Kinetics of Complex Formation Between Cobalt(II) and the Polyamine Me2Octaen

Abstract

The kinetics and the equilibria of complex formation between Co(II) and the linear polyamine 1,25-dimethyl-1,4,7,10,13,16,19,22,25-nonaazapentacosane (Me₂Octaen) have been investigated in aqueous solution under anaerobic conditions by the stopped-flow and potentiometric method. Static titrations and kinetic experiments indicate that below pH 5.6 the binding of Co(II) to the ligand gives rise to several 1:1 complexes differing for their degree of protonation, whereas above pH 5.6 binuclear complexes are formed as well. The analysis of the kinetic data reveals that the mostly reactive form of the ligand (denoted in its fully protonated form as H₉L₉₊) is H₆L⁶⁺. The species H₅L⁵⁺ and H₄L⁴⁺ yield only a minor contribution to the overall process of complex formation. Measurements at different ionic strengths have shown positive salt effects, as expected for reactive processes involving particles with charges of the same sign. The analysis of the results shows that Co²⁺ and H₆L⁶⁺ react according to the internal conjugate base mechanism.     

Reaction of benzoquinones and naphthoquinones with 1,8-diamino-3,6-dioxanonane and with 1,11-diamino-3,6,9-trioxaundecane

Reaction of 1,4-naphthoquinone or 2,3-dichloro-1,4-naphthoquinone with α,ω-diamino-derivatives of poly(alkylenoxides) leads to the formation of α,ω-bis(quinonyl) amines. A similar reaction with chloranil, bromanil, dichlorodicyanobenzoquinone, S-phenylbenzoquinone and 1,4-benzoquinone itself, leads to the formation of quinoid crown ethers.     

Effect of elasticity of a polymer solution on the Hele-Shaw flow

In this study, the Hele-Shaw cell is used to examine the effect offluid elasticity on the flow patterns of two-dimensional potential flow. Flows around a circular cylinder, a square cylinder and flows through abruptly converging-diverging channels (slits) with different throat lengths are tested for water and 0.2 wt % polyacrylamide aqueous solution (PAA-solution). The viscosity of the latter is well modeled by the power law, and the first normal stress difference in the steady shear flow is around ten times higher than the shear stress. Although the PAA-solution is highly shear-thinning, the flows of PAA-solution well reproduce the two-dimensional potential flow patterns that correspond to the respective flow configurations when the flow rate is very low. The potential flow patterns ofPAA solution are disturbed in the opposite way of inertia effect observed for water. The streamlines near the upstream stagnation point of cylinders are shifted upstream separating from the cylinder surface when the flow rate is higher, while streamlines in the wake approach closer to the downstream stagnation point. Streamlines offlow through the slit at flow rates higher than the potential flow region show that a pair ofvortices is formed upstream the slit entrance, while the streamlines remain attached to the downstream wall after passing the slit.     

Effective spin spin interactions in the damped ferromagnets

Simanek's theory is extended by taking into account the nuclear spin excitations due to the motion of the electronic system. Damping of the magnons is found to be an extra criteria for having a finite interaction range for the nuclear spin system. The resonance excitation of Simanek's theory is due to the neglect of the second order in the hyperfine interaction.     

A study of degradation of low density polyethylene under natural weathering conditions

The effects of natural weathering on mechanical properties and chemical structure of low density polyethylene have been studied. It is found that no simple correlation exists between the development of carbonyl groups and mechanical properties such as stress or strain at break or elastic modulus. It appears that there is recovery in the mechanical properties during the winter months.     

Noncoplanar correlation spectra from the 2H(p, 2p)n reaction at Einc = 44.9 MeV

The differential cross section $\text{d}{}^3\text{σ/}\text{d}\text{Ω}{}_3\text{d}\text{Ω}{}_4\text{d}\text{E}{}_3$ for the ²H(p, 2p)n reaction at E_inc = 44.9 MeV is measured in noncoplanar geometry. The Amado model in general gives a good fit to the absolute cross section. The dependence of the cross section on the momentum of the undetected particle Q₅, on the scattering angle θ₃₄, as well as on the angle of the undetected particle is investigated.     

Cyclopropane derivatives from the lithium aluminium hydride reduction of methoxyalkynols

Lithium aluminium hydride reduction of methoxyalkynol(1) yields cyclopropane derivatives (2) and (3), both formed by loss of a methoxy group; a reaction scheme for their formation is presented.     

Quantification of total petrol hydrocarbons (TPH) in soil by IR-spectrometry and gas chromatography – conclusions from three proficiency testing rounds

Due to the utilisation of 1,1,2-trichlorotrifluoroethane (CFE) as extraction solvent the IR-spectrometric determination of total petrol hydrocarbon (TPH) in soil according to ISO/TR 11046 has been replaced by gas chromatography/flame ionisation detection (GC/FID) after extraction with a halogen-free solvent according to ISO/DIS 16703:2001. The results obtained with both methods by field laboratories in three proficiency testing (PT) rounds are compared. The consensus means obtained with GC/FID are typically 10%–20% (ranging between 0% and 25%) higher than those found with IR-spectroscopy. On the contrary, coefficients of variation (CV) are roughly double in case of GC/FID and are briefly discussed against the background of the Horwitz equation. Received: 19 November 2001 Accepted: 17 March 2002     

A sufficient condition for a graph to contain three disjoint 1-factors

Ore derived a sufficient condition for a graph to contain a Hamiltonian cycle. We obtain a sufficient condition, similar to Ore's condition, for a graph to contain a Hamiltonian cycle and a 1-factor which are edge disjoint.