ࡱ> }~stuvwx_ c w#`|[bjbjmm:2   ---8-r/ ^U20(Z0.000555TTTTTTT$JVhXdTi 65566T 00/U===6N 0 0T=6T==1Mp ^ O0&0 0$jr-:1NR.U0^UGNY;Y,OOY O5"5=5 6555TTG=555^U6666 !- -  0 ?@020E @C:>?8A8C@:8=0 0;8=0 ;5:A0=4@>2=0:8A;5=85 2>4K @A:84>@>A;O=0;L=K<8 E8<8G5A:8<8 45;OA=>25 :;0AB5@>2 MnIV 8 CoIII02.00.04  D878G5A:0O E88A:0=85 CG5=>9 AB5?5=8 :0=4840B0 E83>;>2:0  2008 01>B0 2K?>;=5=0 2 =AB8BCB5 ?@>1;5< E89 D878:8 0CG=K9 @C:>2>48B5;L:4>:B>@ E8<8G5A:8E =0C:601852 "09??>=5=BK:4>:B>@ 18>;>38G5A:8E =0C:02 0E8@ 60D0@ >3;K 254CI89 =0CG=K9 A>B@C4=8: >B45;0 18>M=5@35B8:8  D878:>-E89 18>;>388 875@A:>3> # 8=>A>203. >A:20:0=4840B D878:>-<0B5<0B8G5A:8E =0C:!8<18@F520 0;8=0 ;0482=0$8;80; 8=AB8BCB0 M=5@35B8G5A:8E ?@>1;5< E89 D878:8 3. '5@=>3>;>2:054CI0O >@30=870F8O:&5=B@ $>B>E8A:200I8B0 A>AB>8BAO ________________2008 3. 2 ___ G =0 70A540=88 8AA5@B0F8>==>3> !>25B0  002.082.02 ?@8 =AB8BCB5 ?@>1;5< E89 D878:8  ?> 04@5AC: 142432, >A:>2A:0O >1;., 3. 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oIIIn, 345 n B 4 4> 24 8 1>;55, >:8A;ONBAO =5A:>;L:> ;5:C; 2>4K 8 >1@07CNBAO 2 MB>;;5:B82=>F5AA5 4> H5AB8 ;5:C; :8A;>@>40. @>3>, 87CG5=K =5:>B>@K5 0A?5:BK >:8A;5=8O 2>4K :;0AB5@0:8A;KE @0AB2>@0E.@C38A=>2=KB:@KB85 @50:F88 H5AB8M;5:B@>==>3> >:8A;5=8O 2>4K 4> >7>=0 2 E;>@>?;0AB0E 1C@KE (Cystoseira barbata) 8 :@0A=KE (Callithamnion corymbosum) @A:8E 2>4>@>A;OE 2 ?@>F5AA5 D>B>A8=B570. 50:F8O H5AB8M;5:B@>==>3> >:8A;5=8O 2>4K 4> >7>=0 1C@K<8 @A:84>@>A;OABL B5<K.7CG5=85 <5E0=874=>3> D>B>A8=B570 O2;O5BAO 0:BC0;L=>9 B59 =5 B>;L:> 87-70 206=>AB8 MB>3> ?@>F5AA0 4;O ?>445@60=8O 687=8 =0 5 8 4;O ?>43>B>2:8 : >ACI5AB2;5=8N  8A:CAAB25==>3> D>B>A8=B570 2=5 :;5B:8.  MB>9 A2O78 25AL 8AA;54>20=85 DC=:F8>=0;L=KE E8<8G5A:8E 45;59 3> :>D0:B>@0 >:A8407K D>B>A8AB5B>A8=B570 =0 >A=>25 :;0AB5@>2 MnIV 8 CoIII. 0 @5H5=85 MB>9 0:BC0;L=>9 B5OI0O 48AA5@B0F8>==0O @01>B0. &5;L @01>BK.&5;LN 48AA5@B0F8>==>9 @01>BK 1K;> CB>G=5=85 <5E0=87:8A;5=8O 2>4K 4> :8A;>@>40 8 2KOA=5=85 2>76=>AB8 >:8A;5=8O 2>4K 4> >7>=0 2 DC=:F8>=0;L=>9 E89 45;8 3> :>D0:B>@0 >:A8407K D>B>A8AB54=>3> D>B>A8=B570  2 A5@=>:8A;KE @0AB2>@0E MnIV, 0 B0:65 ?