Investigation of the composition of linear alkylbenzenes with emphasis on the identification and quantitation of some trace compounds using GS/MS system in both electron impact and chemical ionization modes

Linear alkylbenzenes, LAB, formed by the Alel3 or HF catalyzed alkylation of benzene are common raw materials for surfactant manufacture. Normally they are sulphonated using S03 or oleum to give the corresponding linear alkylbenzene sulphonates In >95 % yield. As concern has grown about the environmental impact of surfactants,' questions have been raised about the trace levels of unreacted raw materials, linear alkylbenzenes and minor impurities present in them. With the advent of modem analytical instruments and techniques, namely GCIMS, the opportunity has arisen to identify the exact nature of these impurities and to determine the actual levels of them present in the commercial linear ,alkylbenzenes. The object of the proposed study was to separate, identify and quantify major and minor components (1-10%) in commercial linear alkylbenzenes. The focus of this study was on the structure elucidation and determination of impurities and on the qualitative determination of them in all analyzed linear alkylbenzene samples. A gas chromatography/mass spectrometry, (GCIMS) study was performed o~ five samples from the same manufacturer (different production dates) and then it was followed by the analyses of ten commercial linear alkylbenzenes from four different suppliers. All the major components, namely linear alkylbenzene isomers, followed the same elution pattern with the 2-phenyl isomer eluting last. The individual isomers were identified by interpretation of their electron impact and chemical ionization mass spectra. The percent isomer distribution was found to be different from sample to sample. Average molecular weights were calculated using two methods, GC and GCIMS, and compared with the results reported on the Certificate of Analyses (C.O.A.) provided by the manufacturers of commercial linear alkylbenzenes. The GC results in most cases agreed with the reported values, whereas GC/MS results were significantly lower, between 0.41 and 3.29 amu. The minor components, impurities such as branched alkylbenzenes and dialkyltetralins eluted according to their molecular weights. Their fragmentation patterns were studied using electron impact ionization mode and their molecular weight ions confirmed by a 'soft ionization technique', chemical ionization. The level of impurities present i~ the analyzed commercial linear alkylbenzenes was expressed as the percent of the total sample weight, as well as, in mg/g. The percent of impurities was observed to vary between 4.5 % and 16.8 % with the highest being in sample "I". Quantitation (mg/g) of impurities such as branched alkylbenzenes and dialkyltetralins was done using cis/trans-l,4,6,7-tetramethyltetralin as an internal standard. Samples were analyzed using .GC/MS system operating under full scan and single ion monitoring data acquisition modes. The latter data acquisition mode, which offers higher sensitivity, was used to analyze all samples under investigation for presence of linear dialkyltetralins. Dialkyltetralins were reported quantitatively, whereas branched alkylbenzenes were reported semi-qualitatively. The GC/MS method that was developed during the course of this study allowed identification of some other trace impurities present in commercial LABs. Compounds such as non-linear dialkyltetralins, dialkylindanes, diphenylalkanes and alkylnaphthalenes were identified but their detailed structure elucidation and the quantitation was beyond the scope of this study. However, further investigation of these compounds will be the subject of a future study.

Preconditioning and iterative solution of symmetric indefinite linear systems arising from interior point methods for linear programming

We study the preconditioning of symmetric indefinite linear systems of equations that arise in interior point solution of linear optimization problems. The preconditioning method that we study exploits the block structure of the augmented matrix to design a similar block structure preconditioner to improve the spectral properties of the resulting preconditioned matrix so as to improve the convergence rate of the iterative solution of the system. We also propose a two-phase algorithm that takes advantage of the spectral properties of the transformed matrix to solve for the Newton directions in the interior-point method. Numerical experiments have been performed on some LP test problems in the NETLIB suite to demonstrate the potential of the preconditioning method discussed.

Linear-wavelet models for system identification

A model structure comprising a wavelet network and a linear term is proposed for nonlinear system identification. It is shown that under certain conditions wavelets are orthogonal to linear functions and, as a result, the two parts of the model can be identified separately. The linear-wavelet model is compared to a standard wavelet network using data from a simulated fermentation process. The results show that the linear-wavelet model yields a smaller modelling error when compared to a wavelet network using the same number of regressors.

Efficient non-linear data assimilation in geophysical fluid dynamics

New ways of combining observations with numerical models are discussed in which the size of the state space can be very large, and the model can be highly nonlinear. Also the observations of the system can be related to the model variables in highly nonlinear ways, making this data-assimilation (or inverse) problem highly nonlinear. First we discuss the connection between data assimilation and inverse problems, including regularization. We explore the choice of proposal density in a Particle Filter and show how the ’curse of dimensionality’ might be beaten. In the standard Particle Filter ensembles of model runs are propagated forward in time until observations are encountered, rendering it a pure Monte-Carlo method. In large-dimensional systems this is very inefficient and very large numbers of model runs are needed to solve the data-assimilation problem realistically. In our approach we steer all model runs towards the observations resulting in a much more efficient method. By further ’ensuring almost equal weight’ we avoid performing model runs that are useless in the end. Results are shown for the 40 and 1000 dimensional Lorenz 1995 model.

