Modeling the heteroleptic equilibria of organized molecular systems by using a double-titration technique: a novel determination of the fundamental equilibrium constants in a ternary system involving a macrocyclic cobalt(II) complex, dioxygen, and competing axial ligands

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.).

Download Full-text

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.).

Download Full-text

Recognition of hydrogen isotopomers by an open-cage fullerene

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

10.1098/rsta.2011.0629 ◽

2013 ◽

Vol 371 (1998) ◽

pp. 20110629 ◽

Cited By ~ 4

Author(s):

Yasujiro Murata ◽

Shih-Ching Chuang ◽

Fumiyuki Tanabe ◽

Michihisa Murata ◽

Koichi Komatsu

Keyword(s):

Equilibrium Constants ◽

Equilibrium Mixture ◽

Size Difference ◽

Binding Affinities ◽

Kinetic Isotope ◽

Molecular Sizes ◽

Lower Temperature ◽

Kinetics Of ◽

Pressure Hydrogen

We present our study on the recognition of hydrogen isotopes by an open-cage fullerene through determination of binding affinity of isotopes H 2 /HD/D 2 with the open-cage fullerene and comparison of their relative molecular sizes through kinetic-isotope-release experiments. We took advantage of isotope H 2 /D 2 exchange that generated an equilibrium mixture of H 2 /HD/D 2 in a stainless steel autoclave to conduct high-pressure hydrogen insertion into an open-cage fullerene. The equilibrium constants of three isotopes with the open-cage fullerene were determined at various pressures and temperatures. Our results show a higher equilibrium constant for HD into open-cage fullerene than the other two isotopomers, which is consistent with its dipolar nature. D 2 molecule generally binds stronger than H 2 because of its heavier mass; however, the affinity for H 2 becomes larger than D 2 at lower temperature, when size effect becomes dominant. We further investigated the kinetics of H 2 /HD/D 2 release from open-cage fullerene, proving their relative escaping rates. D 2 was found to be the smallest and H 2 the largest molecule. This notion has not only supported the observed inversion of relative binding affinities between H 2 and D 2 , but also demonstrated that comparison of size difference of single molecules through non-convalent kinetic-isotope effect was applicable.

Download Full-text

A Potentiometric Study on Proton-Transfer Equilibria and Cationic Conjugation in Pyridine N-Oxide Systems in Acetone and Methanol

Australian Journal of Chemistry ◽

10.1071/ch9960931 ◽

1996 ◽

Vol 49 (9) ◽

pp. 931 ◽

Cited By ~ 20

Author(s):

L Chmurzynski ◽

E Kaczmarczyk ◽

M Nesterowicz ◽

G Wawrzyniak ◽

Z Warnke

Keyword(s):

Proton Transfer ◽

Equilibrium Constants ◽

Proton Donor ◽

Heterocyclic Amines ◽

Transfer Reactions ◽

Oxide Systems ◽

Experimental Systems ◽

Proton Transfer Reactions ◽

Potentiometric Titration Method

The potentiometric titration method has been used to study the equilibria of cationic in sytems formed by substituted pyridine N-oxides in the polar, non-aqueous solvents acetone and methanol. For comparison, the systems with trimethylamine N-oxide as a representative of aliphatic amine N-oxides and pyridine representing parent heterocyclic amines were also studied. The cationic heteroconjugation constants, i.e. the equilibrium constants for conjugation reactions between free and protonated N-bases leading to the formation of unsymmetric BHB'+ cations, were determined in experimental systems with and without proton transfer. It was found that there were significant differences in the values of the cationic heteroconjugation constants determined in these two acid-base systems. The proton-transfer reactions limit and even preclude the determination of the cationic heteroconjugation constants. On this basis it was concluded that the heteroconjugation constants should be determined in systems without proton transfer. In such systems, in the amphiprotic solvent methanol, cationic heteroconjugation was ascertained in all substituted pyridine N-oxide systems, the values of heteroconjugation constants being relatively low (logarithms of their values of the order of 2-2.5), and only negligible in systems involving trimethylamine N-oxide. A more pronounced tendency towards cationic heteroconjugation of the [OHO]+ type was observed in the aprotic protophobic acetone, where heteroconjugation constants were determined for all amine N-oxide systems studied including those containing protonated trimethylamine N-oxide as a proton donor. However, the values of the cationic heteroconjugation constants were found to be, in methanol likewise, relatively low (log KBHB'+ of the order of 2-3). On the contrary, a greater extent of cationic heteroconjugation equilibria was observed in methanol than in acetone in the case of systems containing pyridine, i.e. [NHO]+ type bridges formed by amine N-oxides and heterocyclic amines. In methanol the heteroconjugation constants turned out to be determinable for all such systems studied (logarithms of the equilibrium constants being of the same order as for N-oxide systems), whereas in acetone the hetero constants were indeterminable for all systems.

Download Full-text

The experimental determination of hydromagnesite precipitation rates at 22.5–75ºC

Mineralogical Magazine ◽

10.1180/minmag.2014.078.6.07 ◽

2014 ◽

Vol 78 (6) ◽

pp. 1405-1416 ◽

Cited By ~ 11

Author(s):

U.-N. Berninger ◽

G. Jordan ◽

J. Schott ◽

E. H. Oelkers

Keyword(s):

Low Temperature ◽

Experimental Determination ◽

Closed System ◽

Equilibrium Constants ◽

Magnesium Silicate ◽

Silicate Mineral ◽

Dissolution Rates ◽

Dissolution And Precipitation

Natural hydromagnesite (Mg5(CO3)4(OH)2·4H2O) dissolution and precipitation experiments were performed in closed-system reactors as a function of temperature from 22.5 to 75ºC and at 8.6 < pH < 10.7. The equilibrium constants for the reaction Mg5(CO3)4(OH)2·4H2O + 6H+ = 5Mg2+ + 4HCO3– + 6H2O were determined by bracketing the final fluid compositions obtained from the dissolution and precipitation experiments. The resulting constants were found to be 1033.7±0.9, 1030.5±0.5 and 1026.5±0.5 at 22.5, 50 and 75ºC, respectively. Whereas dissolution rates were too fast to be determined from the experiments, precipitation rates were slower and quantified. The resulting BET surface areanormalized hydromagnesite precipitation rates increase by a factor of ~2 with pH decreasing from 10.7 to 8.6. Measured rates are approximately two orders of magnitude faster than corresponding forsterite dissolution rates, suggesting that the overall rates of the low-temperature carbonation of olivine are controlled by the relatively sluggish dissolution of the magnesium silicate mineral.

Download Full-text