Stability boundaries, percolation threshold, and two-phase coexistence for polydisperse fluids of adhesive colloidal particles

We study the polydisperse Baxter model of sticky hard spheres (SHS) in the modified mean spherical approximation (mMSA). This closure is known to be the zero-order approximation C0 of the Percus-Yevick closure in a density expansion. The simplicity of the closure allows a full analytical study of the model. In particular we study stability boundaries, the percolation threshold, and the gas-liquid coexistence curves. Various possible subcases of the model are treated in details. Although the detailed behavior depends upon the particularly chosen case, we find that, in general, polydispersity inhibits instabilities, increases the extent of the nonpercolating phase, and diminishes the size of the gas-liquid coexistence region. We also consider the first-order improvement of the mMSA (C0) closure (C1) and compare the percolation and gas-liquid boundaries for the one-component system with recent Monte Carlo simulations. Our results provide a qualitative understanding of the effect of polydispersity on SHS models and are expected to shed new light on the applicability of SHS models for colloidal mixtures.     

The use of “actinometer” gases in optical diagnostics of plasma etching mixtures: SF6-O2

The spectroscopic emission intensities from excited F atoms in SF₆-O₂ discharges at 1 torr have been correlated to the densities of atoms in their ground electronic state by measuring the excitation efficiencies of the electrons in the energy range 11 to 17 eV with a method which essentially consists in the analysis of the emission of Ar or N₂, added as actinometer gases to the discharge mixtures. The general applicability of the method has been tested by a direct titration of F atoms with chlorine. The spectroscopic analysis has allowed the determination of useful information on the trends of both the electron densities and their energies as a function of the oxygen percent in the feed.     

Plasma deposition of thin films from a fluorine-containing cyclosiloxane

Thin films have been deposited from radio-frequency glow discharges fed with vapors of a silicon- and fluorine-containing organic compound, namely 2,4,6-tris[(3,3,3-trifluoropropyl) (methyl)] cyclotrisiloxane, in mixture with argon. 2,4,6-tris[(3,3,3-trifluoropropyl)(methyl)]cyclotrisiloxane A triode reactor has been utilized to deposit films by independently changing substrate temperature and bias-induced ion-bombardment. Laser interferometry, electron spectroscopy for chemical analysis and Fourier-transform infrared spectroscopy have been used to monitor film growth rate and composition. Results unambiguously show an activating effect of the ion-bombardment, which confirm the validity of the ion-assisted deposition model utilized for the plasma deposition of both teflon- and silicone-like films. In our experiments, low substrate temperature and bias conditions results in films with a “monomer-like” stoichiometry, while drastic conditions give origin to materials with a completely different composition and a markedly increased hardness. © 1994 John Wiley & Sons, Inc.     

N-Haloamidines-V: Reaction of N-chloro-N'-aroyl-acetamidines and -benzamidines with enamines

The reaction between N-chloro-N'-aroyl-amidines and β,β-disubstituted enamines affords 1 - aroyl - 4 -amino - 4,5 - dihydro - imidazoles in low yields, the main reaction product being N - (2 - morpholino - 2,2 -disubstituted) - ethylidene - N' - aroyl - amidines. A similar reaction course was not observed with enamines bearing a hydrogen atom in the β-position. In this case only products derived from electrophilic chlorination on enamines were isolated.     

On the use of symmetry in first-order perturbed HF theory. II

A method is described whereby molecular symmetry is employed to reduce the number of two-electron integrals in perturbed Hartree–Fock calculations of second-order properties. The method is a generalization of the Dacre–Elder procedure. First- and second-rank perturbing tensor operators are examined in the coupled HF approach to electric dipole polarizabilities, magnetic susceptibilities, quadrupole polarizabilities, and spin-dopolar contributions to spin–spin coupling constants. The procedure sketched here permits a large saving of computer efforts, which is shown by some illustrative examples.     

Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions

The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal > 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.     

Reduction of cyclohexanone 2-nitrophenylhydrazone. Formation of cyclohexane-3-spiro-3,4-dihydro-1,2,4-benzotriazine

The structure of compound C₁₂H₁₅N₃, obtained by Perkin and Riley in 1923, through the reduction of cyclohexanone 2-nitrophenylhydrazone, was reexamined. This compound, considered originally as 3,4-cyclotetramethylene-4,5-dihydro-1,2,5-benzotriazepine (I) and later as 2-aminophenylazocyclohexene (II), is now defined through the nmr spectrum and chemical behaviour as cyclohexane-3-spiro-3,4-dihydro-1,2,4-benzotriazine (V). It is formed by spontaneous oxidation of the cyclic form of cyclohexanone 2-aminophenylhydrazone (namely, cyclohexane-3-spiro-1,2,3,4-tetrahydro-1,2,4-benzotriazine) obtained through amino group addition on the hydrazone double bond.     

