Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Inclusive\bar K^{0*} (892) andK 0*(892) production on silicon by 200 GeVK − andπ −

The production of the neutralK ^? (892) resonances by 200 GeVK ^? andπ ^? has been studied over the kinematic range 0.0<x _f<1.0 andp _t ² <5.0 GeV². Longitudinal and transverse momentum distributions are presented. In addition the decay angular distributions inK ^? fragmentation to \(\bar K^{0*} \) have been investigated.     

Structure and properties of the ion pair charge-transfer complex of octacyanotungstate(IV) with the 2,2′-bipyridinium dication

The X-ray crystal structure of (bpyH2)2[W(CN)8]·4H2 O (bpyH2=2,2-bipyridinium) is described. The [W(CN)8]4– anion has an approximately square antiprismatic (D4d) conformation, seemingly imposed by strong anion–water–cation hydrogen-bonding interactions. Bond distances in the anion are: WC 2.150(5), 2.163(5); CN 1.128(6), 1.145(6)Å and the angles WCN are 177.6(5), 178.3(5)°. The dihydrate and the anhydrous salt are both intensely black solids, exhibiting ion-pair charge-transfer interaction between cation and anion. E.s.r. spectra indicate that 30% of the tungsten is present as WV in the solid state, but that in solution only the WIV complex is present. The electron withdrawing effect of the cation is discussed and compared with that in a series of salts with different bipyridinium cations.     

Lifetimes of charged and neutralD mesons

We have measured the lifetimes of hadronically produced charged and neutralD mesons using silicon microstrip detectors and an active silicon target in the NA32 spectrometer at the CERN SPS. We obtainτ _D± = (10.9± _1.5 ^1.9 )·10^?13s andτ _D ^(?)10 = (4.2±0.5)·10^?13s based on 59 and 90 fully reconstructed decays respectively, giving a ratioτ _D±/τ _D ^(?)10 of 2.6 ±0.5.     

Cyanide attack at low-spin iron(II)–diimine complexes: the structure of a cyanide-containing derivative of a leaving ligand

The isolation and structural characterisation of the product of addition of HCN to the Schiff base derived from phenyl 2-pyridyl ketone and 3,4-dimethylaniline (Me2bsb) provides evidence in favour of a mechanism involving nucleophilic attack at the coordinated ligand for reaction of the complex [Fe(Me₂bsb)₃]²⁺ with cyanide.     

The influence of ion pairing at the electrode/solution interface on the kinetics of heterogeneous electron transfer

A model is developed for the accelerating effect of non-reacting ions adsorbed on the inner Helmholtz plane on the kinetics of electron transfer to a reactant which is also situated on the same plane near the electrode. It is assumed that the charge density of non-reacting ions around the reacting ion can be described by a two dimensional distribution function analogous to that used by Fuoss to describe ion pairing in the bulk of the solution. Kinetic equations are presented in which the discreteness-of-charge terms are explicitly included and the magnitude of these terms is estimated on the basis of a simple model. The estimates show that the acceleration of hydrogen ion in the presence of adsorbed iodide ions can be attributed to the electrostatic effect of the surrounding ionic atmosphere.     

Application of the hypernetted chain approximation to the electrical double layer for 2:1 and 1:2 electrolytes

The equations needed to estimate the potential drop across the diffuse layer according to the hypernetted chain approximation (HNCA) are derived in this paper for 2:1 and 1:2 electrolytes at the restricted primitive level. It is shown that HNCA results can be expressed in the same format as the corresponding Gouy-Chapman equations with inclusion of two modifying functions. One function depends on the fraction of the solution volume occupied by the ions, and the other depends on the reciprocal thickness of the ionic atmosphere surrounding each ion. In addition, an expression for the potential profile in the diffuse layer for 2:1 and 1:2 electrolyte solutions is derived according to Gouy-Chapman theory. The modifying functions in the HNCA are then estimated using the Henderson-Blum approach for solutions containing ions with diameters of 300 and 400 pm for concentrations in the range from 0.1 to 2 M. It is shown that the Henderson-Blum approach is inadequate for systems with multivalent ions except for charge densities very close to the point of zero charge.