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T& gֳgֳ ?"P   LUSQdkYkHrh7h_    Tx{gֳgֳ ?"``   Z*  T({gֳgֳ ?"`    \*  TW{gֳgֳ ?"`    \*   0x{ "   8USQdkYkHre,g7h_ ,{N~ ,{ N~ ,{V~ ,{N~  `  Hd޽h? ? f3f3 Soaring0    @(  T t  "tZ  S BsC5 DEHFPv @?3 r4 rv$[I_l3HxF 3 %(@" 2  3 CRENGCJRQ1? `TO`TR`TO`TRR`TRR"t  TH{gֳgֳ ?"/O { LUSQdkYkHrh7h_    T[{gֳgֳ ?"pp  { NUSQdkYkHroRh7h_   T{gֳgֳ ?"`` { Z*  T{gֳgֳ ?"`  { \*  T-{gֳgֳ ?"`  { \*`  Hd޽h? ? f3f3  2 * 0  (    Tܔ ??p ( 2F  T ??T  ,{4z MTirS^:gtTRRf[ l(2$$$$ $r   f Ԕ??`J  Z ??  S^ :gtvxvz xvz[a: Co3+ , Cr3+ , Ni2+ ,Pt2+I{-N_yP[, {USMSO xvzveh(time scale )V: 100s (`'`STir) ms (;m'`STir) ms (5uwyT5uP[ly)  xBx0x     A     f ??0dC dMSOSN (NbcS^)  0   f ?? :5uP[lyS^('lS؏SS^) Taube , Marcus     T@ ??P@p Z $N{| 2    f Ԕ??@ pP   T ?? 0  f MSONbc 2H  0޽h ? f3f3d  @L(  Ll L T$ ??4TLD___PPT9& MMOSN(substitution)S^ S^:gt: ϑsQ|, se z mB\!kv:gtxvz,q_TS^svV } -N_yP[ v5uP[~g(LFSE, HS, LS), N`, JS_ ySWV(leaving group) ( TMv\O(u) ۏeQWV(entering group) ( gq_Tbeq_T) eMOWV(spectator ligands) (OY, [MOHe^) zzHe^(steric effects) 2 2$ s2 s2$'   ;   H L 0޽h ? fDW&cC3 6.P P(  P P T$ ?? - n1. kQbSOMTirvSNS^ 2 p P HA ?? P T ??[PH@___PPT9" < y:gt(dissociative), D:gt B 2 2&  @`p P HA?? @p   P T ?? @ g ^-NSO, SKm[ 2 H P 0޽h ? fDW&cC3{  + # `T (  T T Z ??p. O $  T Z  ??  hYvSm^T'`(esQ SNwYMTirvSm^ gsQ Vdkse z:N S^s= k[ML5 X] ( se zNۏeQWVyvSm^esQ SN1USRP[N8h) Co(CN)5H2O2- Co(CN)52- + H2O Co(CN)52- + Y- Co(CN)5Y3-     &       "    ,|% AQN T C A "0 vN  T C A"   T T0 ??P +  xnY-R+R:NBr-, I-, SCN-, N3-e k1` ZD??`B ?` ZD??  @` Tos ??   z6~MSONbcS^vsNۏeQWVesQ cdT:gt0 2 H ` 0޽h ? 1. (򣩻PowerPoint ʾĸPowerPoint ʾĸPowerPoint ʾĸ2. ڽ磨򣩻PowerPoint ʾĸPowerPoint ʾĸPowerPoint ʾĸ  õʾĸģ_ Q**wangzhy õƬ fDW&cC3c      (  x  c $ }s&  s   <A  "p s  Z4s ?? - Bsks[MTir] + ky[MTir][Y-] nBRSǏ z YMMOvSRP[Ǐ z RRf[SMOHe^(kinetic trans effect) H2O < OH- < F- RNH2 py NH3 < Cl-< Br- < SCN- I- NO2- C6H5- < SC(NH2)2 CH3- < NO H- PR3 < C2H4 CN- CO j~S   X -X  TT{ ?? 