2014 re symp dushanbe tajikistan
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-
10- -
(28-29 2014 )
2014
-
2
(V)
* .., .. *
- . . , - . , [R-S-S-R]/[RS]2, RS-3--1,2,4--5 2/, 4 /, 6 / HCl 298, 250,14; 226,98 211,5. , 0, . , 273 338 0 6/ HCl 183,5 273,2. , HCl - E0. , 6/ HCl 273-338 E0 89,7, 4/ 2 / HCl 84,3 75,5 . , HCl E0. E0 1,2,4-. E0 :
2-ThioPir < 2-M < I-Met-2M < Pthiol < 3-Met-1,2,4-Tthiol <
129,9 165,3 179,0 184,8 209,5
< 3-t-1,2,4-Tthiol < 1,2,4-Tthiol < 3,4-DiMet 1,2,4- Tthiol <
211.5 266,0 290,3
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3
< 4- Met-1,2,4-Tthiol
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4
(-) - , , 3, , . . , , , , , , , . . - [3].
1. .., .., .. . .
: , 2007. 298 . 2. .. //
. IV . . -2010, 28-29 2010 ., , 2010. - 54 . . 37.
3. 2523892. . .., .., .., .. . 27.07.2014. . 21.
CHCl3
.., * .., ..
, . , , * , . ,
() () (I-, NO3
-. SCN
-, CCl3COO
-, ClO4
-) .
- , - [Sc()3]I3, [Sc()3](NO3)3, [Sc()2(SCN)2]SCN,
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5
[Sc()2(CCl3COO)2]CCl3COO [Sc()3](ClO4)3. CHCl3 . [Sc()3](ClO4)3, CHCl3.
. , , (k:103-,-1) :
SCN- (5,99) > I
- (3,56) > NO3
- (2,25).
, (): I
- -
3,4510-13; NO3- - 1,0310-13; SCN- - 5,0410-13; ClO4
- - 2,210-15; CCl3COO
- -
4,1110-14. .
, , - . , 6 / HCl + 1 / NaClO4 Sc(III) 0,05 / CHCl3 , , Cu(II), Co(II), Ni(II), Zn(II), Cd(II), Mn(II), Al(III), Cr(III), Zr(IV), Th(IV), V(V).
(V) 1--2- 7/ HCl 273
* .., .., .., ..
* ,
*
(V) , . (+5) . (V) . , .
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6
. (V) , 1--2- 7/ HCl 298. (V) 1--2- 7/ HCl 273 (.1).
.1. (V) c 1--2-
7/ HCl 273
, 2[ReOCl5]- 1--2--7/ HCl 273 pKi: pK1=5,98; (2=9,5510
5) 2=4,86; (2=7,2410
4) 3=3,96; (3=9,12103) 4=3,29; (4=1,9510
3) 5-=2,89; (5=7,7610
2 ). ( 1).
, .
- ; [L]- 1--2-. Excel Borland Delphi, Windows 7. 5=0 . 1--2- 0,1 5,0 0,1. (V) 1--2- 7/ HCl 273 ( 2).
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7
.2. (V) c 1--2-
7/ HCl 273,
. 2 pKi
:n*
1 =6,06 (1*=1,15106);
*
2 =4,90 (2*=7,941,15104);
*
3 =4,02; (3=1,05104);
*
4 =3,35; (4*=2,24103);
*
5 =2,65; (5*=4,47102).
, pKi -1--2- (V) . pK5.
*
i
2[ReOCl5]- 1--2--7/ HCl 273 (.3).
. 3. (V) 1--2-
7 / HCl 273
i) 1--2- (V) 273 7/ HCl .
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8
1--2-
(V) 7/ HCl 273
maxi
[ReOLCl4]-
5,6
[ReOL2Cl3] 4,6
[ReOL3Cl2]+ 3,8
[ReOL4Cl3]2+
3,2
[ReOL5]3+
2,6
,
max
i 1--2-.
(V)
* ..., ..
* ,
. , , . (V) . (V) . , , (V). (V) 2 1--2-.
[ReO(2-M)4]222 900 (
) 120 0 ( ) -, . . 380 0 - . . [ReO(2M)23]22
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9
90-100 0. , 260 0. : [ReO(2M)4r2]r222 400
0 43,7, 70,0. , 2- , . 1--2- (V).
[ReO(2-M)2r3] 22 c (V) 1-Met-2-M , 2- . , -2- 2600, 1--2- 3600. , 2- 1--2- , . , -, 1--2- .
(III) , ,
( ) ,
.., * .., .., .., ..
, . , , * ,
. ,
(III) . , 350 , (), () (, Br, ), HCl, . 1,8-2,2 . HCl, . , Fe (III). HCl
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10
0,25 4,0 / (99 %) 3 4 / HCl. Br 2,0-4,0 / HCl.
() Fe (III) , . HCl H2SO4, (H2SO4) 0,25 /. , , HCl, 1 / (, ), 0,5 / (Br) NaCl KCl 1 / Fe (III) 92 94 %. [FeCl4]
1- ( . H)Cl.
(III) Br , : 99,32 Fe (III) 19,2 0,1 ; Br 98,76 Fe (III) 19,2 0,1 / 17,8 17,7 0,1 / FeCl3 .
R : H+ : Fe3+ : Cl- : = 2 : 2 : 2 : 7 : 0,9, (RH)[Fe2Cl7]
. RH(Br), R .
(Br) HCl H2O (III), .
-
.., .., .., ..*
, . , , * , . ,
() () Ca(II), Mg(II), Sr(II), Ba(II), Co(II), Ni(II) Cu(II) . Ca(II) Cu(II) CHCl3
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11
(0.05 /) NH3
0,1-0,8 / (.). Sr(II), Ba(II) Co(II) NH3 (NH3)=0,25-0,80 /. Ni(II) (NH3)=0,1 /. 9:1. pH50 Ca (7,3) < Sr (8,1) < Ba (8,5), lgD Ca Ba. 10% pH50 Ca(II) 6,0, Mg(II) 6,2. pH50 : Co (4,3) < Ni (4,10) < Cu (1,3).
CHCl3 , Mg(II) Ca(II) NH3 0,1-0,5 /.
Ca Mg 0,1 / CHCl3. D(Ca) 5,2, D(Mg) 2,6. . , , (NH4)2CO3 Cu(II) Ni(II), Co(II) 93% ((NH4)2CO3)>0,5 /. (II).
lgD(Me)-lgC(R) R:Me=2:1. Cu, Co CHCl3: 2HR() + [Me(NH3)4](NO3)2() [MeR2](o) + 2NH4NO3() + 2NH3(), Me Cu,
Co, Ca
2HR() + [Ni(NH3)4](NO3)2() [Ni(NH3)2R2](o) + 2NH4NO3() [Me(H2O)R2](o).