Syntheses, structures, and reactivity of new pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) 4-acyl-5-pyrazolonate complexes

New [CpM(Q)Cl] complexes (M = Rh or Ir, Cp = pentamethylcyclopentadienyl, HQ = 1-phenyl-3-methyl-4R(C=O)-pyrazol-5-one in general, in detail HQ(Me), R = CH(3); HQ(Et), R = CH(2)CH(3); HQ(Piv), R = CH(2)-C(CH(3))(3); HQ(Bn), R = CH(2)-(C(6)H(5)); HQ(S), R = CH-(C(6)H(5))(2)) have been synthesized from the reaction of [CpMCl(2)](2) with the sodium salt, NaQ, of the appropriate HQ proligand. Crystal structure determinations for a representative selection of these [CpM(Q)Cl] compounds show a pseudo-octahedral metal environment with the Q ligand bonded in the O,O'-chelating form. In each case, two enantiomers (S(M)) and (R(M)) arise, differing only in the metal chirality. The reaction of [CpRh(Q(Bn))Cl] with MgCH(3)Br produces only halide exchange with the formation of [CpRh(Q(Bn))Br]. The [CpRh(Q)Cl] complexes react with PPh(3) in dichloromethane yielding the adducts CpRh(Q)Cl/PPh(3) (1:1) which exist in solution in two different isomeric forms. The interaction of [CpRh(Q(Me))Cl] with AgNO(3) in MeCN allows generation of [CpRh(Q(Me))(MeCN)]NO(3).3H(2)O, whereas the reaction of [CpRh(Q(Me))Cl] with AgClO(4) in the same solvent yields both [CpRh(Q(Me))(H(2)O)]ClO(4) and [CpRh(Cl)(H(2)O)(2)]ClO(4); the H(2)O molecules derive from the not-rigorously anhydrous solvents or silver salts.     

Dynamical space and gravitation within a purely geometrical framework: A new approach to gravitation

We state a purely geometrical framework apparently implementing Machian ideas on inertia. Only coupling constants dimensionless in natural units have been introduced in the theory. In anynonvacuum cosmos the field equations describing the gravitational phenomena in cosmological units turn out to be identical to Einstein's equations, with the Einstein gravitational coupling expressed in terms of the parameters defining the cosmological structure. This dependence, however, is not detectable. Indeed, such equations do not need to incorporate the standard Machian requirements (apart from the requirement that they are not conceivable in the total absence of matter) in order to be Machian, since, just on the basis of Mach's principle, one cannot expect to be able to detect Machian effects in Nature by using a system of units based on gravitational phenomena. On the contrary, the equations describing the gravitational field in local atomic units are Machian in the standard sense and, in particular, they incorporate the ideas that the frame has to be fixeddirectly in connection with the observed distribution and motion of matter and that there does not exist any kind of space-time in the total absence of matter. Finally, to reconcile, at least in the weak-field approximation, Einstein's equations (considered as equations describing the gravitational phenomena in local atomic units) with Mach's principle and to be in agreement with cosmological observations, we suggest that our cosmos be identified with a superuniverse model in which the background structure is homogeneous (in space and in time) and isotropic, while our universe is represented by one of the local inhomogeneities of the background. Then we prove that in any region of our universe in which the gravitational field issufficiently weak and smooth the equations, describing the gravitational field in local atomic units, are expected to approximate Einstein's equations all the better, the more the dimensions of our universe are negligible with respect to the dimensions of the background and the background curvature is small. As regards the experimental predictions of the present approach, any prediction for experiments involving only purely gravitational measurements is identical to that of Einstein's theory and the above result also guaranteesa fortiori the agreement with the available experimental data, also asnonpurely gravitational experiments are concerned.This paper appeared as Istituto Matematico L. Tonelli, preprint 78–10 (April 1978) (unpublished).     

Statistical thermodynamics models for polyatomic adsorbates: application to adsorption of n-paraffins in 5A zeolite

Experimental adsorption isotherms of five n-paraffins (ethane, propane, butane, pentane, and hexane) in 5A zeolite were described by means of a statistical thermodynamics model for linear adsorbates (MLA) developed by Ramirez-Pastor et al. (1999) and compared with the well-known multisite Langmuir model (MSL) of Nitta et al. (1984). The experimental data, obtained by different authors in a wide range of temperatures and pressures, were correlated by using an algorithm of multiple fitting. Two main conclusions were drawn from the analysis of experimental data: (i) for small molecules (ethane, propane), MLA is the more accurate model, validating the hypothesis of the linear rigid character of the adsorbate and reinforcing previous results obtained from the analysis of computational experiments developed for dimers and linear trimers; (ii) for large molecules (n-butane, n-pentane, n-hexane), the better performance of the MSL model suggests that the admolecules adsorb in a nonlinear structure. The isosteric heat of adsorption dependence on the number of carbons obtained from our study, ranging between 23.84 kJ/mol for ethane and 59.26 kJ/mol for hexane, showed a very good agreement with previous results reported in the literature, confirming the consistency of our analysis.