T r a n s a c t i o n. P a p e r. Synopsis. Introduction. Experimental

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1 Sy h g f W. 2. h lhml lhg bhvu f mll lly dvd fm w d u bd by D.R. G* d J.A.N. v d Ld* S d u bd w lvly mld C du mll lly hvg h h. h h w dfd ld-h h, lw lh bz h, d hgh dl h. Elhml lhg ud h lly w d 1 ml/dm3 ulfu d 2 ml/dm3 hydhl d (djud gh f 3 ml/dm3). h ld h h w m gly vd ulf md, d h mdum h hgh dl bz w m h h lw lh bz h. I hld mdum h ld h d bh bz h dd dly, bu wh u d bu d f mgud lw h ulf mdum ( d) f h bz h. h hgh dl bz h w fud fm vg ly ulf md. A ml ly w hld mdum. h lhg ud ulf mdum l hwd h x f lh bz h f lw h f h lh h g. h h w qu lhg ulf mdum. Idu I l 1 w hw h hgu mll lly g f vu h my b dud by h lv mlg f l d u bd. h lly w hzd ug SEM-EDS, d by ug mb f h dgm d hmdym lul, w hw h h bu 56 m f lh bz h, bu 35 dl bz h wll 9 f ld-h h. M lm uh kl, z, gld d lv dbud bw h vu bz h d h ld h. A dvg f lv mlg u h d l wll lumum jd, whh dvgu f ubqu hydmllugl g. h lly dud by lv mlg hv uff mhl gh d ll duvy d f mkg mu d b ud dd fy. A mj m f h lly, vz. 70 m, wuld m bl u h u f dug lbl ml. Oh ml uh ld,, gld,. wuld h h d lm h lly, d uld vully b vd. F h lly fu ffvly mu d lfg, w m blh lhml lhg bhvu. I hd b blhd whh lv lhg f h wuld u, whh v w lkly, d whh h d ml wuld uff mhl gh. Alhugh h lv mlg uful dug xmly mlx d hgu fd muh ml md, h md vl mll h wh umb f m mll u. I d dl wh h mlx fd ml, hydmllugl mhd uld b ud b h lvy h qud. Hydmllugl x uld fllw f w bd u, vz. lv -lv lhg, fllwd by ubl d vy mhd. h wk d h ud h l lhg f hydmllugl g f h lly. Exml Rg dk ld w md u fm u ml w ml lly d. h ml d w mud ubl fl hld ug Im xy. Ell w md h hf ug mv w. A Ium w ud. Eld w d by gdg h ld uf, fhg wh g. h ld w h ld h dxygd * Dm f Ml S d Mllugl Egg, Uvy f. h Suh Af Iu f Mg d Mllugy, SA ISSN X/ vd S. 2008; vd vd Ju h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 109 REFEREED AER DECEMBER

2 h g f W. 2 lly, d gv hd m du uf xd d b dubl ld uf. h l ud w 0.8 V x h f, wh l f 0.4 d 0.5 V w ud ulf d hld md vly. h ulf d hld lly w md u ml gh f 3 ml/dm3 1 ml/dm3 ulfu d, 2 ml/dm3 hydhl d wh ddd dum hld. I gh ud h h ml mg, x h ml w ud h u. A dd h ld lhml ll w ud, wh h g dk ld h wkg ld. h ll mu w lld 25 C by ug w jk. h u ld w h 5 mm gh d ( ulf md) lum w ( hld md). h Ag/AgCl f ld (-222 mv v SHE) w ld ubl Lugg lly, uh h h f h lly w wh 2 mm fm h wkg ld uf. h lly ub w flld wh h ud lu f dum ulf um hld, h h f h bdgg lu mhd h f h wkg lly. A Sl SI 1287, lld v l mu ug h fw, w ud. S w 20 mv/. Elly w dxygd ug g g, d xm w dud g mh. h lu f h xml gm h u l w mud, d w fud h z. hu h d u d