Error analysis: a tool for selecting travel demand models

In developing travel demand models it is generally assumed that the base-year data used in developing the parameters, as well as the forecasted data to be used as independent variables for the design year, are of acceptable quality. The purpose of this paper is to present the application of error propagation theory in assesing the predictive quality of one type of travel demand forecasting model (multinomial logit models) and to demonstrate how error considerations can be used as a tool for identifying the optimal model. The general conclusions of this study are that: (1) it is indeed possible to quantify errors in dependent variables in logit models as a consequence of errors in independent variables; and (2) error consideration can be used as a tool for identifying the optimal model from a set of candidate models. Further research is recommended to develop better insights into the phenomenon of error propagation so that the consideration of errors can be a factor in decisions on model selection.     

Determination of trace levels of diosmin in a pharmaceutical preparation by adsorptive stripping voltammetry at a glassy carbon electrode.

A systematic study on the electrochemical behavior of diosmin in Britton-Robinson buffer (pH 2.0-10.0) at a glassy carbon electrode (GCE) was made. The oxidation process of the drug was found to be quasi-reversible with an adsorption-controlled step. The adsorption stripping response was evaluated with respect to various experimental conditions, such as the pH of the supporting electrolyte, the accumulation potential and the accumulation time. The observed anodic peak current at +0.73 V vs. Ag/AgCl reference electrode increased linearly over two orders of magnitude from 5.0x10(-8) M to 9.0x10(-6) M. A limit of detection down to 3.5x10(-8) M of diosmin at the GCE was achieved with a mean recovery of 97+/-2.1%. Based on the electrochemical data, an open-circuit accumulation step in a stirred sample solution of BR at pH 3.0 was developed. The proposed method was successfully applied to the determination of the drug in pharmaceutical formulations. The results compared favorably with the data obtained via spectrophotometric and HPLC methods.     

Miscibility of bisphenol-A polycarbonate with poly(methyl methacrylate)

The miscibility of bisphenol-A polycarbonate (PC) with poly(methyl methacrylate) (PMMA) has been reexamined using differential scanning calorimetry (DSC) and optical indications for phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Various methods have been used to prepare the blends including methylene chloride (CH₂Cl₂) and tetrahydrofuran (THF) solution casting, melt mixing, and precipitation of PC and PMMA simultaneously from THF solution by using the nonsolvents methanol and heptane. It is shown that the resulting phase behavior for PC/PMMA blends is strongly affected by the blend preparation method. However, these blends are miscible over the whole blend composition range (unambiguous single composition-dependent T_g's and LCST behavior) when prepared by precipitation from solution using heptane as the nonsolvent. To the contrary, solution-cast and melt-mixed PC/PMMA blends were all phase separated, which may be attributed to the “solvent” effect and LCST behavior, respectively, not discovered in previous reports. Methanol precipitation does not lead to fully mixed blends, which demonstrates the importance of the choice of nonsolvent when using the precipitation method.     

Quantum chaos and fractals with atoms in cavities

We study the coupled translational, electronic, and field dynamics of the combined system “a two-level atom + a single-mode quantized field + a standing-wave ideal cavity”. In the semiclassical approximation with a point-like atom, interacting with the classical field, the dynamics is described by the Heisenberg equations for the atomic and field expectation values which are known to produce semiclassical chaos under appropriate conditions. We derive Hamilton–Schrödinger equations for probability amplitudes and averaged position and momentum of a point-like atom interacting with the quantized field in a standing-wave cavity. They constitute, in general, an infinite-dimensional set of equations with an infinite number of integrals of motion which may be reduced to a dynamical system with four degrees of freedom if the quantized field is supposed to be initially prepared in a Fock state. This system is found to produce semiquantum chaos with positive values of the maximal Lyapunov exponent. At exact resonance, the semiquantum dynamics is regular. At large values of detuning |δ|1, the Rabi atomic oscillations are usually shallow, and the dynamics is found to be almost regular. The Doppler–Rabi resonance, deep Rabi oscillations that may occur at any large value of |δ| to be equal to |αp₀|, is found numerically and described analytically (with α to be the normalized recoil frequency and p₀ the initial atomic momentum). Two gedanken experiments are proposed to detect manifestations of semiquantum chaos in real experiments. It is shown that in the chaotic regime values of the population inversion z_out, measured with atoms after transversing a cavity, are so sensitive to small changes in the initial inversion z_in that the probability of detecting any value of z_out in the admissible interval [−1,1] becomes almost unity in a short time. Chaotic wandering of a two-level atom in a quantized Fock field is shown to be fractal. Fractal-like structures, typical with chaotic scattering, are numerically found in the dependence of the time of exit of atoms from the cavity on their initial momenta.     

Explicit Formulas for Generalized Action–Angle Variables in a Neighborhood of an Isotropic Torus and Their Application

Different versions of the Darboux–Weinstein theorem guarantee the existence of action–angle-type variables and the harmonic-oscillator variables in a neighborhood of isotropic tori in the phase space. The procedure for constructing these variables is reduced to solving a rather complicated system of partial differential equations. We show that this system can be integrated in quadratures, which permits reducing the problem of constructing these variables to solving a system of quadratic equations. We discuss several applications of this purely geometric fact in problems of classical and quantum mechanics.     

Rate constants for the gas‐phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250–430 K

The rate constants k₁ for the reaction of CF₃CF₂CF₂CF₂CF₂CHF₂ with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250–430 K using the flash photolysis–laser‐induced fluorescence (FP‐LIF) technique and the laser photolysis–laser‐induced fluorescence (LP‐LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253–328 K in an 11.5‐dm³ reaction chamber with either CHF₂Cl or CH₂FCF₃ as a reference compound. OH radicals were produced by UV photolysis of an O₃–H₂O–He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k₁ (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (FP‐LIF method) and (1.72 ± 0.07) × 10^?15 cm³ molecule^?1 s^?1 (LP‐LIF method), whereas the K₁ (298 K) values determined by the relative method were (1.87 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CHF₂Cl reference) and (2.12 ± 0.11) × 10^?15 cm³ molecule^?1 s^?1 (CH₂FCF₃ reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K₁ = (4.71 ± 0.94) × 10^?13 exp[?(1630 ± 80)/T] cm³ molecule^?1 s^?1. Using kinetic data for the reaction of tropospheric CH₃CCl₃ with OH radicals [k₁ (272 K) = 6.0 × 10^?15 cm³ molecule^?1 s^?1, tropospheric lifetime of CH₃CCl₃ = 6.0 years], we estimated the tropospheric lifetime of CF₃CF₂CF₂CF₂CF₂CHF₂ through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26–33, 2004