00@ ASN2" 2H  0޽h ? fDW&cC3  $_(  $N $ C A"N $ C A"N $ C A": $ TP ??  SMOHe^ NH3 < Cl- P 2$H $ Z ??P V  SMOHe^ Cl-< NO2-`   $ c $(   '  H $ 0޽h ? fDW&cC3 nf(  N  T ??%bZR___PPT94, `p SMOHe^vʑ T(SMOWV, s~SOTpSSO) NMv\O(u:_1_ gSt, SMOWVvSb_'`'Y(fgS)v 2 2 2  @   @`p  HA??` H  0޽h ? fDW&cC3 l,(  l@ l T ?? 43q_TSNS^svV }  -N_MvJS_ 5uw8 2  , l C AlD:\inorgCDROM\Ic3\ChaptersFigures\ch7gif\fig0725c.gif`O3H l 0޽h ? fDW&cC3 nf (    Th ??+  B^4lNbcsv'Y\ S:SdMgTBeNY 0s'Y d:S0s-NI{ d100;m'` zW0;m'` ^ 2& 2 2#  b  H  0޽h ? fDW&cC3  Dp1(  px p c $xs T  s  F   9p Pp` @   7p @ J 4pJ 1p Z ??+ ]/d0 d1 d2 d4(HS) d5(HS) d6(HS) d7(HS) d8 d9 d10 x, x  3p Z ??Jt@ J  6pJ  2p Zs ??u   CaEDTA2-, Sc(H2O)5OH2-, TiCl62- Ti(H2O)63+ , VO(H2O)52+, MoOCl52- V(phen)33+, ReOCl53- Cr(H2O)62+ Mn(H2O)62+, Fe(H2O)4Cl2+ Fe(H2O)62+ Co(NH3)62+ Ni(en)32+ Cu(NH3)4(H2O)22+ Ga(C2O4)63- $x x  NJO  5p Z ??J  8p T ?? 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MMOB\ NS< 2 2 2 @`p  HA?? d H  0޽h ? fDW&cC3 TL`D(  D D C ApD:\inorgCDROM\Ic3\ChaptersFigures\ch14gifs\fig1410c.gif@  D T ??p p"FeMTirv5uP[NbcS^vS^PWh(2H D 0޽h ? fDW&cC3 pN(    C A pD:\inorgCDROM\Ic3\ChaptersFigures\ch14gifs\fig1411c.gif ^  Z ??p  (a) ;mSDGؚ,S^1uDGؚ (b)S^MRTϑvI{ Gibbs1uDG:N (c)NirϑNO ;mSDGTDGNO (d) ;mSDG=0, NirϑNO S^1uDGg\, 5uP[lySۏL s         H  0޽h ? fDW&cC3 >(    ZP ??P  |R.A.Marcusb NV }[ϑh:N k2= fk1k2K (Marcuse z) K:;`S^vs8^pe k1Tk2:$N*NNbcS^vs8^pe K:;`S^vs^a8^pe f/f1us8^peTibces~bv YTSpe   >                  +   H  0޽h ? fDW&cC3\   0(  r  S ܡ{M   { r  S { @ { p  HA??PpH  0޽h ? fDW&cC3 P(    TK{ ?? ,$D 0 *YUOf/fQLu:gt? Sl: GPHQly5uP[ [Cr(II)(H2O)6]2+ (t1/2 = 10 9s) Cr(H2O)63+ (t1/2 = 106s) 000000000000000`'` GPHQlyClMSO [Co(III)(NH3)5Cl]2+`'` W 2 2 CKCKCKG.&CKCKKG.&O  CKCKCKG<KC(b=>(H  0޽h ? fDW&cC3a  4(  4 4 T. ?? 