f lu. Eld l d g h Ag/AgCl f. Cu d luld bd h gml. Suf hz f h ld w d ug h ubl l m, Jl JSM 6300 g l m wh N EDS (gy dv X-y y) fl. Bf uf hz h ld w whd hughly wh dlld w. Wh lyg ml wh h SEM, h ml w dd ud hgh vuum mv d w. Wh EDS w ud f h ly, yl u w f h d f fw hud. ubx (Eh-H) dgm w gd ug h W32-SABCAL 2000 fw2. Rul d du Dlu ulf md Du h mlxy f h lly ml, f m u ld w l md f h u mj m ml, vz., d ld. h vlmmgm f h lly ml w h md h f h u ml. h d bhvu f hw h mbd yl lz dgm, Fgu 1. C my b d vly bv bu 0.05V, whh g wll (wh h l vd h SHE l) wh h ubx dgm Fgu 2. h bly g f uu mll, d dlu k xd h vlmmgm. h xd f u w h u hugh h uu 3. Byd bu 0.3 V v f h uf u, bbly hugh h fm f ld hydd u ulf. Sml v wll kw blm h lfg f 4, wh h v ly fd blu. Wh v dud, h k hgh bu 0.3 V, wll h lmg u dy h lu g byd 0.5 V. A ulfu d 2 ml/dm3 hw h v u bu 0.1 V blw h l dd 1 ml/dm3. A v mhm vlvg u ulf gm wh h bv. ml l d hgh 1 ml/dm3 ulfu d mdum, v ud d whu fd v. Fgu 1 llu h. A vy lw dlu f ld w xd ulf md, ld dly fm v v flm f ld ulf h lw l, whl ld dxd uf ly xd b h hgh l dg h ubx dgm f ld, Fgu 3. h vlmmgm f ld, Fgu 4, h wll dfd k fm V -0.4 V f whh v u. I xd h ld ulf uf ly fm V wh h l k u dy d ff dly. Fgu 1 Vlmmgm 20 mv/ f lly,, ld d ld dxygd 1 ml/dm 3 ulfu d Fgu 2 ubx dgm f 1 ml/dm 3 ulfu d d f 1x10-6 ml/dm DECEMBER 2009 VOLUME 109 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy

3 h g f W. 2 Eh (vl) Fgu 3 ubx dgm f ld 1 ml/dm 3 ulfu d d ld f 1x10-6 ml/dm 3 Fgu 4 h lw l g f Fgu 1 h vlmmgm f lly dlu ublly h m h f, u bu 0.5 V. v u lw u dy d hgh l h f u. h d hf f bu 0.1 V d h h bz h m h u. Ally f m h h l u ml m h lly, h Cu-C-F ym5 7, h Cu-N b ym8, d h Cu-S bz ym9. h dlu f lly ml b lv lv, ddg h dx l whh dlu u, wll h m f h lly. N-lv dlu u wh gl h lly (ld lu), f h dff dd l f h m ml mll, lg vvlg. h bhvu dd h dff dd l, d h lly m10. Ally wh h m bl m xdg 50 (whh h ) hv dlu l hgh h h f h l bl m11. Wh lv dlu f by lly u, h lz dgm wuld hv w g du h dff dd l f h m bg lg. h f g u wh h l g l h dlu l f h l bl m. Slv dlu f h l bl m glly u h l g9. h g hzd by lw lmg u dy h d wh h dmg dlu f h l bl u. Wh h l h dlu l f h m bl m, hgh f dlu f h h l bl m ly, h dlu f bh m. h d g h hgh u d, wh l dg h dlu l f h m bl m. h u f h l l h b hd. Slv dlu u fquly wh h m bl f h lly u mll 10. I h lfg f d, d lm g bl ml hu ld fm h mx du lv dlu f h mx. h vlmmgm bd f lly dlu w xmd h lw l g. A xml hw Fgu 4. I h lw l, ud 0.5 V, lhd lw fm h bz h. h uggd by h mll d k 0.5 V, d h dg du k 0.57 V, d d h f l g md bv. Slv dlu f h b hw u h l g lh h bz9. Abv 0 V h m bl bz h d, my b fm Fgu 1. Wh h u, du k 0.02 V. h du k hgh h mxmum ld l, u 