg[ R ] 3, E 1/ 2 20 mv, p H > 4, Phosphatide tribenzol methyl bromide, (d) TritonX- 100 TritonX-100, [ R ] 3,

5 1 : 103 lg[licl ] 3, E 1/ 2 40 mv ( 3) 2 4 E = V : mol/ L TritonX mol/ L LiCl mol/ L FDN CH 2 Cl 2 CH 2 Cl 2 Kolfer ( 60 %) , ( 40 %) [3 ] FDN ( ), [3 FDN EHD ] ,2,3,4-3 [13 EHD ] lg[ R ] 3, E 1/ 2 20 mv, E 1/ 2 p H, TEA- PTS TritonX-100 FDN : R + e Ω E R - ; 2R - k R2 2 - ;R H + = R 2 H 2 (1) r d s (r d s) R - (1) E lg[1 - ( i/ i d ) / ( i/ i d ) 2/ 3 ] R T/ F = 59 mv, (1) E = E 1/ 2 + R T F ln[21/ ( i/ i d ) ( i/ i d ) 2/ 3 ] (2) E 1/ 2 = E 0 + R T/ 3 Fln [ k [ R ] 3 2 / 3 D ] ; ; k R - ;D R FDN 2, R RH 2 [14 ], H + [14 ] R -, FDN EHD Tri2 tonx-100, 10-3 R - mol/ L TritonX-100, R -, R -,, R - RH 2 TEA- PTS TritonX-100 LiCl, FDN

6 E 1/ 2 : E 0 R + e Ω R - R - + C + = C + R - 2C + k R - dimer (3c) r d s (3c), (3) - (2), E 1/ 2 = E 0 + ( R T/ 3 F) ln [ k [ R ] 3 2 K[C + ] 3 (1 + K[C + ] 3 ) / 3 D ] (4) [ C + ] 3 ; K = [ C + R - ] [ C + ][ R - ] (3b), K[ C + ] 3 ν 1, (4) [ C + ] 3, lg[ R ] 3, E 1/ 2 20 mv ( 2) [ R ] 3 lg[ C + ] 3, E 1/ 2 40 mv ( 3) (3) EHD (3a) (3b) [1 8 ] FDN EHD,, Electrohydrodimerization of Fumarodinitrile on Liquid Gallium Electrode He Wei 3 Huang Ying ( Dept of A ppl Chem, U ES T of China, Chengdu ) Zhang Shengtao ( Coll of Chem and Chem Eng, Chongqing U niv, Chongqing ) Abstract Electrohydrodimerization ( EHD) of fumarodinitrile on liquid gallium elec2 trode can take place not only in hydrotropic solution of tetraethylammonium p-toluenesulphonate ( TEA- P TS), but also in aqueous solution containing low concent ration of st rong surfactant s, such as TritonX-100 In solution without organic surfactant, FDN yields a single two-electron re2 duction wave corresponding to t he formation of a sat urated monomer called as butanedinit rile If some TEA- PTS or TritonX-100 is added into the solution, the original two-electron wave is split2 ted into two continuous single- elect ron reduction wave and corresponding EHD of f umarodinit rile is obtained marodinit rile Key words Gallium, Electroreduction, Electrohydrodimerization, Polarography, Fu2

7 1 : 105 Reference s 1 Baizer M M, Petrovickh J P Progress in physical organic chemistry New York : Interscience, 1970, 17 : Baizer M M Organic electrochemistry New York : Marcel Dekker, 1973 : Moncelli M R, Guidelli R Mechanism of electrohydrodimierization fumarodinitrile on mercury from aqueous media J Electroanal Chem, 1983, 143 : Moncelli M R, Guidelli R Mechanism of electro- hydrodimerization of chaleone on mercury from aqueous solu2 tion containing strong surfactants J Electronanal Chem, 1984, 172 : Moncelli M R, Guideelli R The mechanism of electrohydrodimerization of chalocne on mercury form aqueous solution J Electroanal Chem, 1985, 183 : J uan Ruiz J Foresti M L Chronocousometric investigation of benzophenone electroreduction on mercury from acidic aqueous media J Chem Soc, Faraday Trans 1, 1988, 84(12) : Yolanda M, Guidelli R Mechanism of electrohydrodimerization of cyclohex-2-en-1-one on mercury from aqueous solutions( Part 1) J Chem Soc Faraday Trans 1, 1988, 84(1) : ibid( Part 2) 1988, 84 (2) : Pezzatini G, Guidell R A dropping gallium electrode for dobule layer and kinetic studies J Electroanal Chem, 1985, 196 : Pezzatibi G Guidell R Comparatie adsorption study of tert-pentanol and isopropanol on mercury and gallium from aqueous 0 5 M Na 2 SO 4 J Colloid Interface Sci, 1991, 146 : Pazzatibi G, Guidelli R Comparative adsorption study of thiourea on mercury and gallium from aqueous 0 5 M Na 2 SO 4 J Electroanal Chem, 1991, 301 : Guidell R Aloisi G Electrifield interface in physics, chemistry and biology, NA TO ASI series, kluwer, Dor2 drecht 1992 : Nadjo L, Saveant J M The diagnostic criteria for electrohydrodimerization J Electroanal Chem, 1973, 44 : Guidell R, Moncelli M R Electrohydrodimerization of fumarodimitrile on mercury from aqueous mdeia ( Preliminary result) J Electroanal Chem, 1981, 129 :