Diffusion coefficients from stopped-flow gas chromatography

Summary Mutual diffusion coefficients of two gases A and B can be determined in an empty gas chromatographic column by letting component B enter at an intermediate position of the column and continuously flow through a part only of it, as a carrier gas. The other component A is injected in a small amount instantaneously at the closed end of the column with the detector placed at the other end. By repeatedly stopping and then restoring after a short time the flow of B, narrow extra peaks are produced on the chromatographic elution curve, owing to diffusion of A into B. An equation is derived giving the area under the curve of each stop-peak as a function of time of the corresponding stop. Plotting the experimental data according to this equation permits the determination of the diffusion coefficient of A into B. Some results obtained by this method show negligible variations with changes in the experimental parameters.     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

The ionization of perchloric and hydrofluoric acids in aqueous solution

Cyclical bifurcated hydrogen bonded structures are proposed for aqueous solutions of hydrofluoric acid and for the bifluoride ion which are consistent with the spectral data. The structure proposed for HF is also applicable to solutions in organic solvents. Raman spectra of tetramethylguanidinium perchlorate suggest that the corresponding Raman spectra of perchloric acid solutions may not be interpreted in terms of a completely dissociated acid. Other evidence including activity coefficient, heat capacity and partial molal volume data suggest that there is some association in relatively dilute perchloric acid solutions between the perchlorate ion and the hydrated proton. This association decreases in concentrated aqueous solutions.     

Covalence reduction factors of four-coordinated pseudo-tetrahedral paramagnetic compounds inD 2d symmetry

Theoretical expressions for the covalence reduction factors of orbital angular momentum and spin-orbit coupling in pseudo-tetrahedral four-coordinated paramagnetic complexes withD _2d symmetry, denoted ask's andR's respectively, have been derived. p ]The mixing coefficients in the antibonding MO's for the CuCl ₄ ^2- ion in three complexes are estimated using suitable approximations. It is shown thatk's must be less thanR's in Tinkham's approximation. Certain misconceptions existing in the literature regarding the value of the integral 〈p _u |???u|s〉 have been clarified.     

Differential operators in terms of Clebsch-Gordon (C-G) coefficients and the wave equation of massless tensor fields

The quantum theory of angular momentum affords a treatment of tensors and vectors in a spherical basis. By using this theory we define the tensor differential operators: divergence, curl and gradient which act on a tensor of any rank, in terms of C-G coefficients. With these definitions we obtain a matrix representation and useful properties for those operators. An interesting application of this formalism is to find the wave equation of a tensor of any rank in a linear theory. This provides a new common way to look at the wave equations associated with both Maxwell's equations and the Maxwell-like equations for the linearized Weyl curvature tensor in gravitoelectromagnetism describing gravitational radiation on a Minkowski spacetime background.     

Hall coefficient in solution for a simple dynamical model

A model Liouville equation is proposed for a system composed of an ion moving in a solvent fluid. Using this model, explicit results are obtained for the Ohmic conductivityL and the Hall conductivityh. These results are then used to calculate the Hall coefficientR = ehL^–2, which is a measure of the effect of non-Brownian motion, for several charge carriers of interest. Our results are in agreement with earlier findings based on a stochastic model which predictR > 1 for H⁺(aq). Our results also indicate thatR 1 for charge carriers such as Na⁺, Cl^–, and K⁺ which have a mass greater than that of a solvent molecule (here taken as 18 amu).This research was supported in part by grants from the National Science Foundation and by the Research Foundation of the State University of New York.     

Optical functions of InGaP/GaAs epitaxial layers from 0.01 to 5.5 eV

In_0.49Ga_0.51P films, both undoped and doped n- and p-type (up to 10¹⁸ cm^-3), were grown lattice matched on GaAs substrates, with different miscut angles, by Metal-Organic Vapour Phase Epitaxy (MOVPE) at different temperatures. The shift of the fundamental gap E₀, caused by “ordering effect” was measured as a function of temperature by photoluminescence. The complex refractive index = n + ik and the dielectric function = ɛ ₁ + iɛ ₂ at room temperature were determined from 0.01 to 5.5 eV by using complementary data from fast-Fourier-transform far-infrared (FFT-FIR), dispersive, and ellipsometric spectroscopies. The effect of the native oxide was accounted for and the self-consistency of the optical functions was checked in the framework of the Kramers-Kronig causality relations. In the restrahlen region the dielectric function was well fitted by classical Lorentz oscillators; in the transparent region below E₀, the refractive index was modelled by a Sellmeier dispersion relation; in the interband region the dielectric function was well reproduced by analytical lineshapes associated to seven critical points. Thus parametrized analytical expressions were obtained for the optical functions all over the spectral range, without discontinuities, to be used in the modelling and characterization of multi-layer structures, also on opaque substrates. Received 13 December 2001 Published online 25 June 2002     

Semiparametric random coefficient regression models

Linear regression models with random coefficients express the idea that each individual sampled may have a different linear response function. Technically speaking, random coefficient regression encompasses a rich variety of submodels. These include deconvolution or affine-mixture models as well as certain classical linear regression models that have heteroscedastic errors, or errors-in-variables, or random effects. This paper studies minimum distance estimates for the coefficient distributions in a general, semiparametric, random coefficient regression model. The analysis yields goodness-of-fit tests for the semiparametric model, prediction regions for future responses, and confidence regions for the distribution of the random coefficients.This research was supported in part by NSF Grant DMS 9001710.