d_ f_
. . . , . .
29.12.2008 .
_ I = 0.1 20
(II) 1: 1 1: 2, CuL, L2 _
(2L). [ML]+ _
[ThL]2+ La3+, Gd3+, Y3+, Sc3+, Th4+, Fe3+. ,
, , .
(H2Viol, _, )
.
_, [1, 2]. _ _
_
_ [3]. , , [4]. , , , [58],
, [9, 10].
, : =NOH, _O =NH:
, = і. ( 5) ( 4) ( II)
, ,
[7, 11, 12]. d_
_ . [8] (H3L), 1 5.7 0.1, 2 = 9.6 0.2 3 = 13.4 0.5, , _ _
. [7] M(H2L)+ M(H2L)2
Cu2+, Ni2+ Co2+. i, Cu2+ 4.3 0.1 3.1 0.2; Ni2+ 3.5 0.1 2.8 0.2; Co2+2.4 0.2 2.3 0.3. [7], Fe2+ H3L [Fe(H2L)3],
, , _
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8.40 0.05 8.60 0.05. [9] La3+, Y3+ Sc3+ _ , . , [L]+
Sc, La, Y. , ( La3+ 2.26 12.13; Y3+ 2.30 13.29 Sc3+ 5.69 10.42). _, , _ (, _ .). , , _
d _ f _
(Cu2+, Fe3+, Sc3+, Y3+, La3+, Th4+), . .
_ _673 , 0.1 /
(H,Na)Cl HCl 5 × 1031 102 /.
(II) (II) ..,
(III) ..., FW 175.1 _
Sigma Chemical Co. , , _
... _
, [13].
, , _ .
I = 0.1, .
. _ 1: 1,
1: 1 1: 2, , .. ..
[14]. 2 105
5 103 / , (III) _ UV_2800.
20.
(. 1) (II) (II), (III). 1: 1 (II), (II), (III), , , n +: H2L ≈ 1, _ H2L + M n + x H+ + [MH2 x L] n x. (II) β11, 1: 1 1: 2. 3.53.8 Cu2+: H2Viol = 1: 1.03.
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(II) 1: 1 1: 2 , :
Cu2+ + HViol [CuHViol]+,
Cu2+ + 2HViol [Cu(HViol)2]0,
_ (. 1) β11 = β12 =
= = (4.60 } 0.05) =
= (8.38 } 0.10). ( 4.55.2) [CuHViol]+ [CuViol]0, β1 =
= _
[CuHViol]+ [CuViol]0 . , (. 2), s 2 = 2.45 102 8.70 [CuViol]0 4.33 [CuHViol]+.
[CuHViol+] (4.60 0.05 4.33 0.10) [CuViol]0 ( 34) [Cu(HViol)2]0 [CuHViol+] [CuViol]0 ( 45).
[8] 25 (= 9.78, = 14.06) [15], I <
< 0.8. 0.1 _
(= 4.26, 20 4.41, 25 ) [12], (= 4.35, 25)
[8]. _ . _ (III) M: L ≈ 2: 1 (. 3) [FeViol]+ (= 11.86 } 0.04).
(. 4). [16].
_ (I = 0.1,20C) 1: 1 1: 2 Cu2+, Fe2+, Fe3+, La3+, Gd3+, Y3+, Sc3+, Th4+ . 5. (II) _ 1: 1 , _
. (II), (III), .
Cu2+, Fe3+, Y3+, Sc3+ Th4+ ( , _ ) 26 _. Cu2+ H2Viol :[CuHViol]+ [Cu(HViol)2]0, 3.54; [CuViol]0 >> 4.5. Fe3+, Y3+, Sc3+ Th4+ _ HViol 1: 1, pH 26; _ . _ (II) _ (II), , , _ , _
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_ HViol , Viol2, . _ _ , _ , _ .
, .
(II), (III) (II) (. 1), . 3.57.0 (V = 3.37 ). (II) , Cu2+ (V = 3.40 ). (II) _
> 4 (. 5). 3.54.6 (II): [CuHViol]+, [Cu(HViol)2]0 [CuViol]0.
Fe2+ Cu2+, 2.83.2 Fe2+H2Viol Cu2+H2Viol 4.56.0 Fe2+ H2Viol (V = 6.80 ). [FeHViol]+
[12]. , Cu2+ Fe2+ 24
2+ + H2Viol HViol+ + +, .
(. 2) H2Viol (~10050%) 04.
Cu2+ (4.04.6), ( 3.54.0). , > 5 [CuViol]0 (= 8.60 0.08) [11]. Fe3+H2Viol (II) (II), Fe3+ (c = 5.16 × 103 /, = 2.29, = 2.26) :
Fe3+ + H2Viol 2+ + FeViol+.
_ Fe3+ .
, Cu2+, Fe2+ > 7, < 7. pH, 3 ~ 1314
. , , , [7] . , , CuHL+ = 4.33 0.10, 4.60 0.05 ( pH, ), _ [7] [Cu(H2L)]+ 4.3 } 0.1 ( ). [ML]+ _
, La3+, Gd3+, Y3+, Sc3+, [ThL]2+ . La3+, Gd3+, Y3+, Sc3+ Th4+. s 2 p 6, .
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ThViol2+ (= 10.78)
I = 0.1 c [10]. [8],
, , HViol (2+) :
[CuHViol]+ _
GAUSSIAN98W [17].
CuCl2H2Viol [12], 420 , Cu2+ [18]. (II) ( ), , Cu2+ , [19, 20].
(. 3) 2 105 / , (III) , _ (200360 ), , (III) 230260 290330 . (. 4) Fe3+H2Viol , FeCl3NaCl,
. , (III), _, 430480 . (II) _
(III), , , (t 2 g)4(eg)2 (Fe2+)