0.5 V. Slv dlu h b fud u fm h lh bz h ulf md l h d g9. h uxd, bu b du h fm f xd v ly. h ly vy v, llwg ubl dlu. Ahlgl bz hw ml hd. I h v g, bv 0.5 V Fgu 1, h lly bhvu mkdly dff fm h f. v f h ld bly l h h f. Wh h ld lzd h l h du k hgh d, bu huld fmd 0.1 V, d h du k l hgh. h du 0.1 V bbly du h du f (I). I m h h v ly hd, bu h (I) l fmd. C(I) xd hv b fud h v ly fmd dug bz 12. Alhugh h ubx dgm hw uu xd b bl ly H vlu hgh h bu 4 lw dlvd, bly lw H vlu mkdly h dlvd. Hgh h ld lu f wuld b xd uffly hgh ld l h b f v. h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 109 REFEREED AER DECEMBER

4 h g f W. 2 I w fud h h blk ly h dl bz wh h ld lzd 0.2 V hgh. EDS ly f h ly hw bl hm, ld, gld d lv, whl ll hvg hgh. h v ly fmd h lly hu b qu mlx m. A fm h vlmmgm, h ml u fm d m v ud h d f h udy. l d v h b d u ly ulfu d bv 3 ml/dm3, wh ld l >0.35 V. h v ly mly h (. 100 m), mhu SO ly13. Dug h f bz ul lu xd ly h l b fud fm. h ly ll llw dlu f udlyg 9. I ludd h h h v ly l xd h ddlly h yl d lm m fmd dug lfg4. Evully, fm k l f 0.8 V h u dy h gv ml h f h vd ld. I lkly h hydd ulf du hu l fmd h lly. Slv lly dlu wll ul uf g v h fm f u uu. Wh ud m l d, h lhml dlu k f uh ym wuld b xd hg wh m, du hg h uf f h lly h, wll du hg h m f d du. M xm f h ld uf h udy fmd h h lh bz (lw ) h dd flly md h dl bz h. h gm wh h fdg f Mbll9, wh fud fl dlu hzd by lw. Fgu 5 hw l mgh f ld ubjd l fm 0.3 V 1.2 V. h y du lv dlu f h lh bz h, wll h (lw lf ) wh lhg h. I m h h w h ml h lh bz h, wh lghly hgh d lvl, bu mwh lw. I w h f h lh h g, d hu h ml fmd dug lg. Ud h l m h h uld b dffd fm h h. h lly bhvu w fuh udd ud l d. A l f 0.2 V w ud f 600. h l wll wh h g f v l f bh d lly dlu. h u dy w fud d wh m. Slv dlu f bmuh ud fm h ld h h. Ag fl dlu f h lh bz w, wll h h, blk ly h dl bz h. h ly uld b hd ff ly. Fm h l ud d h vlmm wk w bl dm whh lly h dd ul l g. h fdg ummzd bl I. h lh (lw ) bz h w fud lh m dly h h dl h. C hld md Chld md glly m ggv h ulf md m f lhg, du h bly f hld ffvly blz my ml quu lu. L lv dlu hu xd. C w fud dlv ffvly hld mdum, my b fm Fgu 6. Dlu u lw l h ulf md, fm -0.2 V, du blz f h. h mxmum u dy hd bf v k l ( bu 0.05 V) lw hld mdum h ulf. h ldlu f hld md h b vwd by K14. A lw vl CuCl - 2 fmd ud d f mxd hg f d du m l. I h x l g, Fgu 5 Ol mgh f lhd lly ld uf bl I h f lhg bvd f vu lly h 1 ml/dm 3 H2SO4 Ally m Elm Ld Bz, Bz, I h lw hgh h m % m % m % m % Ag Al Au B Cl Cu F N b S Z ml/dm3 H 2 SO 4 R f lhg l g (V) Vy lw N N N N N N N N Hgh Slw N 704 DECEMBER 2009 VOLUME 109 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy

