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research of processes kompleksoobrazovanija uohobNi2 +, Cu2 +, Zn2+c optical isomerides kompleksonov pH-potentsiometricheskim titration

For research of stability of complexes of 3 d-metals with isomers synthesised kompleksonov made pH-potentsiometricheskoe titration of water solutions of a mix kompleksona C=0,001 a mole/l and salts of corresponding metal C=0,001 a mole/l in aliquot volume of 50 ml with ionic strength of solution I=0,1 created by a solution of nitrate of potassium.

Curves of pH-potentiometric titration L-КМАК, D-КМАК and L - KMGK in the presence of ions Ni2 +, Cu2 +, and Zn2+представлены on fig. 4.

Fig. 4.4.1. The curve of neutralisation L-КМАК with ions metallovpri I=0,1 (and - number a mole of the alkali, added counting on 1 mole kompleksona).

Fig. 4.4.2. The curve of neutralisation D-КМАК with ions metallovpri I=0,1 (and - number a mole of the alkali, added counting on 1 mole kompleksona)

Fig. 4.4.3. The curve of neutralisation L-КМГК with ions metallovpri I=0,1 (and - number a mole of the alkali, added counting on 1 mole kompleksona).

From rice 4.4.3 it is visible, that for all isomers in the field of values before jump pH ^^ b ^ neutralisations in the presence of ions of 3d-metals coincide with curves

Neutralisations free kompleksonov. Such coincidence specifies in absence of processes kompleksoobrazovanija, and discrepancy of curves of titration in area where occurs vozrastaniern, and komplekson exists basically in the form of a free ligand, specifies in formation kompleksonatov metals.

Logarithms of constants of stability of various complex forms kompleksonatov metals have been calculated by means of the program New DALSFEK, results are presented to tab. 4.4.1, in it logarithms of constants of stability komplesonatov racemic substance metals are presented.

Table 4.4.1.

Logarithms of constants of stability of complexes of 3d-elements with L-КМАК

(X), D-КМАК (Y), L, D-KMAK (L), L-КМГК (Z), L, D-КМГК (A), Asp, Glu, t=25C,

At I=0,1

Комплекс* Ni2 + Cu2 + Zn2 +
MeAsp 7,02 [109]

7,35[110] 7,16 [4]

8,81 [109]

8,57 [4]

6,40 [109]

11,2[115] 5,84 [4]

MeX 10,490,03 12,630,04 9,090,08
MeY 9,960,05 11,090,02 8,520,09
MeL 10,250,03 [111] 10,98 [180]

12,80 [11]

8,600,05 [111]
MeGlu 6,54 [109]

6,46 [110]

5,60 [4]

8,08 [109]

7,87 [4]

4,87 [109]

4,59 [4]

MeZ 9,110,03 10,770,05 7,350,07
MeAsp2 12,75 [110]
MeX2 16,110,2 16,780,04 12,340,05
MeY2 14,960,1 15,440,05 11,290,06
MeL2 15,200,04 [112] 15,820,05 [113]

19,580,06 [114]

11,650,06 [111]
MeGlu2 10,34 [110]
MeZ2 14,190,05 14,850,05 10,210,05
MeHX 15,090,04 16,690,02 12,290,03
MeHY 13,620,03 14,970,06 13,640,05
MeHL 14,260,05 [112] 15,070,05 [113]

20,450,02 [114]

12,770,05 [111]
MeHGlu 21,15 [116]
MeHZ 12,700,05 13,210,05 11,590,05
MeHA [117] 10,56

*Заряды anions are lowered

From table 4.4.1 it is visible, that stability of complexes of 3d-metals changes with addition to aspartic and glutamic acids of one atsetatnoj groupings (all forms KMAK and KМГК). Stable growth of stability of complexes on 1,5-2 orders is unequivocally defined by growth dentatnosti the studied connections, for example, from complexes of copper with D-КМАК to copper complexes sk-KmAk.

For complexes of all kompleksonov with ions of Sd-metals stability change will be co-ordinated with reduction of atomic radius among Irving - Williams Ni2 + Zn2+и nitrogen - and kislorodosoderzhashchih ligands in comparison with akvaionami speaks stabilisation of complexes in the field.

On the received data diagrammes of share distribution of various complex forms, obrazuemyh by ions of the investigated metals with optical isomerides kompleksonov, depending on rn are constructed. For example, on fig. 4.4.1показана the diagramme of distribution of complex forms L-КМАК with ion Ni. For system H3X, with Ni2 +, other diagrammes for ions Ni2 +, Cu2 +, Zn2 "^ investigated kompleksonami, are in the appendix.

Fig. 4.4.1. The diagramme of distribution of various complex forms L -

KMAK with ion Ni at I=0,1.

5.

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A source: Biberina Evgenie Sergeevna. COMPLEX FORMATION OF SOME ZE-METALS WITH L-, D-FORMES H- (CARBOXYMETHYL) ASPARAGINOUS AND L-N- (CARBOXYMETHYL) ACID GLUTAMINE. Thesis for the degree of candidate of chemical sciences. Tver - 2018. 2018

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