(II) CHCl3 , , .
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12
Potentiometric and thermodynamic investigation of rhenium(V) complexes
with 4,5-dihydro-1H-imidazole-2-thiol
Gouda G.A., *Aminjanov A.A.
Faculty of Science, Al-Azhar University, Assiut, 71524, Egypt
*Tajik National University
Corresponding author. E-mail: ggouda1973@yahoo.com
Stability constants of 4,5-dihydro-1H-imidazole-2-thiol with rhenium(V)
were determined potentiometrically in acidic medium (4 M HCl) at different
temperatures. The dissociation constants pK of 4,5-dihydro-1H-imidazole-2-thiol
as well as the stability constants (lg K) of their complexes were determined at
varieties temperatures. The corresponding thermodynamic parameters (Go, Ho and So) were determined and discussed. The formation of the metal complexes has been found to be exothermic.
Key words: Potentiometric, rhenium(V), formation constants, thermodynamics.
Characteristic stability constants may be important for predicting various
chemical processes, such as isolation, extraction and concentration methods,[1,2]
since many elements are present in trace amounts, and can be separated by
complexion reagents. Bejerrums[3] dissertation being initiative in developing this field. Metal complexation not only brings the reacting molecules together to give
activated complex [4]
but also polarized electrons from the ligands towards the
metal. The relation between stability and basicity of the ligands is indicated by the
formation constant and free energy change values. The stability constant dependent
on several factors such as: electronegativity, hardness or softness of the donor
atoms on the ligand, the metal ion, nature of the ligand, the ionic radius and charge
of the oxidation state on the metal core respectively. One available method is the
potentiometric titration using ligand redox electrodes based on sulfur compounds
and their oxidized forms. Many workers [5-18]
have reported their results on metal-
ligand stability constants and their oxidized forms.
Experimental
To determine the formation constants of rhenium(V)- 4,5-dihydro-1H-
imidazole-2-thiol in 4 M HCl at different temperatures a potentiometric method of
employed. Equilibrium concentrations of 4,5-dihydro-1H-imidazole-2-thiol are
calculated by the following equation:
all
initialinitial
Liinitial
V
VC
T
EEL lg
2
1lg
109837.1]lg[
4
where Einitial - initial equilibrium potential of the oxidation-reduction system
in the absence of rhenium(V); Ei - equilibrium potential at end point of titration. initial
LC - initial analytical concentration of 4,5-dihydro-1H-imidazole-2-thiol;
Vinitial/Vall - the ratio of the initial volume to the total volume of the system: T - the
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13
temperature of the experiment in Kelvin degree. Determined at each point of the
titration equilibrium concentration of the ligand. The function n was calculated at each titration by the formula:
)Re(
][
V
L
C
LCn
where n is the average degree of formation derived from the titration curves of a ligand with metals; CL is the concentration of 4,5-dihydro-1H-imidazole-2-
thiol; [L]- equilibrium concentration of 4,5-dihydro-1H-imidazole-2-thiol; CRe(V)-
the concentration of rhenium(V). All the calculations are employed using a
computer Intel Core i7. Results and discussion
Among the ligand redox electrodes used for the study of complexes represent an
important type on the basis of sulfur-containing organic compounds and their
oxidized forms. The preparation of such electrodes is based on the reversible
oxidation of thione or thiol-containing compounds to the corresponding disulfides.
The synthetic method[19]
involved the synthesis of 4,5-dihydro-1H-imidazol-2-thiol
by refluxing 1,2-diaminoethane and carbon disulphide. The synthesis route of
compounds is outlined in the following:
The complexation process of rhenium(V) with 4,5-dihydro-1H-imidazole-2-thiol
proceeds stepwise and reversible. It is natural that the stability of these complexes
depends on the nature of the substituent in the 4,5-dihydro-1H-imidazole-2-thiol.
The addition of H2[ReOCl5] to a solution (0.0759 M) containing 4,5-dihydro-
1H-imidazole-2-thiol (0.0259 M) and its oxidized form in the acid medium (4 M
HCl) causes a change in color of solution to deep green, with increasing
concentration of H2[ReOCl5] the solution is changed to purple, blue and finally to
green. The adding, to the green solution 4,5-dihydro-1H-imidazole-2-thiol color
change of the solution is reversed. This fact indicates the gradation and
reversibility of the complexation of rhenium(V) with 4,5-dihydro-1H-imidazole-2-
thiol. In the titration of rhenium(V)- 4,5-dihydro-1H-imidazole-2-thiol system and
its oxidized form, an increase in the magnitude of the equilibrium potential,
indicating a other participation in complexation of rhenium(V) with 4,5-dihydro-
1H-imidazole-2-thiol than its oxidized form. At each point, equilibrium is
established within 5-10 minutes. By potentiometric titration each values of the
equilibrium concentration of 4,5-dihydro-1H-imidazole-2-thiol and E are
determined. Using values of [L] and taking together with both the analytical
concentrations of H2[ReOCl5] and 4,5-dihydro-1H-imidazole-2-thiol formation
constants can be calculated. Some data determined by potentiometric titration of
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14
rhenium(V) with 4,5-dihydro-1H-imidazole-2-thiol in 4 M HCl at 273 oK, are
presented in Table 1.
Table 1. Data obtained by potentiometric titration of rhenium(V) with 4,5-dihydro-
1H-imidazole-2-thiol in 4 M HCl at 273 oK
Re(V).103 L.10
2 , mV -lg [L] n
Mole/l
4.536 2.323 61.54 2.745 4.73
4.773 2.309 74.54 2.986 4.62
5.240 2.281 108.98 3.624 4.31
5.808 2.247 155.54 4.487 3.86
6.358 2.214 178.98 4.923 3.48
6.892 2.182 185.21 5.041 3.17
7.413 2.151 188.32 5.101 2.90
7.917 2.121 193.21 5.195 2.68
8.409 2.092 196.47 5.258 2.49
8.886 2.063 199.14 5.310 2.32
9.351 2.035 201.44 5.355 2.18
10.245 1.982 203.35 5.396 1.93
11.092 1.931 207.24 5.474 1.74
12.664 1.837 215.57 5.638 1.45
14.089 1.752 220.54 5.740 1.24
14.754 1.712 225.32 5.834 1.16
15.996 1.638 228.62 5.904 1.02
17.135 1.570 230.87 5.955 0.92
18.184 1.508 233.36 6.010 0.83
19.608 1.422 236.56 6.081 0.73
20.881 1.346 238.47 6.128 0.64
22.024 1.278 240.21 6.172 0.58
23.692 1.178 244.55 6.270 0.50
25.118 1.093 246.08 6.314 0.44
Figure (1) showed potentiometric titration formation curves of rhenium(V)-
4,5-dihydro-1H-imidazole-2-thiol complexes at different temperature in 4 M HCl.