5 h g f W. 2 Fgu 6 Cylvlmmgm 20 mv/ f lly,, ld d ld dxygd 2 ml/dm 3 hydhl d (djud gh f 3 ml/dm 3 ) (bv bu 0.1 V 4.0 ml/dm3 NCl) CuCl flm fm u d lu. h x f flm fm dd h hld d v. A ll hgh l bh h dhl (I) mlx d u fmd. I h f h bhvu hld mdum ml h ulf mdum, bu v hgh u d w. h w d f v, whh mgh b xd u hugh h fm f, f, SO 2. h ubx dgm Fgu 7 hw h hgh dy d hld lvl vg ld uh SO 2 ly fmd. Ld dlv hgh hld md h ulf, my b fm Fgu 6, lly wh md Fgu 1. Ld hld bly m lubl h ld ulf. Ld fm15 h gly lubl ld hld lu wh lvly lw f hld, d g mu f bcl 4-2 wh h f hld byd 0.1 ml/dm3. v by ld hld 0.5 V. Rdu f h ly k l h v, g fm 0.55 V. If h f h ld d, h du k d, du mvd m f hld h dlv h ld hld v ly. Fm h ud h u ml my b ludd h d ld wll dlv m dly hld mdum h ulf, bu f h v. h h vlmmgm llud Fgu 6. Ag h lly bhvu ublly ml h f, bu wh lw u h g bv 0 V. h ly Cu-13S lly h b fud b hk d m bl h h h u ml12. h bly f h ly h b bud h fm f -g 16. Adg h uh h lhml bhvu f h lly l bv bu 0 V mlx, vlvg bh d, h dffu f hld d mlx ml du, wll u ly fm. Ig d h u h l g bv 0.2 V. Imvd m f hld wuld b xd ld mll mu f CuCl h ly, d hu l v. h du k dug h hd 0.2 V d wh dud. h k du h du f CuCl, whh u 0.2 V 1 ml/dm3 HCl lu17. Wh d m h CuCl ly wll hmlly wh hld fm lubl mlx. Wh h d lm f lly ld w d w fm 0.3 V 1.3 V, h u h v g md uhgd, bu h hgh f h du k d wh g d lm, du h ld bg h hgh l g f lg m, fmg m f h uu h ly. A m f lly lhg h w md hw Fgu 8. h blz f d h g x f v hld md lly. C l d dlu xm w d 0.05 V d 0.3 V, h v l d v dlu g h hld md. h Fgu 7 ubx dgm f hld mdum Fgu 8 Vlmmgm 20 mv/ f lly ld dxygd 1 ml/dm 3 ulfu d 2 ml/dm 3 hydhl d djud gh f 3 ml/dm 3 h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 109 REFEREED AER DECEMBER

6 h g f W. 2 hld dfy h h h lhd h vu ld l g. bl II ummz h ul bd fm h xm d h vlmm wk. Af 600 lz 0.05 V h lly uf w u, d ml h bd ulhu d. Hwv, l f h ld h w. lz 0.3 V uld u f bu 100, dg f dffu. h w du m v f h lly uf, wh ll y dvld. h ld h dd d m lwly h h bz h, d f ld d ud f h uf. h h w g vbly lhd. Clu h lhg bhvu ulf d hld md f lly fmd by h hgh mu mlg f d u bd ml w md h f h u ml,, d ld. Svl mll h w fmd d dfd h lly: ld h h, d w bz h wh dffg. Elhml lhg ud hwd h h bhvu f h lly dffd h w md udd. A xd, h ld h h w m gly vd ulf md, d h mdum h hgh dl bz w mkdly m h h lw lh bz h. I hld mdum bh bz h dd dly, bu wh u d bu d f mgud lw h ulf mdum ( d). h hgh dl bz h w fud fm vg ly ulf md. A ml ly w hld mdum. Af lhg ulf mdum h lly uf hwd vd f fuh h whh w m h h dl bz h. h ml w h f lh h g, d b mwh hd. I m bu 79 m bl II h f lhg bvd f vu lly h 2 ml/dm 3 HCI (djud gh f 3 ml/dm 3 ) Ally m Elm Ld Bz, Bz, I h lw hgh h m % m % m % m % Ag Al Au B Cl Cu F N b S Z ml/dm3 HCI