Origem física das curvas sigmoidais respiratórias pressão-volume: recrutamento alveolar e elasticidade não-linear

An important unsolved problem in medical science concerns the physical origin of the sigmoidal shape of pressure volume curves of healthy (and some unhealthy) lungs. Such difficulties are expected because the lung, which is the most important structure in the respiratory system, is extremely complex. Its rheological properties are unknown and seem to depend on phenomena occurring from the alveolar scale up to the thoracic scale. Conventional wisdom holds that linear response, i.e., Hooke s law, together with alveolar overdistention, play a dominant role in respiration, but such assumptions cannot explainthe crucial empirical sigmoidal shape of the curves. In this doctorate thesis, we propose an alternative theory to solve this problem, based on the alveolar recruitment together with the nonlinear elasticity of the alveoli. This theory suggests that recruitment may be the predominant factor shaping these curves in the entire range of pressures normally employed in experiments. The proposed model correctly predicts the observed sigmoidal pressure volume curves, allowing us to discuss adequately the importance of this result, as well as its implications for medical practice

Reactive power dispatch and planning using a non-linear branch-and-bound algorithm

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Design of a control system using linear matrix inequalities for the active vibration control of a plate

The study of algorithms for active vibration control in smart structures is an area of interest, mainly due to the demand for better performance of mechanical systems, such as aircraft and aerospace structures. Smart structures, formed using actuators and sensors, can improve the dynamic performance with the application of several kinds of controllers. This article describes the application of a technique based on linear matrix inequalities (LMI) to design an active control system. The positioning of the actuators, the design of a robust state feedback controller and the design of an observer are all achieved using LMI. The following are considered in the controller design: limited actuator input, bounded output (energy) and robustness to parametric uncertainties. Active vibration control of a flat plate is chosen as an application example. The model is identified using experimental data by an eigensystem realization algorithm (ERA) and the placement of the two piezoelectric actuators and single sensor is determined using a finite element model (FEM) and an optimization procedure. A robust controller for active damping is designed using an LMI framework, and a reduced model with observation and control spillover effects is implemented using a computer. The simulation results demonstrate the efficacy of the approach, and show that the control system increases the damping in some of the modes.

On an Optimal Linear Control of a Chaotic Non-Ideal Duffing System

In this work, we use a nonlinear control based on Optimal Linear Control. We used as mathematical model a Duffing equation to model a supporting structure for an unbalanced rotating machine with limited power (non-ideal motor). Numerical simulations are performed for a set control parameter (depending on the voltage of the motor, that is, in the static and dynamic characteristic of the motor) The interaction of the non-ideal excitation with the structure may lead to the occurrence of interesting phenomena during the forward passage through the several resonance states of the system. Chaotic behavior is obtained for values of the parameters. Then, the proposed control strategy is applied in order to regulate the chaotic behavior, in order to obtain a periodic orbit and to decrease its amplitude. Both methodologies were used in complete agreement between them. The purpose of the paper is to give suggestions and recommendations to designers and engineers on how to drive this kind of system through resonance.

On an Optimal Linear Control Applied to a Non-Ideal Load Transportation System, Modeled with Periodic Coefficients

In this paper, a load transportation system in platforms or suspended by cables is considered. It is a monorail device and is modelled as an inverted pendulum built on a car driven by a DC motor. The governing equations of motion were derived via Lagrange's equations. In the mathematical model we consider the interaction between the DC motor and the dynamical system, that is, we have a so-called non-ideal periodic problem. The problem is analysed and we also developed an optimal linear control design to stabilize the problem.

A reducing of a chaotic movement to a periodic orbit, of a micro-electro-mechanical system, by using an optimal linear control design

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Designing a modified Hopfield network to solve an Economic Dispatch problem with nonlinear cost function

Economic Dispatch (ED) problems have recently been solved by artificial neural networks approaches. In most of these dispatch models, the cost function must be linear or quadratic. Therefore, functions that have several minimum points represent a problem to the simulation since these approaches have not accepted nonlinear cost function. Another drawback pointed out in the literature is that some of these neural approaches fail to converge efficiently towards feasible equilibrium points. This paper discusses the application of a modified Hopfield architecture for solving ED problems defined by nonlinear cost function. The internal parameters of the neural network adopted here are computed using the valid-subspace technique, which guarantees convergence to equilibrium points that represent a solution for the ED problem. Simulation results and a comparative analysis involving a 3-bus test system are presented to illustrate efficiency of the proposed approach.