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15
Fig. 1. Plots of n against (-lg K) for rhenium(V) with 4,5-dihydro-1H-imidazole-2-thiol complexes in 4 M HCl at different temperatures.
Potentiometric titration curves showed that rhenium(V)-4,5-dihydro-1H-
imidazole-2-thiol system in presence of 4 M HCl at different temperatures
consistently produced four types of complexes. The log Ki values of rhenium(V)
with 4,5-dihydro-1H-imidazole-2-thiol from the titration curves by Bjerrum
method at half-integer values [20-21]
of the degree of formation ( n ) is presented in Table 2.
Table 2. Formation constant values of rhenium(V)-4,5-dihydro-1H-imidazole-2-
thiol in 4 M HCl at different temperatures
T, oK
[ReOLCl4] [ReOL2Cl3] [ReOL3Cl2]
+ [ReOL4Cl]
2+
lg K1 lg K2 lg K3 lg K4
273 6.27 5.61 5.26 4.92
288 6.10 5.43 5.10 4.71
298 5.81 5.17 4.86 4.53
308 5.55 5.03 4.64 4.31
318 5.31 4.78 4.48 4.10
328 5.13 4.65 4.39 3.45
338 5.02 4.57 4.32 3.11
These data show that with increasing amount coordinated molecules 4,5-
dihydro-1H-imidazole-2-thiol lg Ki decreases. Stepwise formation constant ratios
were as follows: K1/K2 = 4.57; K2/K3 = 2.24; K3/K4 = 2.19 at 273 oK. These data
indicate that the ratio stepwise formation constants are not so large enough, so it
was necessary to clarify the estimated constants either successive approximation
method or by the "pH-meter program [22]. However, attempts to refine the estimated formation constants were not sufficient.
The equilibrium constant (K) varies with temperature according to the Van't
Hoff [23-24]
equation:
R is the universal gas constant, T is the absolute temperature (in oK) and Ho is the
enthalpy change. To obtain the integrated equation, it is convenient to first rewrite
the Van't Hoff equation as
Thus, for exothermic reactions, the Ho is negative and K decreases with temperature, but for endothermic reactions Ho is positive and K increases with temperature. In accordance with the data
[25] values of stability constants after
verifying these methods vary slightly. In this regard, the stability constant of
rhenium(V)-4,5-dihydro-1H-imidazole-2-thiol complexes, some of the
potentiometric titration curves, were used to estimate the thermodynamic
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16
properties of the complexation by the temperature coefficient. The Ho values were determined from the slope of the straight line obtained by plotting log Ki
against 1/T (Fig. 2). The change in entropy is determined by the interval intercepts on the y-axis, these lines (So = R * interception)
[26,27]. Gibbs energy
[28] was
calculated from the equation Go = Ho-TSo (Table 3). Calculated
thermodynamic function showed that the isobaric-isothermal capacity becomes
less negative with increasing number of coordinated molecules of 4,5-dihydro-1H-
imidazole-2-thiol. This experimental finding may be due to an increase in the steric
hindrance that prevent in entering molecules of 4,5-dihydro-1H-imidazole-2-thiol
to center the inner sphere complexes [29]
.
2.5
3
3.5
4
4.5
5
5.5
6
6.5
7
2.9 3.1 3.3 3.5 3.7 3.9
log i
1/*10-3 (oK-1)
1
2
3
4
Fig. 2. Plots of log Ki against 1/T for rhenium(V)- 4,5-dihydro-1H-imidazole-2-
thiol complexes in 4 M HCl at different temperatures.
Table 3. The thermodynamic parameters of the formation rhenium(V)- 4,5-
dihydro-1H-imidazole-2-thiol complexes in 4 M HCl at different temperatures
Species -Ho, kJ/mole -Go, kJ/mole -So, J/mole
[ReOLCl4]
36.97 32.88 13.70
[ReOL2Cl3] 22.36 28.97 3.05
[ReOL3Cl2]+ 27.84 27.65 0.65
[ReOL4Cl]2+
48.78 24.99 79.86
The values of the entropy changes for the mono-substituted complex compared
to the disubstituted complex have a much greater significance [30]
. Thus, as the
higher value of So can be interpreted in favor substitution of chloride ion in the trans-position to the oxygen oxorhenium groups is apparently due to the fact that
Re-Cl distance being in trans-position to the oxygen of the oxorhenium group in
the equatorial plane [31]
. Significant decrease of So is probably due to the fact that
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17
the introduction of a second molecule of 4,5-dihydro-1H-imidazole-2-thiol in the
inner coordination sphere becomes more difficult and that such molecule may
replace one of the four chloride ions that are in the equatorial plane [32]
.
Mole fractions are commonly used to calculate the concentrations of the
individual complexes on the basis of the formation constants. Mole fractions of a
particular form of the complex compressed as ratio of the concentration of the
complex to the total concentration of the metal ion ([MLi]/[Metal ion] = Xi). To
determine the field dominance of a complex in the form of rhenium(V)-4,5-
dihydro-1H-imidazole-2-thiol in 4 M HCl was calculated from the distribution
curves at different temperatures. Figure 3 shows the distribution curves of complex
models at 328 oK.
0
0.2
0.4
0.6
0.8
1
0
0.2
0.4
0.6
0.8
1
1 2 3 4 5 6 7
Xi
-lg[L]
X0
X1
X3
X2
X4
Fig. 3. Distribution curves of rhenium(V)- 4,5-dihydro-1H-imidazole-2-thiol
complexes at 328 oK; where X0 = [ReOCl5]
2-, X1 = [ReOLCl4]
-, X2 = [ReOL2Cl3],
X3 = [ReOL3Cl2]+, X4 = [ReOL4Cl2]
2+.
Analysis of the distribution curves show that increasing temperature has
little effect on the proportions of the maximum output value for all complexes.