@8@>4=KE D>B>A8=B578@CNI8E >@30=873>, =5>1E>48 1K;> 87CG8BL :8=5B8:C 8 <5E0=87:8A;5=8O 2>4K :;0AB5@010;LB0(III) % ?5@A?5:B82=>3> :0B0;870B>@0 >:8A;8B5;L=>9 G0AB8 D>B>:0B0;8B8G5A:>3> ?@5>1@07>20B5;O A>;=5G=>9 M=5@388 2 E820=8O. ;O 4>AB865=8O C:070==>9 F5;8 1K;8 ?>AB02;5=K A;54CNI85 7040G8:7CG5=85 :8=5B8:8 B5@- 8 D>B>AB820==>3> >:8A;5=8O 2>4K 2 DC=:F8>=0;L=>9 E89 45;8 Mn  co (A5@=>:8A;K5 @0AB2>@K AC;LD0B0 ;8G5AB25==>5 8AA;54>20=85 :8=5B8:8 >1@07>20=8O >7>=0 2 87CG5==KE A8AB58A: 18>;>38G5A:8E >1J5:B>2, A?>A>1=KE >:8A;OBL 2>4C 4> >7>=0.7CG5=85 :8=5B8:8 8 <5E0=87:8A;5=8O 2>4K A>548=5=8O :8A;>@>40.0CG=0O =>287=0. 7CG5=> =58725AB=>5 @0=55 O2;5=85  H5AB8M;5:B@>==>5 >:8A;5=85 2>4K 4> >7>=0 E;>@>?;0AB0<8 :@0A=KE (Callithamnion corymbosum) 8 1C@KE (!ystoseira barbata) @A:8E 2>4>@>A;59. 7CG5=K :8=5B8:0 8 <5E0=87:8A;5=8O 2>4K :;0AB5@0ABL. #AB0=>2;5=K =>2K5 <5E0=87<K 3>M;5:B@>==>3> >:8A;5=8O 2>4K 4> :8A;>@>40, :>B>@K5 3CB A;C68BL B5>@5B8G5A:>9 107>9 4;O ?>41>@0 MDD5:B82=KE :0B0;870B>@>2 >:8A;5=8O 2>4K 2 D>B>:0B0;8B8G5A:8E ?@5>1@07>20B5;OE A25B>2>9 M=5@388, ?@54AB02;ONI8E ?@0:B8G5A:CN F5==>ABL 4;O ?@>1;5;=5G=>9 M=5@388. @C3>9 ?@0:B8G5A:>9 F5==>ABLN 6=> AG8B0BL 2K45;5=85 O3 1C@K<8 (!ystoseira barbata) 8 :@0A=K<8 (Callithamnion corymbosum) @A:84>@>A;O385 2>4>@>A;8 8A?>;L7CNBAO 4;O 18>>G8AB:8 AB>G=KE 2>4. "5?5@L AB0=>28BAO OA=K MB> A2O70=>, A:>@55 2A53>, A D>B>35=5@8@>20=85< 87>=0.?@>10F8O @01>BK. 57C;LB0BK 48AA5@B0F8>==>9 @01>BK >1AC640;8AL =0 A;54CNI8E A5@>AA89A:8E 8 4=KE :>=D5@5=F8OE 8 A878C<0E:XVII !878C2@5<5==0O E8AA89A:0O H:>;0  A878C< ;>4KE CG5=KE ?> E89 :8=5B8:5 (>A:>2A:0O >1;0ABL, ?0=A8>=0B  5@57:8 , 2006), XV( !878C2@5<5==0O E8AA89A:0O H:>;0  A878C< ;>4KE CG5=KE ?> E89 :8=5B8:5 (>A:>2A:0O >1;0ABL, ?0=A8>=0B .=>ABL, 2007), 564C=0@>4=0O =D5@5=F8O !8=5@35B8:0 2 5AB5AB25==KE =0C:0E, 3. "25@L, 2007, Voevodsky Conference  Physics and chemistry of elementary chemical processes Chernogolovka, Moscow Region, Russia, 2007, A5@>AA89A:89 !878CD>B>=8:0", 3. '5@=>3>;>2:0, 2007, VII 564C=0@>4=CO ;>456=CO :>=D5@5=F8O %$ -#K "8>E8A:20, 2007 3.C1;8:0F88. 57C;LB0BK 48AA5@B0F88 ?