Equilibrium constants of phosphoryl transfer from C(1) to C(6) of α-d-glucose 1-phosphate and from glucose 6-phosphate to water

The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the reactions of formation of the ML and ML2 complexes of both reagents with cadmium(II) ions were determined by graphical analysis and numerical interpretation of the absorbance-pH curves by the modified SQUAD-G program. Optimal conditions were proposed for the spectrophotometric determination of Cd in 10% v/v ethanol medium in the presence of 0.1% w/v Triton X-100 or 1% w/v Brij 35. BrPADAP and ClPADAP are the most sensitive spectrophotometric reagents for the determination of cadmium(II) ions (ε = 1.28-1.44 . 105 mmol-1 cm2 at 560 nm and pH 8.0-9.5) with a high colour contrast in the reaction (Δλmax ~117 nm) and a selectivity similar to that of other N-heterocyclic azodyes (PAR, PAN, etc.).

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Oxidation of (1-hydroxybenzyl)ferrocene and its derivatives substituted in phenyl ring with bis(triphenylsilyl) chromate

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19823375 ◽

1982 ◽

Vol 47 (12) ◽

pp. 3375-3380 ◽

Cited By ~ 1

Author(s):

Jaroslav Holeček ◽

Karel Handlíř ◽

Milan Nádvorník ◽

Milan Vlček

Keyword(s):

Linear Dependence ◽

Rate Constants ◽

Oxidation Rate ◽

Phenyl Ring ◽

Equilibrium Constants ◽

Aprotic Solvents ◽

Protonation Equilibrium ◽

Oxidation Of Alcohols ◽

Hammett Σ Constants ◽

Sulphuric Acid Medium

Kinetics have been studied of oxidation of (1-hydroxybenzyl)ferrocenes substituted in phenyl ring with bis(triphenylsilyl) chromate in benzene solutions as well as protonation of these alcohols in sulphuric acid medium. Logarithms of the oxidation rate constants (kobs, 20-40 °C) and those of the protonation equilibrium constants (KR+, 25 °C) show linear dependence on the Hammett σ constants, the ρ constant values being -0.86 to -0.40 and -2.50, respectively. These negative values suggest that the both processes are influenced by the same effects and confirm the mechanism proposed earlier for oxidation of alcohols with ferrocenyl substituent by action of bis(triphenylsilyl) chromate in aprotic solvents.

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Extraction of strontium and barium salts by the nitrobenzene solution of dicarbolide in the presence of glymes

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19850581 ◽

1985 ◽

Vol 50 (3) ◽

pp. 581-599 ◽

Cited By ~ 41

Author(s):

Petr Vaňura ◽

Emanuel Makrlík

Keyword(s):

Stability Constants ◽

Organic Phase ◽

Equilibrium Constants ◽

Minor Role ◽

Nitrobenzene Solution ◽

Ligand Structure ◽

Stability Constants Of Complexes ◽

Separation Factors ◽

The Stability ◽

A Minor

Extraction of microamounts of Sr2+ and Ba2+ (henceforth M2+) from the aqueous solutions of perchloric acid (0.0125-1.02 mol/l) by means of the nitrobenzene solutions of dicarbolide (0.004-0.05 mol/l of H+{Co(C2B9H11)2}-) was studied in the presence of monoglyme (only Ba2+), diglyme, triglyme, and tetraglyme (CH3O-(CH2-CH2O)nCH3, where n = 1, 2, 3, 4). The distribution of glyme betweeen the aqueous and organic phases, the extraction of the protonized glyme molecule HL+ together with the extraction of M2+ ion and of the glyme complex with the M2+ ion, i.e., ML2+ (where L is the molecule of glyme), were found to be the dominating reactions in the systems under study. In the systems with tri- and tetraglymes the extraction of H+ and M2+ ions solvated with two glyme molecules, i.e., the formation of HL2+ and ML22+ species, can probably play a minor role. The values of the respective equilibrium constants, of the stability constants of complexes formed in the organic phase, and the theoretical separation factors αBa/Sr were determined. The effect of the ligand structure on the values of extraction and stability constants in the organic phase is discussed.

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Europium and cerium extraction by the nitrobenzene solution of dicarbolide in the presence of polyethylene glycols

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19860498 ◽

1986 ◽

Vol 51 (3) ◽

pp. 498-515 ◽

Cited By ~ 13

Author(s):

Emanuel Makrlík ◽

Petr Vaňura

Keyword(s):

Molecular Weight ◽

Polyethylene Glycol ◽

Organic Phase ◽

Perchloric Acid ◽

Equilibrium Constants ◽

Polyethylene Glycols ◽

Individual Species ◽

Nitrobenzene Solution ◽

Separation Factors ◽

Equilibrium Data

Extraction of Eu3+ and Ce3+ microamounts from 0.1-0.4M perchloric acid by the nitrobenzene solution of dicarbolide H+[Co(C2B9H11)2]- in the presence of polyethylene glycols (Mr = 200, 300, 400) has been studied. The equilibrium data and the typical maxima on the dependence of the metal distribution ratio on the total analytical concentration of polyethylene glycol in the system can be explained assuming that the species ML3+org, ML3+2org, ML3+3org, MLH2+-1org, and HL+org (where M3+ = Eu3+, Ce3+; L = polyethylene glycol) are extracted into the organic phase. The values of extraction and equilibrium constants in the organic phase were determined and the effect of the polyethylene glycol molecular weight on the equilibrium constants and on the abundances of individual species in the organic phase is discussed. It has been found that the addition of polyethylene glycol to the acid - nitrobezene - dicarbolide system increases the values of the separation factors αCe/Eu.

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Spectrophotometric study of the acid-base and optical properties of the 5-bromo and 5-chloro derivatives of 2-(2-pyridylazo)-5-(diethylamino)phenol (BrPADAP, ClPADAP) and their complexation equilibria with zinc(II) ions

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19822676 ◽

1982 ◽

Vol 47 (10) ◽

pp. 2676-2691 ◽

Cited By ~ 6

Author(s):

Miroslav Macka ◽

Vlastimil Kubáň

Keyword(s):

Equilibrium Constants ◽

Spectrophotometric Study ◽

Graphical Analysis ◽

Alkaline Media ◽

Acid Base ◽

Ethanol Medium ◽

Triton X ◽

Mixed Water ◽

Derivatives Of

The optical and acid-base characteristics of BrPADAP and ClPADAP were studied in mixed water-ethanol and water-DMF media and in 10% ethanol medium in the presence of cationic, anionic and nonionic tensides. The composition, optical characteristics, molar absorption coefficients and equilibrium constants of the ML and ML2 complexes with zinc(II) ions were found by graphical analysis and numerical interpretation of the absorbance curves by the modified SQUAD-G program. Optimal conditions were found for the spectrophotometric determination of Zn(II) in the presence of 0.1% Triton X-100 or 1% Brij 35 in alkaline media with pH = 6.5-10. BrPADAP and ClPADAP are the most sensitive reagents (ε = 1.3-1.6 . 105 mmol-1 cm2 at 557 and 560 nm, respectively) for the determination of zinc with high colour contrast of the reaction (Δλ = 104 nm) and selectivity similar to that for the other N-heterocyclic azodyes (PAN, PAR, etc.).

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