Increasing temperature causes Ximax
being shifted towards higher values of
equilibrium concentration of 4,5-dihydro-1H-imidazole-2-thiol (Table 4).
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18
Table 4. The Ximax
output equilibrium values for rhenium(V)-4,5-dihydro-1H-
imidazole-2-thiol complexes in 4 M HCl at different temperatures
Species Values -lg [L] at Xi
max
273 oK 288
oK 298
oK 308
oK 318
oK 328
oK 338
oK
[ReOLCl4]
6.0 5.8 5.6 5.4 5.2 5.0 4.8
[ReOL2Cl3] 5.4 5.2 5.0 4.8 4.6 4.4 4.4
[ReOL3Cl2]+ 5.0 4.8 4.6 4.4 4.2 3.8 3.6
Based on these data it is possible to choose the optimum conditions for the isolation of
certain complex, establishing their composition and structure.
REFERENCES
1. Andres Garcia E. and Blanco Gomis D., Microchem. Acta, 1996, 4, 124. 2. Cao S. and Zhang M., J. Trace Microprobe Tech., 1999, 17, 157. 3. Bjerrum J., Metal amine formation in aqueous solutions: theory of the reversible step
reactions, Haase P. and Sons (Copenhagen, Denmark), 1941, 296.
4. Florence A.T. and Attwood D., Physical principles of pharmacy, Macmillan (London), 1981.
5. Poddar S.N., Dey K. and Poddar N.G., Indian J. Chem., 1970, 8, 364. 6. Schwarzenbach G. and Ackerman H., Helv. Chim. Acta, 1948, 31, 1029. 7. Pund D.A., Bhagwatkar R.A., Tayade D.T. and Rathod D.B., Rasayan J. Chem., 2010,
3(2), 246.
8. Tihile M.S., Journal of Chemical and Pharmaceutical Research, 2012, 4(4), 2223. 9. Dipak T.T., International Journal of Chemistry, 2011, 3(1), 36. 10. Gudadhe S., Narwade M.L. and Jamode V.S., Acta Ciencia Indica (Chem.), 1985, 11, 234. 11. Saha N., Dalia M. and Sinha S., Indian J. Chem., 1986, 25A, 629. 12. Rana A.K. and Shah J.R., J. Indian Chem. Soc., 1986, 63, 281. 13. Fukuda V., Morishita R. and Sone K., Bull. Chem. Sep. Jpn., 1985, 49, 1017. 14. Jolly V.S., Arora G.D. and Taiwar P., J. Indian Chem. Soc., 1990, 61, 1001. 15. Natrajan C. and Thormaraj P., Indian J. Chem., 1991, 30A, 722. 16. Narwade M.L., Chincholkar M.M. and Sathe S.W., J. Indian Chem. Soc., 1985, 62, 194. 17. Sawalakhe P.D. and Narwade M.L., J. Indian Chem. Soc., 1995, 70, 25. 18. Kadu M.V. and Jamode V.S., Asian J. Chem., 1999, 11, 420. 19. Hamid R.J. and Hadi n.Z., E-Journal of Chemistry, 2012, 9(3), p. 1518-1525. 20. Bjerrum J. and Bang E., Acta Chem. Scand. Ser., 1979, A33, 297. 21. Irving H.M. and Rossotti H.S., J. Chem. Soc., 1953, 3397; J. Chem. Soc., 1954, 2904.
22. Valeria M. Nurchi, Guido Crisponi, Tiziana Pivetta, Martina Donatoni and Maurizio Remelli, J. of Inorg. Biochem., 2008, 102(4), 684.
23. Atkins, Peter; De Paula, Julio (10 March 2006). Physical Chemistry (8th ed.). Freeman W.H. and Company, p. 212.
24. Ives D.J.G., Chemical Thermodynamics, University Chemistry, Macdonald Technical and Scientific, 1971.
25. Rigano C., Rizzarelli E. and Sammartano S., Thermochim. Acta, 1979, 33, 211. 26. Abd Erbary H.M., Shehata H.A., El Arab M.A.F., Mohamed A.A. and Emara M.M., J. Ind.
Chem. Soc., 1996, 73, 25.
27. Nair U.S.A. and Nancollas G.H., J. Chem. Soc., 1961, 255, 4367.
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28. Dickerson R.E., Geis I. and Benjamin I.W.A., Chemistry, Matter and the Universe, (USA), 1976.
29. Amindzhanov A.A. and Kurbanov N.M., Journal of Inorganic Chemistry (Russian Federation), 1990, 35(3), p. 672-678.
30. Promila D.T. and Lonibala R., J. Chem. Eng. Data, 2010, 55, 1166. 31. Amindzhanov A.A. and Gagieva S.Ch., Journal of Inorganic Chemistry (Russian
Federation ), 1996, 35(3), p. 1867-1871. 32. Amindzhanov A.A., Akhmedov K.U. and Kotegov K.V., Journal of Inorganic Chemistry
(Russian Federation ), 1988, 33(2), p. 379-384.
(CnH2n+1)4NReO4 (1
-
20
Tc (C5H11)4NTcO4 ( NaNO3) (1 1,2) HNO3 , (1,5 8,5) 10
-2 /
4 HNO3, 7,510-8
/ 239PuO2(NO3)2 4,3 / 106
Ru(NO)(NO3)3, 239Pu 106Ru (1,2
2,5)102 (6,8 8,5)102 . (C6H13)4NMeO4 ( ), - Tc.
( ) (C3H7)4NTcO4 (C5H11)4NTcO4 , a = 3,98 TcC1-x 0,61 < x < 0,85 . , 94 % 6 % , (C3H7)4NTcO4, (C5H11)4NTcO4 (C5H11)4NReO4 .
, . , , (. NbCl6) CH2 , (=20 3).
(CnH2n+1)4NMO4 (=Tc, Re ; n=3, 5, 6) .
- - - - . 20 /.
- , , , .
(1-2 . %) , .
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21
(V) 1--2- 4,5 / HCL 298
.., .., ..
- 1--2- H2[ReOCl5]1--2- 4,5/ Hl 298. , , : 1=2,310
5; 2=1,3104; 3=1,010
4; 4=4,1102.
(V) 1--2- . i 1--2- (V) 4,5 / 5,5 / HCl 298 , . , 298 1 4,5 / HCl 2,3105, 5,5 / HCl 8,1105. 2 HCl 4,5 5,5 / 1,3104 7,0104.
H2[ReOCl5]1--2- 4,5 / HCl 298 .