@54AB02;5=K 2 3 AB0BLOE 8 9 B578A0E 4>:;04>2.>;>65=8O, 2K=>A83>M;5:B@>==>5 >:8A;5=85 2>4K 2 E89 DC=:F8>=0;L=>9 45;8 3> :>D0:B>@0 (4Mn-co) >:A8407K D>B>A8AB54=>3> D>B>A8=B570.(5AB8M;5:B@>==>5 >:8A;5=85 2>4K 4> >7>=0 :@0A=K<8 8 1C@K<8 @A:84>@>A;O<8.8=5B8:0 8 <5E0=87:8A;5=8O 2>4K A>548=5=8OIII 2 E;>@=>:8A;KE @0AB2>@0E.!B@C:BC@0 8 >1J5AB>8B 87 22545=8O, >17>@0 ;8B5@0BC@K (3;020 1), M:A?5@89 G0AB8 (3;020 2), >1AC645=8O @57C;LB0B>2 8AA;54>20=8O (3;02K 3-4), 2K2>4>2 8 A?8A:0 ;8B5@0BC@K. 01>B0 87;>65=0 =0 113 AB@0=8F0E ?8A=>3> B5:AB0, 8;;NAB@8@>20=0 40 @8AC=:03@0D8O 2:;NG05B 153 =0820=8O.! !  "+> 22545=88 >1>A=>20=0 0:BC0;L=>ABL 8AA;54>20=8O, AD>@20=K F5;8 @01>BK, 55 =0CG=0O =>287=0 8 ?@0:B8G5A:0O 7=0G8ABL. ;020 1. 17>@ ;8B5@0BC@K. ;8B5@0BC@=>17>@5 @0AAB@5=K ?@>F5AAK >:8A;5=8O 2>4K 2 ?@8@>4=>B>A8=B575 8 2 E8=0;L=KE 45;L=KE A8AB5A=>25 8>=>2 ?5@5E>4=KE 2. ;020 2. -:A?5@8B5 8A?>;L7>20;8 48AB8;;8@>20==CN 2>4C, E;>@=CN :8A;>BC <0@:8 E.G. D8@:>>G8I5==K9 B@8DB>@84 :>10;LB0 CoF3 D8@BK ?@8BC .A.G., ?5@B>2;5=8O @0AB2>@>2 @5035=B>2 8A?>;L7>20;8 48AB8;;8@>20==CN 2>4C. 0AB2>@K Mn(IV) ?>;CG0;8 2>AAB0=>2;5=852 ?@8 :>9 B5 A;54CNI8< A0?@>872>;L=K< @50:F8O2 ?@>2>48;8 =0 ?@81>@5  Specord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nIV (<5=LH5 3 <;L/;) 8 2KA>:8E B5:8A;5=85 2>4K 2 A5@=>:8A;KE A@540E ?@>8AE>48B 2 :>>@48=0F8>==>9 AD5@5 18O45@=>3> :>= MnIV 2KABC?05B 2 :0G5AB25 42CEM;5:B@>==>3> >:8A;8B5;O (?5@5E>4 MnIV ( MnII), 0 A0==K:8A;8B5;5548=5=8O MnII 1KAB@> >:8A;ONBAO <0@30=F5 MnIII, ?>A:>;L:C =0;8G85 42CE 87>A15AB8G5A:8E B>G5: ?@8 510 8 650 =BACBAB285 2 @50:F8>==>9 A<5A8 70;8G5AB2 8=KE A>548=5=89 , GB> 18O45@=K9 :>==K:8A;8B5;5A>15= 35=5@8@>20BL >7>=  ?@>4C:B H5AB8M;5:B@>==>3> >:8A;5=8O 2>4K. 'B>1K ?>;CG8BL >7>=, =5>1E>48 8A?>;L7>20BL 1>;55 2KA>:85 :>=F5=B@0F88 MnIV, :>340 AB0=>28BAO 2>76=K1@07>20=85 1>;55 :@C?=KE :;0AB5@>2 <0@30=F0, G5<?;5:A MnIV2.  8A. 1. 73;>I5=8O @50:F8>==>9 A<5A8 ?@8 B5@AB820==>AAB0=>2;5=88 Mn(IV) ! Mn(III) 2 12  A5@=>9 :8A;>B5. "5F5AA0 930!, [Mn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n (IV) (2) 2 ?@>F5AA5 >:8A;5=8O 2>4K ?