l g (V) R f lhg Slw N N N Slw Hgh N N Slw Hgh Hgh N d 9.5, whl h lh bz d 75 d 13. h h ll lh bz, lh bz hv vyg bw 0 d 15.8 wgh. A hgh lg mgh v fm. h lly h w fmd hugh d mlg d m b ubl f mkg d f lfg. I ulhu d h dm lw (13 S - 75 Cu) lh bz h lh flly h h h, d mll v m ( 10 S 79 Cu) md h h lhg ud h d f h ud. h mhl gy f ld lfg hu lkly b blm, whl ubl mu f ml m h dlu. Addl wk wuld hv b d dm whh mxd ulf/hld lly wuld hv bf mmg fl dlu f m h. I wuld l b m blh whh h v ly wuld b uff -dh fm ml d lm. Flly, mhl huld b d u h lly f l lhg u h uff mhl gh d. A lv u wuld m bfl dd u h CB ml, h h fll blw 10 m. h wuld u h fm f gl lh h bz, vdg h fm f h h. h bf wuld b mvd, h vd f h fm f gly v ly ulf md, d mvd mhl gy h d. h ld h wuld b vdd, hwv, h ulf lly fl dlu f h bz h wuld ll u. Akwldgm h uh wh x h wd f Ch u f h vlubl mm d ugg. h m ublh d u f h Uvy f kwldgd wh. Rf 1. GROO, D.R. d VAN DER LINDE, J.A.N. h g f W. 1. h d hz f mll lly dvd fm h mlg f d u bd. Jul f h Suh Af Iu f Mg d Mllugy, vl. 109,. 12, W32-SABCAL H-Hug Hug. Mllugl Egg, M h. 3. CHENG, X. AND HISKEY, J.B. Fudml Sud f C Ad v Dug Elfg: II. Suf Mhlgy, M. d M.., vl. 27B, DAVENOR, W.G., KING, M., SCHLESINGER, M., d BISWAS, A.K. Exv Mllugy f C. gm BuRZYNSKA, L., GUMOWSKA, W., AND RUDNIK, E. Iflu f h m f Cu-C-F lly h dlu mml lu, Hydmllugy, vl. 71, DECEMBER 2009 VOLUME 109 REFEREED AER h Jul f h Suh Af Iu f Mg d Mllugy

7 h g f W BURZYNSKA, L., GUMOWSKA, W., d RUDNIK, E. h flu f h uu h dlu f Cu-C-F lly ulhu d lu, Hydmllugy, vl. 71, HURADO, M.R.F., SUMODJO,..A., d BENEDEI, A.V. Elhml ud wh Cu-5w.%N lly 0.5 M H 2 SO 4, Elhm A, vl. 48, BADAWY, W.A., ISMAIL, K.M., d FAHI, A.M. Eff f N h bhv f Cu-N lly ul hld lu, Elhm A, vl. XX, MABILLE, I., BERRAND, A., SUER, E.M.M., d FIAUD, C. Mhm f dlu f Cu-13S lly lw ggv d, C. S, vl. 45, BURZYNSKA, L. Cm f h u d d dug dlu f b, C S, vl VVEDENSKII, A.V. d GRUSHEVSKAYA, S.N. K ul f d dlu f d gld lly md by h fm f lubl Cu(I) du, C. S, vl. 45, AMMELOO, F., FIAUD, C., d SUER, E.M.M. Chz f h xd ly Cu-13S lly NCl quu lu whu d wh 0.1 M bzzl. Elhml d hhml bu. Elhm A, vl. 44(15), LAIINEN,., SALMI, K., SUNDHOLM, G., VIINIKKA,., d YLI-ENI, A. h d bhvu f ulhu d lu. Elhm A, vl. 37,. 10, KEAR, G., BARKER, B.D., d WALSH, F.C. Elhml f ullyd hld md l vw. C S, vl. 46, AN, K.G., BARELS, K., d BEDARD,.L. Ld Chld Slubly d Dy D By Aquu Slu. Hydmllugy, vl. 17, SOUISSI, N., SIDO, E., BOUSSELMI, L., RIKI, E., d ROBBIOLA, L. C bhvu f Cu-10S bz d NCl quu md Elhml vg. C S, vl 49, BARD, A.J. Eyld f Elhmy f h Elm. vl. II. Ml Dkk, h Jul f h Suh Af Iu f Mg d Mllugy VOLUME 109 REFEREED AER DECEMBER