. -1--2- (V) 4,5/ HCl 298 , 0-[ReOl5]
2, 1-[ReOLl4]
, 2-[ReOL2l3], 3-[ReOL3l2]+, 4-[ReOL4l]
2+
-
22
. *., . *., . .** , *,
**,
, , , , . . . - . , . , . , , . -. , , , -, , , . . -, : . , 10 % . . . [Zn(NH3)4]SO4, - [Zn(NH3)4](ReO4)2. :
ZnSO4 + 4NH4OH = [Zn(NH3)4]SO4 + 4H2O,
-
23
[Zn(NH3)4]SO4 + 2NH4ReO4 = [Zn(NH3)4](ReO4)2 + (NH4)2SO4.
:
[Zn(NH3)4](ReO4)2 + 4H2O = Zn(OH)2 + 2NH4ReO4 + 2NH4OH,
[Zn(NH3)4](ReO4)2 + 2H2SO4 = ZnSO4 + 2NH4ReO4 + (NH4)2SO4.
. , %: 86 , 99 , 96 . .
,
.., .., .., .. , ,
, .
- . - . Re. , - .
Re- ( ) , . - Re- , Re ( 924 -1, ReO4
-).
- (20-100 /3) ReO4
-, .
-
24
Re . Re- (3-20 / NaF)
3(F4) ReO4- 924 -1
(900, 915, 930 -1), .
Re . Re , .
Re, , . Re 4, .. 1:4. , ReO4
-
4. , 1:1 1:4, ()
(G) : 1:1, 1:2, 1:3. :
:
Re Re
G, / G, /
1:1 3,8010-3 13,79 7,2010-3 12,22
1:2 6,2210-7 35,39 1,3310-4 22,11
1:3 2,0010-8 43,90 6,2210-7 35,38
Re , , Re .
[ReO(H2Cit)4(OH)2]
-, - [ReO2F4]
-.
-
25
.., .., .., .. , . , . , 101, -mail:
harin-ei@mail.ru
, , , . , Re2O7 3. .1 50 60% Re 90% . .2
, , .
- , , , , . , , . - (. , ).
: 1.
, SO2 - .3
2. .
3. Purolite -172, .4,5
-
26
1. .., .., .., ..
// - . 2011. 12. . 170-175.
2. .., .., .., .. // . 2011. 4. . 221-229
3. .., .., .., .. 2393253, . 18, 27.06.2010
4. .., .., .., .., .. , // XI - . : - , 2012. . 4-8
5. .., .., .., .., .. , // IX - . .: , 2012. . 455-457
(V)
(V)
1 .., 1 .., 2 ..
1 .., 1 .. 1 ,
2
, .. . . (Pb4Re3Mo3)S16 , , . .
-
27
, , , . . VI VII . Mo (IV) Re (IV) 0,68 0 0,67 0. . . , + 4 - S2, ReS2 . , .
- -, -, - - . (V) Re (V) (S),1--2- (1-Met-2-Mi),1,2,4-(1,2,4-Triaz), 1,3,4-(Thiad) .
, - (V) Re (V) , . , Mo(V) Re (V) . , (HCl, H2SO4, HNO3) (HCOOH, CH3COOH) (V) Re(V) :[OL(SCN)2(2)] , [ReOL(SCN)2(2)] [OL23]2H2O, [ReOL23]22, [OL4]22, [ReOL4]32 ,L-SC, 1-Met-2-Mi, 1,2,4-Triaz 1,3,4-Thiad.
, =____=, (-, Re) . . [Mo2O3L2(H2O)2Cl4]2H2O, [R2O3L2(OH)2Cl2]2H2O,
*[Mo2O3L4Cl4]2H2O
[R2O3L2(OH)2Cl2]2H2O*,
[Mo2O3L4Br4]2H2O, [Re2O3L4(NH3)4]4 22 , ,
-
28
. - .
, (V) Re(V) .
, (V) Re(V) - - , , (V) (V), .
, , , . , (V) Re (V) . (V) - 1-Met-2-Mi,1.2.4- -Triaz, 1.3.4-Thiad :(N2H5)2[Mo2O4L(OH)4(H2O)],(N2H5)2[Mo2O4L2(OH)4], (N2H5)2[Mo2O4L2(24)2], (N2H5)2[Mo2O4L2(SN)2(OH)2],(N2H5)2[Mo2O4L2l4] , 24., (V) - . , (V). SC, 1- Met-2-Mi, (V) Re (V) , (). (V) (V). - (V) (V) , .
(II) 3--1,2,4--5
6 / l 273
.., ..
[1.2] (II) 1,2,4--5 1-6 / HCl 273-338 .
-
29
[3] (II) 1,2,4--5 (NaNO3) . , - (II) 3--1,2,4--5.
(II) 3--1,2,4--5 6 / HCl 273 . - 3--1,2,4--5 273 (II) 6 / HCl. , CuCI2 3--1,2,4--5 6 / HCl . (II) 3--1,2,4--5 (.).
(II)
3--1,2,4--5 6 / HCl(273).
T, 1 2 3 4
273 4,98 3,82 3,30 2,93
(II) (.), 3--1,2,4--5 6 / HCl 273, .
. (II) 3--1,2,4--5 6 / HCl 273 ,0-CuCl2;
1-[CuL(H2O)2Cl]+; 2-[CuL2(H2O)2]
2+; 3-[CuL3(H2O)]
2+; 4-[CuL4]
2+.
-
30
, 4- 3--1,2,4- (II) 6 / HCI.
1. .., , ..
(II) 1,2,4--5 6 / HCI 298 // . 2011. -.54, 9. .759-764
2. .., , .. (II) 1,2,4--5 6 / HCI 288 // , 2011.-.71. 7. .19-22.
3. .., .. (II) 1,2,4--5 0.01 / // . 2012 .55, 6 -. 471-477.
--
.., .., .. - ,
360032, . 446, .33. alakaeva-L@mail.ru
- .
. . , Vll 6- d-. Re . Re (Vll) Re (lV, V) SnCl. Re n10-4 % Re.
, . , Re .
-
31
. .
Re (Vll) - (-) , - =520, Re (Vll) - =560. =7,6 2 , Re: -=2:3, Re (Vll) n10-10 / . Re, .. . n10-18- n10-21 / .
(V) (II) C 1--2,3--5- 6 /
I 318
.,. .., .., .. ,
. , , . (V) (II) 1--2,3--5- 6 / I 318 . , (V) 1--2,3--5- 5-- , : 1=3,2310
4; 2=9,33103; 3=4,6710
3; 4=2,18103;
5=1,51102 ( ).