@8 B5!. @820O 1 ?@54AB02;O5B A>1>9 87?B8G5A:>9 ?;>B=>AB8 D @50:F8>==>9 A;=K  = 417 =<.1. "5<?5@0BC@=0O 7028A8ABL :>=AB0=BK A:>@>AB8 @50:F88 2>AAB0=>2;5=8O :;0AB5@0 MnIV12 2 :>>@48=0B0E @@5=8CA0.0 @8A. 20 ?>:070=0 :8=5B8G5A:0O :@820O 2>AAB0=>2;5=8O A>548=5=89 Mn (IV) (:@820O 2) 8 55 ;8=59=0O 0=0@D>70 (:@820O 3) 2 :>>@48=0B0E {[C]-5, }. %>@>H0O ;8=50@870F8O :8=5B8G5A:>9 :@82>9 ?>:07K205B, GB> 2 CA;>28OE >?KB0 >A=>2=>9 2:;04 2 ?@>F5AA 2=>AOB 35:A045@60I85 ?> 425=04F0BL 8>=>2 Mn (IV), ?>A:>;L:C :8=5B8G5A:8 =57028A8<K:8A;8B5;5< 2 MB8E A8AB5<0E O2;O5BAO =>1>9 18O45@=K9 :>B=>A8B5;L=> C7:>< B5B 60 4> 720!) >?@545;8;8 M=5@38N 0:B820F88 ?@>F5AA0 A8=5@35B8G5A:>3> >:8A;5=8O 12 ;5:C; 2>4K 4> 4 ;5:C; >7>=0 2 :>>@48=0F8>==>9 AD5@5 :;0AB5@0 MnIV12 ?> :>=AB0=B0@>AB8 @50:F88 (@8A. 21). >;CG5==0O ?@8 MB>< M=5@38O 0:B820F88 6 = 68 :6/;L >:070;>AL =865, G5:8A;5=88 2>4K 4> :8A;>@>40 2 :>>@48=0F8>==>9 AD5@5 18O45@=>3> :><?;5:A0 MnIV2 0 = 102,5 :6/;L. @0240, ?@54M:A?>=5=F80;L=K9 68B5;L (k0 = 5107 c-1) >:07K205BAO ?@8 MB> 1KG=>3> 7=0G5=8O ~ 1013 A-1.ACI5AB2;5=85 MB>3> 65 ?@>F5AA0 ?@8 1>;55 2KA>:8E B5B 78 4> 900!) ?>:07K205B, GB> 2 MB>A=>2=>9 2:;04 2 @50:F8N 2=>AOB :;0AB5@K E3 (B.5. MnIV6) A =51>;LH8@>3> ?8AK2053> M:A?>=5=F80;L=>9 :8=5B8G5A:>9 :@82>9 8 >1CA;>2;5==>3>, 25@>OB=55 2A53>, 2>AAB0=>2;5=852 E6, ?@8ACBAB2CNI8E 2 =57=0G8B5;L=>;8G5AB25 2 @50:F8>==>9 A2KH5==KE B5@>ABL ?@>F5AA0, >1CA;>2;5==K9 :;0AB5@0<8 MnIV6, ?@545;8;8 :>=AB0=BK A:>@>AB8 @50:F88 MB8E :;0AB5@>2 ?@8 @07;8G=KE B5 MB8< 40==K;CG5=0 M=5@38O 0:B820F88 >:8A;5=8O 6 ;5:C; 2>4K 4> 42CE ;5:C; >7>=0 2 :>>@48=0F8>==>9 AD5@5 35:A0O45@=KE :;0AB5@>2 AL, GB> 2 MB>< A;CG05 M=5@38O 0:B820F88 3 = 98,2 :6/;L  >B;8G05BAO >B 0 = 102,5 :6/;L 4;O @50:F88 >:8A;5=8O 2>4K 4> :8A;>@>40 18O45@=K<?;5:A0=5=F80;L=K9 68B5;L k0 >:07K205BAO 1;87:8@<C 4;O =>;5:C;O@=KE @50:F89 @0A?040 :;0AB5@>2 =0 ?@>4C:BK (~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n(IV) A?>A>1=K >:8A;OBL 2>4C :0: ?@8 =03@520=88, B0: 8 ?@8 >A25I5=88 8E A25B>9 B5:070=> D>B>AB820==>5 2>AAB0=>2;5=85 MnIV ! 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