1  2p 4 HA?? 4 4 TH  ?? @ 4Co(III)TCr(II)5uP[lyvQLu:gt:yaV(2A<H 4 0޽h ? fDW&cC3 `X`(    Tx ??i 4`[[(uCr3+aq)6RYCr(en)33+e RZnv\O(u/fNHN e:gSf[[ N1 2  b H  0޽h ? fDW&cC3r  m@ ^l)LQ#Wa2gpqy3,(!!  &mg+g7  ,!( / 0DTimes New Roman\8|dv 0|( 0hD[SOes New Roman\8|dv 0|( 0h DArial Blackman\8|dv 0|( 0h"0DArialBlackman\8|dv 0|( 0h"@DWingdi$/:ңH!f$ -"$ "N(PKEfQ7"$$ξb(ihVK"$ q޲ũx[/Oab$Aez^;72$qe>^T6 or$2$8$$D{2$p"FK-H+2$'1ZćY( 0e0e A@A5%8c8c     ?1d0u0@Ty2 NP'p<'p@A)BCD|E? @8+,uʚ;2Nʚ;g4CdCdv 0pRppp@ <4!d!d` 0,H9<4dddd` 0,H9 <4BdBd 0, ___PPT9nfFu88 PNG  IHDRW?sRGBgAMA7 cHRMz&u0`:pQ< B B  & 2.s^bVeb_MTir  $  !((2). D:SCQ }vLFSE0G$`'`(inert)MTir   $   "#N. 'lS؏S(5uP[ly)S^$ N Tvё^\yP[ly 'lS؏SS^( gQSf[SS) Tyё^\yP[ly 5uP[NbcS^(eQSf[SS) OY [Co(NH3)6]3+ + [Cr(H2O)6]2++6H3O+ [Co(H2O)6]2+ + [Cr(H2O)6]3+ + 6NH4+ ('lS؏S) Fe(H2O)62+ + *Fe(H2O)63+ *Fe(H2O)62+ + Fe(H2O)63+ (5uP[Nbc)G3 BJBJBNJBJBJBNBJBJBBJBJBNJBJBJBNJBJJBB              b9H8 $ %&'2. QLut :gt    ^[Co(III)(NH3)5Cl]2+ + [Cr(II)(H2O)6]2++5H3O+ d6 d4 [Co(H2O)6]2+ + [Cr(H2O)5Cl]2+ + 5NH4+ d7 d38 BJBJFBJ BJBJBJBJBJBBF6NFNFBJBJBJBJBJFBJBJJBFNFN)* /8 Z    0  (    T O ??p ( 2F  TR ??T  ,{4z MTirS^:gtTRRf[ l(2$$$$ $r   f Ԕ??`   Z4Y ??` S^ :gtvxvz xvz[a: Co3+ , Cr3+ , Ni2+ ,Pt2+I{-N_yP[, {USMSO xvzveh(time scale )V: 100s (`'`STir) ms (;m'`STir) ms (5uwyT5uP[ly) xB0     A     fn ??0dC dMSOSN (NbcS^)  0   fq ?? :5uP[lyS^('lS؏SS^) Taube , Marcus     T \ T! ??0 0000000000Ǐ!n` NhQ r k[M0] I:gtTA:gtv$Re -NNirintermediate)X[(WYve &TRybhQ OPt(SnCl3)53- T Ni(CN)53-NMMOv-NSOIQ1hQB 2 (2W 29 l      \  `1 ?? H \ 0޽h ? fDW&cC3 TL(    TP4 ?? p00y:gt NN:gt T:gt 0000000000S^:gt:yaV (a), (c) g-NNirX[(W 0(b) e-NNirTf 25  .K   C ApD:\inorgCDROM\Ic3\ChaptersFigures\ch14gifs\fig1401c.gifH  0޽h ? ̙33  c[@`(  `r ` S ; `^   %f M  =` #"P   &` Z> ?? pM  e3.4 @` %` ZF ?? p   e3.5 @` $` ZM ?? p  e3.7 @` #` Zp\ ??p  e4.3 @` "` Ze ??p  Ni2+(aq),  @` !` Zm ?? Mp e5.3 @`  ` Z u ??  