[1] : *
1 =5,24104; *
2 =1,15104; *
3 =4,36103; *
4 =1,38103 *
5 =1,26102
. (II) 1--2,3--5- 4- : 1=5,63 (1=4,2610
5); 2=4,45 (2=2,8110
4); 3=2,57 (3=3,71102); 4=2,45 (4=2,8110
2). *
ip (* ):
*
1p =5,70 (*
1 =5,01105); *
2p =4,40 (*
2 =2.51104); *
3p =2,87 (*
3 =7,41102);
*
4p =2.12 (*
4 =1,31102).
-1--2,3--5- (II) 1--2,3---5- (V) ,
-
32
. , *
1 *
1
9,56 , *2 2,18 .
*
3 *
4 *
3 *
4
5,88 10,53 . 4 1,221015, 3,011015. 2.47 (II) 1--2,3--5-.
1. .., .. . . . , 1983, .28, 12, . 3090-3094
(N --)
.. ,
. , , , . , , N-- , , , .
N-- , , . . .
-
33
. , , - . 4 : 1) - ( )
. - , - , - .
2) ij : Sji = jid = 0 (ij )
3) , : 1 = 2 = 3 = .= i = j id =
4) ji ji =j id .
, , . . , . N--- () , .
(+4)
..,1 .., 1 .., 2 ..2 1 "-
", , , iitcm@yandex.ru
2 .., ,
- , . [1] (3+), -- , ( EtAlCl2 ) [2]. , ,
-
34
. , - - () -(). , , .
, 1,1- . , , - 1- .
ca b
a) COCl2, Et3N, Et2O b) R-2-OH-C6H3-CHO; CoCl2*6H2O; c) Et3N, TiCl4
Ti:Al:Mg 1:500:200.
1. S. Padmanabhan, S. Katao, K. Nomura, Organometallics, 2007, 26, 1616.
2. Abbo H. S., Mapolie S. F., Darkwa J., Titinchi S. J. J. J., Organomet. Chem.,
2007, 692, 5327.
14-43-01014
-
35
L+2.18%FE, 0,03%
NACL
.., .., .., .., ..
.. ., . ,
, . , , . l+2.18%Fe. 0.005 0.5 .%. - (2.18%) (5%). , . 8 140 . ( 50% 50% ). . , , , 0,03%- NaCl ( 4233-77). -200 ML-8. . -50-1 2 /, NaCl. , . , 0,005-0,5% . NaCl , , ( 1).
-
36
1 - Al+2.18%Fe, , 0,03% - NaCl NaCl.
, .%
- .. -. -.. -.
/2 /2.
-
0,005
0,01
0,05
0,1
0,5
0.680
0.620
0.600
0.530
0.500
0,484
0.965
0.950
0.925
0.900
0.880
0,860
0.500
0.480
0.460
0.450
0.420
0,400
0.650
0.640
0.620
0.600
0.600
0,584
0.92
0.74
0.68
0.60
0.52
0,50
3,1
2,48
2,28
2,01
1,74
1,67
, 0.005-0.5% , Al+2,18%Fe.
4- 1,2,4- (II) 6 / HCl
.., .., ..
(II) 4--1,2,4--5 6 / HCl 273-338. . i 4--1,2,4- Cu (II) 6 / HCl 273 : : 1=3.93(1=8.5110
3); 2=3.46(2=2.88103);
3=3.23(3=1.70103); 4=3.08 (4=1.2010
3); : *i (
*
i ):*
1 =4.19(*
1 =1.55104);
*
2 =3.58(*
2 =3.80103); *3 =3.22(
*
3 =1.66103); *4 =2.73(
*
4 =5.37102);
*i (*
i ) 4--1,2,4-
(II) 6 / HCl 273, *i (*
i ):
(V) 4--1,2,4- -5, 6 / HCl 273 , i , : 1 = 3.69; 2 =2.85; 3 = 2.11; 4=1.41 1=4,9010
3;
2=7,08102; 3=1,2910
2; 4=2,6101).
( .).
-
37
1 4-
-1,2,4 (II) 6 / HCl
-,/ -G,/ S,/
[CuL(H2O)5]Cl2 14,06 22,62 28,71
[CuL2(H2O)4]Cl2 12,30 19,49 24,11
[CuL3(H2O)3]Cl2
11,05 17,60 21,98
[CuL4(H2O)]2Cl2
9,70 14,94 17,58
, . 1 , 4--1,2,4- -5 G . .
Al+2.18%Fe,
3%- NACl
.., .., .., .., . . ..
, , . , , . l+2,18%Fe. 0,005 0,5 .%. - , . 8 140. ( 50% 50% ). . , , , 3%- NaCl ( 4233-77). 200 ML-8. .
-
38
-50-1 2 /, 3%- NaCl. , - . , 0,005-0,5% . , , .(.1).
1 - Al+2,18%Fe,
3%- NaCl
- , .
%
-.. -. -.. -. i10 10
/2 /2
- 0.860 0.994 0.600 0.620 0.170 5.70
0.005 0.860 0.998 0.550 0.580 0.162 5.42
0.01 0.848 0.970 0.534 0.580 0.150 5.03
0.05 0.832 0.960 0.518 0.562 0.146 4.89
0.1 0.818 0.954 0.500 0.540 0.134 4.48
0.5 0.800 0.925 0.480 0.522 0.130 4.35
, 0.005-0.5% 50% , Al+2,18%Fe.
(III) (V) C 1--2,3--5- 6 /
I 308 .., .., ..,
.. -
(V) 1--2,3--5- 6 / I 308 . (III) 1--2,3--5- (V) (III). (III) 1--2,3--5- 5 , : 1=5.41(1=2.5710
5);
2=3.61(2=4.07103); 3=3.32(3=2.0910
3); 4=3.05(4=1.12103);
5=2.79(5=6.16102).
-
39
*
i (*
i ):*
1 =5.42(*
1 =2.63105); *2 =3.88(
*
2 =7.58103);
*
3 =3.36(*
3 =2.29103); *4 =3.00(
*
4 =1.10103); *5 =2.47(
*
5 =2.95102).
(V) 1--2,3--5- , pKi (Ki)
n : 1=4.85(1=7.0710
4); 2=4.23(2=1.70104); 3=3.87(3=7.4110
3); 4= 3.47(4=2.9510
3); 5=2.30(5=1.99102).
*i (*
i ):*
1 =5.03(*
1 =1.07105);
*
2 =4.31(*
2 =2.04104); *3 =3.79(
*
3 =6.16103); *4 =3.12(
*
4 =1.31103);
*
5 =1.86(*
5 =7.2101).
*i -1--2,3--5-
(III) 1--2,3--5- (V) , *
1 *
5 -1--
2,3--5- (III) 2.46 4.1 , . , 1--2,3--5- (V) (III) 2.69, 2.68, 1.31 . (III) ( *5 = 1.3410
18)
1.05 ( *5 = 1.2810
18).
VO3+ - VO2+/VO3+
.., ..
- . - v2+/vo3+ vo
3+ 2,4 /,
.
v4+/v5+ . v2+/vo2+
0,8 1,03. v2+/vo3+ .
-
40
- v2+ vo3+ VOSO4 NH4VO(SO4)2. v2+ vo3+ , - . v2+/vo3+ v2+ . . 1 lg[v3+]/[vo2+] 298.
.1. lg[v3+]/[vo2+]
, = f(lg[v3+]/[vo2+]) 0,058, . v2+/vo3+, lg[v3+]/[vo2+] 298, 0,596.
, v2+/vo3+, 298 2,4 / 397 195B. E=f(lgCThio) , vo3+, . vo3+ , . , Fi [Thio] . Fi [Thio] , 1=1,6*10
5, 2=4*107
.
(V) [ReOL4Br]Br22H2O
-
41
.., .., .. ..
-
, . , , , , /1/. , , . , , , /2/.
/3-4/.
(V) , , .
. (V) . 0,000001 0,01%. . . 18-24 , 251 /5/. .
1
(V) c .
1
-
42
(V)
, %
-
1 2 3 4 (2)
45 39 42 43 42,2 -
85 79 89 74 81,7 -
, 0,0001%
48 67 71 66 63,0 20,8
90 88 95 90 90,7 9,0
(V), 0,0001%
60 63 59 67 62,2 20,0
95 96 96 94 95,2 13,5
(V), 0,00001%
49 50 61 74 58,5 16,3
96 93 97 96 95,5 13,8
(V), 0,000001%
51 49 54 67 55,2 13,0
95 93 98 94 95,0 13,3
(V), 0,0000001%
49 51 46 42 47,0 4,8
80 74 64 72 72,5 -9,2
[ReOL4Br]Br22H2O . 2, , (V) 0,001-0,0001%. 0,0001-0,00001%.
-
43
2 (V)
,
,
,
(2) 16,6 13,5 - - ,
0,01% 17,8 16,3 1,2 2,8
(V), 0,001%
18,4 9,7 1,8 -3,8
(V), 0,0001%
18,5 15,2 1,9 1,7
(V), 0,00001%
17,5 18,5 0,9 5,0
(V), 0,000001%
16,8
13,6 0,2 0,1
(V) (. 3).
3 (V)
,
,
,
,
1 2 3 1 2 3 (2) 0,43 0,68 0,40 0,50 4,32 5,38 4,28 4,66
, 0,005% 0,71 0,66 0,56 0,64 4,10 4,91 5,42 4,81
(V), 0,001%
0,45 0,53 0,47 0,48 4,43 4,25 4,1 4,26
(V), 0,0001%
0,80 0,77 0,81 0,79 5,25 5,54 5,13 5,3
(V), 0,00001%
0,84 0,81 0,92 0,85 5,82 6,21 5,96 5,99
(V), 0,000001%
0,54 0,49 0,45 0,49 4,22 4,44 4,75 4,47
(.3), (V) .
-
44
0,0001-0,00001%.
4 .
4
,
3 5 7 9
(2) 34 66 125 162 -
0,005% 33 68 132 174 12
0,00001% 35 68 136 178 16
0,000001%
33 65 128 159 3
1. .. . .: , 1974, .315
2. .., ..
,
//. . . .-
, 1990.-. 55-62.
3. .. . .: , 1976.-.583
4. .. //
. .- .: .- .6.- 1983.- .152-163.
5. 21620-0-76, 21820, 4-76. , , ., 1976. .3-20.
(II) 1/ HNO3 288
.., .., ..
-
Hg(NO3)2--1/ HNO3 288 .
-
45
-
(II) 1 / NO3 288.
- (II) 1 / NO3 288
CHg2+. 10
3 CL
.10
3
E. -lg[L] /
1,98 83,47 80,0 3,29 3,95
2,18 81,84 92,0 3,50 3,61
2,36 80,28 102,0 3,68 3,30
2,604 78,29 113,0 3,88 2,95
2,77 76,86 123,0 4,06 2,73
2,94 75,48 135,0 4,27 2,54
3,10 74,11 145,0 4,45 2,37
3,25 72,87 155,0 4,63 2,23
3,40 71,63 165,0 4,81 2,09
3,54 70,43 177,0 5,02 1,98
3,68 69,27 188,0 5,22 1,87
3,90 67,42 197,0 5,38 1,72
4,11 65,66 206,0 5,55 1,59
4,31 64,00 217,0 5,75 1,48
4,50 62,42 229,0 5,96 1,38
4,68 60,91 239,0 6,14 1,29
4,86 59,48 250,0 6,34 1,22
5,02 58,11 270,0 6,69 1,15
5,18 56,80 277,0 6,82 1,09
5,33 55,55 285,0 6,97 1,04
5,47 54,35 295,0 7,15 0,99
5,61 53,21 306,0 7,34 0,94
5,74 52,11 317,0 7,54 0,90
5,87 51,06 326,0 7,70 0,86
5,99 50,04 337,0 7,90 0,83
6,22 48,14 345,0 8,05 0,77
6,43 46,37 357,0 8,27 0,72
6,63 44,72 365,0 8,41 0,67
6,81 43,19 375,0 8,60 0,63
6,98 41,77 387,0 8,81 0,59
7,22 39,79 390,0 8,88 0,55
-
46
7,44 37,99 394,0 8,96 0,51
7,69 35,84 396,0 9,00 0,46
, n =f(-lg[L]),
1.
. 1. (II) 1 / NO3 288
,
.
pKi (Ki)
: 1=8,97 (K1=9,3108); 2 = 5,72 (K2= 5,210
5); 3 = 4,33 (K3=
2,1104); 4 = 3,58. (K4= 3,8103)
(II)
0,1 / HNO3
.., .., .. -
(II) c 0,1 / HNO3.
lgKi=f(1/) (.)
S ,
. G=H-TS.
-
47
. i (II) 0,1 /HNO3 273-338: 1-1; 2-
2; 3-3; 4-4
(II) 0,1 / HNO3.