p e5.7 @` ` Zt| ??  p e5.1 @` ` Zx} ?? p e6.0 @`" ` Zt ??p Co+(aq),  @` ` Z ?? M fPhen @` ` Z ??   JHF @` ` Ẓ ??   aNH3, @` ` Z  ??  aH2O, @` ` Z4 ?? olgk  @`B '` Zo ??MB (` T1 ??MB )` T1 ??pMpB *` Zo ?? M B +` Zo ?? B ,` T1 ?? B -` T1 ??  B .` T1 ??  B /` T1 ??   B 0` Zo ??MM B >` ZD??`B ?` ZD??  @` T ?? P  |6~MSONbcS^vsNۏeQWVesQ cdT:gt0 2  H ` 0޽h ? fDW&cC3       !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuvwxyz{|}  w o  (  x  c $­&     <A  "p    ZDЭ ?? [ b@sks[MTir] + ky[MTir][Y-] nBRSǏ z YMMOvSRP[Ǐ z RRf[SMOHe^(kinetic trans effect) H2O < OH- < F- RNH2 py NH3 < Cl-< Br- < SCN- I- NO2- C6H5- < SC(NH2)2 CH3- < NO H- PR3 < C2H4 CN- CO dj}  S   X -W  Ṱ ??7 ESN2& 2 H  0޽h ? fDW&cC3 @\(  @$ @ ZX ??m    Fe(CN)64- + Fe(phen)33+ Fe(CN)63- + Fe(phen)32+ d6 d5 d5 d6 /f&TS/fMSONbc YLu(t :gt(outer-sphere mechanism) {USv5uP[ly eeh_-NSOb_b QLut :gt(inner-sphere mechanism) 5uP[1uMMOB\b_bveh_-NSOSuly 6xqi        $     ,/~j H @ 0޽h ? fDW&cC3 ^V(    C A pD:\inorgCDROM\Ic3\ChaptersFigures\ch14gifs\fig1411c.gif   ZT ??  t(a) ;mSDGؚ,S^1uDGؚ (b)S^MRTϑvI{ Gibbs1uDG:N (c)NirϑNO ;mSDGTDGNO (d) ;mSDG=0, NirϑNO S^1uDGg\, 5uP[lySۏL bs         H  0޽h ? fDW&cC38 x(  @  ZP ?? 0$  $R.A.Marcusb NV }[ϑh:N k2= fk1k2K (Marcuse z) k: ;`S^vs8^pe k1Tk2: $N*NNbcS^vs8^pe K: ;`S^vs^a8^pe f/f1us8^peTibces~bv YTSpe    @            C CCKCCKCC CCC +   H  0޽h ? fDW&cC3\   (  r  S hgM    r  S g   p  HA??`H  0޽h ? fDW&cC3 nf(    T  ?? ,$D 0 YUOf/fQLu:gt? Sl: GPHQly5uP[ [Cr(II)(H2O)6]2+ (t1/2 = 10 9s) Cr(H2O)63+ (t1/2 = 106s) 000000000000000`'` GPHQlyClMSO [Co(III)(NH3)5Cl]2+`'` W 2 2 CKCKCKG.&CKCKKG.&O CKCKCKG<KC(\<gH  0޽h ? fDW&cC3 nf(    T0 ??P  B`[[(uCr3+aq)6RYCr(en)33+e RZnv\O(u/fNHN e:gSf[[ \102        b H  0޽h ? fDW&cC3r`a m@ P|KPvVaf7q%0ۦ) ? =˲,!( / 0DTimes New Roman\8|dv 0|( 0h &D[SOes New Roman\8|dv 0|( 0h DArial Blackman\8|dv 0|( 0h"0DArialBlackman\8|dv 0|( 0h"@DWingdingskman\8|dv 0|( 0hPDSymbolgskman\8|dv 0|( 0h`DўSObolgskman\8|dv 0|( 0h ` .  @n?" dd@  @@`` ` X 3% FH #&     AE $! " xb$.1\<#,$b$;buY o8q6b$Y2 [, 59n2$TC#b82pBzb$Ǟf[pj옟b$fA3[4"$R i>mAlxp5xu2$#I?PcSc,sC& #2$/:ңH!f$ -"$ "N(PKEfQ7"$$ξb(ihVK"$ q޲ũx[/Oab$Aez^;72$qe>^T6 or$2$8$$D{2$p"FK-H+2$'1ZćY( 0e0e A@A5%8c8c     ?1d0u0@Ty2 NP'p<'p@A)BCD|E? @8+,uʚ;2Nʚ;g4CdCdv 0pRppp@ <4!d!d` 0,H9<4dddd` 0,H9 <4BdBd 0,N___PPT9nfFu88 PNG  IHDRW?sRGBgAMA7 cHRMz&u0`:pQ< B B  & 2.s^bVeb_MTir  $  !((2). d:SCQ }vLFSE0G$`'`(inert)MTir   $   "#N. 'lS؏S(5uP[ly)S^$ N Tvё^\yP[ly 'lS؏SS^( gQSf[SS) Tyё^\yP[ly 5uP[NbcS^(eQSf[SS) OY [Co(NH3)6]3+ + [Cr(H2O)6]2++6H3O+ [Co(H2O)6]2+ + [Cr(H2O)6]3+ + 6NH4+ ('lS؏S) Fe(H2O)62+ + *Fe(H2O)63+ *Fe(H2O)62+ + Fe(H2O)63+ (5uP[Nbc)G3 BJBJBNJBJBJBNBJBJBBJBJBNJBJBJBNJBJJBB              b9H8 $ %&'2. QLut :gt    ^[Co(III)(NH3)5Cl]2+ + [Cr(II)(H2O)6]2++5H3O+ d6 d4 [Co(H2O)6]2+ + [Cr(H2O)5Cl]2+ + 5NH4+ d7 d38 BJBJFBJ BJBJBJBJBJBBF6NFNFBJBJBJBJBJFBJBJJBFNFN)* /8   $_(  $N $ C A"P@N $ C A"PP@N $ C A"\: $ TD ??  SMOHe^ NH3 < Cl- P 2$H $ Z  ??P V  SMOHe^ Cl-< NO2-`   $ c $(   '  H $ 0޽h ? fDW&cC3 rj(  R  TT ??bZR___PPT94, dp SMOHe^vʑ T(SMOWV, s~SOTpSSO) NMv\O(u:_1_ gSt, SMOWVvSb_'`'Y(fgS)z 20x20x2  @   @`p  HA??@ H  0޽h ? fDW&cC3 l8(  l@ l T) ?? 43q_TSNS^svV }  -N_MvJS_ 5uw8 2  , l c Al, D:\inorgCDROM\Ic3\ChaptersFigures\ch7gif\fig0725c.gif`O3H l 0޽h ? fDW&cC3 nf(    T ??p`  B^4lNbcsv'Y\ S:SdMgTBeNY 0s'Y d:S0s-NI{ d100;m'` zW0;m'` ^ 2& 2 2#  b  H  0޽h ? fDW&cC3  Dp1(  px p c $/ T    F   9p Pp` @   7p @ J 4pJ 1p Z= ??+ ]/d0 d1 d2 d4(HS) d5(HS) d6(HS) d7(HS) d8 d9 d10 x, x  3p Z ??Jt@ J  6pJ  2p ZDT ??u   CaEDTA2-, Sc(H2O)5OH2-, TiCl62- Ti(H2O)63+ , VO(H2O)52+, MoOCl52- V(phen)33+, ReOCl53- Cr(H2O)62+ Mn(H2O)62+, Fe(H2O)4Cl2+ Fe(H2O)62+ Co(NH3)62+ Ni(en)32+ Cu(NH3)4(H2O)22+ Ga(C2O4)63- $x x  NJO  5p Z ??J  8p T ?? 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