(II) 0,1 /HNO3
-,
/
-G,
/
S,
/()
[HgL(H2O)3]2+
27,72 38,02 34,56
[HgL2(H2O)2]2+
16,48 25,49 30,21
[HgL3(H2O)]2+
17,50 19,82 7,73
[HgL4]2+
20,51 15,15 -18,03
(II) (V) 4- -1,2,4 -5 6 / HCL 288
.., .., ..
, - Cu (II) - 4--1,2,4-- 5 6 / HCl 288, , , *i (
*
i ): 1 = 3.75 (1=5,62103); 2 = 3.43
-
48
(2=2,69103); 3 = 3.20 (3=1,5810
3); 4 =3,07(4=1,1710
3).
4--1,2,4- (II) 6 / HCl 288, (V) 4--1,2,4- -5, 6 / HCl 288 1 = 3.35; 2 = 2.79; 3 = 1.81; 4 =1,62. (1=2,2410
3; 2=6,16102; 3=6,410
1; 4=4,2101) ,
i , . , Cu (II) - 4--1,2,4- -5 6 / HCl - 288, 288 (.)
. (II) 4- -1,2,4--5 6 / Cl 288 . 0[u(H2O)6]Cl2;1[uL(H2O)5]Cl2; 2[uL2(H2O)4]Cl2;3
[uL3(H2O)3]Cl2; 4uL4(H2O)2]Cl2
(V) 1--4-
.., ..
, [ReOL2 (OH)2Cl2]2H2O 40
o 80o. 60o. , 1,68% ,
-
49
. , 95 . 2,0% . , [ReOL2(OH)2Cl2]2H2O . 80-156o. 8,40% . 156-292o. 220. 14,28% . , 1--4-. 292-490o . 292-387o , 342o. 18,91% . 387-490 436. 24,79% 24,79 .
[ReOL(SCN)2Cl]2H2O . ( ) .
- (..), :
E
AR
RT
E
Tn
n
ln)1(
)1(1ln
2
1
n 1,
E
AR
RT
E
Tln
)1ln(ln
2
n = 1,
: T (K); R ; (/); .
-a (..):
2
21
ln1
)1(1ln
ss
s
n
RT
E
RT
E
E
ART
n
n 1,
2)1ln(ln
sRT
E n = 1,
: = - Ts; Ts - .
-
50
(V) 1--4- [ReOL2 (OH)2Cl2]2H2O
, /
, /
G, /
S, /
A, -1
I .. ..
69,66
75,44
66,90
72,68
91,57
91,54
-74,08
-56,64
9,34108
7,76109
II .. ..
73,19
79,38
69,93
76,12
114,21
114,23
-112,68
-96,97
1,05107 7,08107
III
.. ..
84,93
91,92
-80,84
-87,83
-20,95
-34,62
-121,50
-107,94
4,60106 2,34107
IV .. ..
127,87
137,11
122,77
132,01
178,63
179,10
-90,83
-76,57
2,29108
1,35109
V .. ..
221,20
238,39
-215,32
-232,51
-230,87
-264,68
21,94
45,37
2,061014
3,631015
(V) 7 / Br 298
.., .., ..
(V) 12,35 7/ HBr 298 1 -12,35 (V) 7 / HBr 298 .
1
-12,35 (V) 7 / HBr
298
Re(V) 104 L 10
2
E, [L]104 n /
24,7 0,856 24,10 20,38 4,63
30,6 0,849 32,20 15,75 4,19
36,5 0,843 38,60 13,31 3,97
-
51
42,2 0,836 44,40 11,24 3,76
47,9 0,830 49,90 9,57 3,51
53,5 0,824 55,20 8,55 3,32
59,0 0,818 60,00 7,37 3,22
64,5 0,812 64,70 6,23 2,98
69,8 0,806 68,90 5,70 2,60
75,1 0,801 72,30 5,05 2,29
80,3 0,795 75,90 5,00 2,05
90,5 0,784 79,40 4,58 1,76
100,4 0,773 83,00 3,73 1,55
110,0 0,763 86,20 3,46 1,24
121,7 0,750 88,80 3,18 1,03
133,0 0,738 91,00 3,07 0,88
154,6 0,714 92,70 2,85 0,62
174,8 0,692 93,90 2,67 0,47
211,7 0,652 94,80 2,55 0,36
-12,35 (V) 7 / HBr 298 . -12,35 (V) : 1= 3,95;
2 = 3,51; 3 = 3,12; 4 = 2,71; 5=2,15. , .
-
52
1. .., ..
(V)
.2
2. .., .., .., ..,
.. -
3
3. .., .., ..
CHCl3
..4
4. .., .., .., ..
(V) 1--2-
7/ HCl 2735
5. .., ..
(V) 8
6. .., .., .., ..,
.. (III)
, ,
( ) ,
9
7. .., .., .., ..
-
10
8. Gouda G.A., Aminjanov A.A. Potentiometric and thermodynamic
investigation of rhenium(V) complexes with 4,5-dihydro-1H-imidazole-2-
thiol...12
9. .., ..
(CnH2n+1)4NReO4 (1
-
53
10. .., .., ..
(V) 1--2-
4,5 / HCl 298 21
11. . ., .., ..
...22
12. .., .., .., ..
,
23
13. .., .., .., ..
.25
14. .., .., .., ..,
..
(V) (V)
...26
15. .., ..
(II) 3--1,2,4--5
6 / l 273.28
16. .., .., ..
-30
17. .,. .., .., .
(V) (II) c 1--2,3-
-5- 6 / l 318 ...31
18. ..
(N--
)32
19. .., .., .., ...
(+4)
33
-
54
20. .., .., .., ..,
.. L+2.18%Fe,
0,03% NaCl35
21. .., .., ..
4-
1,2,4- (II) 6 / HCl....36
22. .., .., .., ..,
.. Al+2.18%Fe,
3%- NaCl37
23. .., .., ..,
.. (III) (V) c 1--2,3-
-5- 6 / I 30838
24. .., .. VO3+
-
VO2+
/VO3+
39
25. .., .., .. ..
(V) [ReOL4Br]Br22H2O
41
26. .., .., ..
(II)
1 / NO3 288.44
27. .., .., ..
(II) 1 / HNO3..46
28. .., .., ..
(II) (V) 4- -1,2,4
-5 6 / HCl 288 .....................................47
29. .., ..
(V) 1--4-
..48
30. .., .., ..
(V) 7 / Br
298 50
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